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Catalytic reactions of titanium alkoxides with Grignard reagents and imines: a mechanistic study.
Kumar, Akshai; Samuelson, Ashoka G
The reactivity of Grignard reagents towards imines in the presence of catalytic and stoichiometric amounts of titanium alkoxides is reported. Alkylation, reduction, and coupling of imines take place. Whereas reductive coupling is the major reaction in stoichiometric reactions, alkylation is favored in catalytic reactions. Mechanistic studies clearly indicate that intermediates involved in the two reactions are different. Catalytic reactions involve a metal-alkyl complex. This has been confirmed by reactions of deuterium-labeled substrates and different alkylating agents. Under the stoichiometric conditions, however, titanium olefin complexes are formed through reductive elimination, probably through a multinuclear intermediate.
Kinetic and Spectroscopic Studies of Heterogeneous Catalytic Reactions
NASA Astrophysics Data System (ADS)
Wilke, Todd E.
The selective oxidation of ethylene was studied on a high surface area colloidal silver catalyst. In 0.1 to 1 torr of 20% ethylene in oxygen, the catalyst produced ethylene oxide with a selectivity of 20 to 30% at temperatures between 473 and 573 K. Surface-enhanced Raman (SER) spectra exhibited a distinct feature at 995 cm^ {-1}. This band was also observed for catalysts exposed to just oxygen, and it shifted to 980 cm^{-1} after heating the catalyst to 873 K in ^{18} O_2. No isotopic shift was observed with ^{18}O _2 at temperatures below 573 K. Similar spectral results were obtained at atmospheric pressure. For silver catalysts that contain adsorbed chlorine, SER bands were observed at 240, 1015, and 1045 cm^ {-1} in oxygen-containing atmospheres; the 995 cm^{-1} band was not evident. The extension of SERS to other metals that do not exhibit the surface-enhanced effect was examined by electrodepositing thin layers (2 to 3 monolayers) of platinum, rhodium, and ruthenium on a roughened gold substrate. At atmospheric pressure and temperatures between 298 and 473 K, metal-oxygen features were observed at 500 cm ^{-1}, and 490 and 600 cm ^{-1} in SER spectra of rhodium and ruthenium surfaces exposed to oxygen, respectively. Bands attributed to adsorbed carbon monoxide were observed in SER spectra of platinum (470, 2060, 390, and 1890 cm ^{-1}) and rhodium (465 and 2040 cm^{-1}) surfaces exposed to carbon monoxide and oxygen mixtures. The temporal replacement of adsorbed carbon monoxide by nitric oxide as well as temperature-induced changes in the surface composition were studied on a seconds timescale with a spectrograph -charge coupled device detector arrangement. The adsorption and oxidation of sulfur dioxide was also studied. A band assigned to the S-O stretch of molecularly adsorbed sulfur dioxide was observed at 1130 cm^{-1} on unmodified gold and platinum-coated gold surfaces exposed to sulfur dioxide at 298 K. Dissociative chemisorption of sulfur dioxide on
Scanning electrochemical microscopy #54. Application to the study of heterogeneous catalytic reactions-hydrogen peroxide decomposition.
Fernández, José L; Hurth, Cedric; Bard, Allen J
A scanning electrochemical microscopy (SECM) approach for the analysis of heterogeneous catalytic reactions at solid-liquid interfaces is described and applied. In this scheme, reactant, generated at a tip, undergoes a reaction (e.g., disproportionation) at the substrate. The theoretical background for this study, performed by digital simulations using a finite difference method, considers a chemical reaction at the substrate with general stoichiometry. In this case, the fraction of regenerated mediator (nu(S)) may differ with respect to a substrate reaction that is the reverse of the tip reaction, resulting in an asymmetric mediator loop. Simulated tip current transients and approach curves at different values of the kinetic rate constant for reactions where nu(S) < 1 were used to analyze this new SECM situation. This approach was used to study the catalytic decomposition of hydrogen peroxide (HO2- --> 1/2O2 + OH-), where nu(S) = 0.5, on supported catalysts. A gold-mercury amalgam tip was used to quantitatively reduce dissolved O2 (mediator) to HO2-, which was decomposed back to oxygen at the catalyst substrate. Rate constants for the decomposition reaction on immobilized catalase and Pt particles were measured at different pH values by the correlation of experimental approach curves with the theoretical dependencies.
An experimental study of catalytic and non-catalytic reaction in heat recirculating reactors and applications to power generation
NASA Astrophysics Data System (ADS)
Ahn, Jeongmin
An experimental study of the performance of a Swiss roll heat exchanger and reactor was conducted, with emphasis on the extinction limits and comparison of results with and without Pt catalyst. At Re<40, the catalyst was required to sustain reaction; with the catalyst self-sustaining reaction could be obtained at Re less than 1. Both lean and rich extinction limits were extended with the catalyst, though rich limits were extended much further. At low Re, the lean extinction limit was rich of stoichiometric and rich limit had equivalence ratios 80 in some cases. Non-catalytic reaction generally occurred in a flameless mode near the center of the reactor. With or without catalyst, for sufficiently robust conditions, a visible flame would propagate out of the center, but this flame could only be re-centered with catalyst. Gas chromatography indicated that at low Re, CO and non-C3 H8 hydrocarbons did not form. For higher Re, catalytic limits were slightly broader but had much lower limit temperatures. At sufficiently high Re, catalytic and gas-phase limits merged. Experiments with titanium Swiss rolls have demonstrated reducing wall thermal conductivity and thickness leads to lower heat losses and therefore increases operating temperatures and extends flammability limits. By use of Pt catalysts, reaction of propane-air mixtures at temperatures 54°C was sustained. Such low temperatures suggest that polymers may be employed as a reactor material. A polyimide reactor was built and survived prolonged testing at temperatures up to 500°C. Polymer reactors may prove more practical for microscale devices due to their lower thermal conductivity and ease of manufacturing. Since the ultimate goal of current efforts is to develop combustion driven power generation devices at MEMS like scales, a thermally self-sustaining miniature power generation device was developed utilizing a single-chamber solid-oxide-fuel-cell (SOFC) placed in a Swiss roll. With the single-chamber design
Environmental Transmission Electron Microscopy Study of Diesel Carbon Soot Combustion under Simulated Catalytic-Reaction Conditions.
Mori, Kohsuke; Watanabe, Keitaro; Sato, Takeshi; Yamashita, Hiromi
Environmental transmission electron microscopy (ETEM) is used to monitor the catalytic combustion of diesel carbon soot upon exposure to molecular oxygen at elevated temperatures by using a gas-injection specimen heating holder. The reaction conditions simulated in the ETEM experiments reconstruct real conditions effectively. This study demonstrated for the first time that soot combustion occurs at the soot-catalyst interface for both Ag/CeO2 and Cu/BaO/La2 O3 catalysts.
Electrochemical promotion of catalytic reactions
NASA Astrophysics Data System (ADS)
Imbihl, R.
The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.
Study of Catalytic Reaction at Electrode-Electrolyte Interfaces by a CV-XAFS Method
NASA Astrophysics Data System (ADS)
Kusano, Shogo; Matsumura, Daiju; Asazawa, Koichiro; Kishi, Hirofumi; Sakamoto, Tomokazu; Yamaguchi, Susumu; Tanaka, Hirohisa; Mizuki, Jun'ichiro
A method combining cyclic voltammetry (CV) with x-ray absorption fine structure (XAFS) spectroscopy, viz. CV-XAFS, has been developed to enable in situ real-time investigation of atomic and electronic structures related to electrochemical reactions. We use this method to study the reaction of a Pt/C cathode catalyst in the oxygen reduction reaction (ORR) in an alkaline electrolyte, using x-ray energies near the Pt LIII edge for XAFS measurements. It was found that the current induced by the ORR was first observed at approximately 0.08 V versus Hg/HgO, although the Pt valence, which is reflected in the oxidation states, remained almost unchanged. The electronic structure of the catalytic surface in the ORR was observed to be different in the negative and positive scan directions of CV measurements. Hydrogen adsorption is also discussed on the basis of the observation of this spectral change. We have demonstrated that CV-XAFS provides dynamical structural and electronic information related to electrochemical reactions and can be used for in situ real-time measurements of a catalyst.
Adsorbate structures and catalytic reactions studied in the torrpressure range by scanning tunneling microscopy
Hwang, Kevin Shao-Lin
High-pressure, high-temperature scanning tunneling microscopy (HPHTSTM) was used to study adsorbate structures and reactions on single crystal model catalytic systems. Studies of the automobile catalytic converter reaction [CO + NO → 1/2 N2 + CO2] on Rh(111) and ethylene hydrogenation [C2H4 + H2 → C2H6] on Rh(111) and Pt(111) elucidated information on adsorbate structures in equilibrium with high-pressure gas and the relationship of atomic and molecular mobility to chemistry. STM studies of NO on Rh(111) showed that adsorbed NO forms two high-pressure structures, with the phase transformation from the (2 x 2) structure to the (3 x 3) structure occurring at 0.03 Torr. The (3 x 3) structure only exists when the surface is in equilibrium with the gas phase. The heat of adsorption of this new structure was determined by measuring the pressures and temperatures at which both (2 x 2) and (3 x 3) structures coexisted. The energy barrier between the two structures was calculated by observing the time necessary for the phase transformation to take place. High-pressure STM studies of the coadsorption of CO and NO on Rh(111) showed that CO and NO form a mixed (2 x 2) structure at low NO partial pressures. By comparing surface and gas compositions, the adsorption energy difference between topsite CO and NO was calculated. Occasionally there is exchange between top-site CO and NO, for which we have described a mechanism for. At high NO partial pressures, NO segregates into islands, where the phase transformation to the (3 x 3) structure occurs. The reaction of CO and NO on Rh(111) was monitored by mass spectrometry (MS) and HPHTSTM. From MS studies the apparent activation energy of the catalytic converter reaction was calculated and compared to theory. STM showed that under high-temperature reaction conditions, surface metal atoms become mobile. Ethylene hydrogenation and its poisoning by CO was
DFT study of the 1-octene metathesis reaction mechanism with WCl6/C catalytic system.
Yüksel, Dilek; Düz, Bülent; Sevin, Fatma
A catalytic system consisting of tungsten carbene generated from WCl(6) and an atomic carbon is investigated theoretically for the metathesis of 1-octene at B3LYP/extended LANL2DZ level of DFT. The ground-state geometries and charge distributions of the structures belonging to the reaction mechanism are located. Energetics for the complete set of reactions, involving the formation of the tungsten carbene precatalyst, Cl(4)WCCl(2), the formation of tungsten methylidene and tungsten heptylidene with this precatalyst, and finally productive and degenerative metathesis steps with these alkylidene species are calculated in terms of total electronic energy and thermal energies. The free-energy (ΔG(298)) surfaces of the structures involved in the related reactions are constructed. In addition, solvent effects on the single point energies of the structures are investigated for two different solvents, namely, cyclohexane and chloroform. The results indicate that the formation of the catalytically active heptylidene is energetically favored in comparison to the formation of methylidene, while the degenerative and productive metathesis steps are competitive. In the catalytic cycle, the formation of ethylene is exothermic, while the formation of 7-tetradecene is endothermic. As expected, solvent effects on the metathesis reactions are minor and solvation does not cause any change in the directions of the overall metathesis reactions.
The effect of subsurface layer on the phase diagram of CO-O 2 catalytic reaction: a computer simulation study
NASA Astrophysics Data System (ADS)
Khan, K. M.; Yaldram, K.
The effect of the subsurface layer in monomer-dimer surface catalytic reaction is studied by computer simulation. This reaction system has been studied on the surface and subsurface of a body-centred cubic structure, which extends to only two layers in the z-direction. The presence of a subsurface adds several extra reaction steps to the usual three in the ZGB model. It is shown that under certain conditions, the usual second-order phase transition of the ZGB model can be eliminated, and the reactive window width can be increased. This situation is close to the experimental situation.
Mechanisms and Kinetics of Catalytic Reactions
CHEMICAL RESEARCH, r- DEVELOPMENT 5 N ENGINEERING CRDE-R-084 "" CENTER CENER(GC-TR-1728-008) ' 04 N MECHANISMS AND KINETICS OF CATALYTIC REACTIONS Q...and Kinetics of Catalytic Reactions &AUTHOR(S) Garlick, Stephanie M. 7. PERFORMING ORGANIZATION NAME(S) AND ADORESS(ES) . PERFORMING ORGANIZATION...Tables........................87 vi MECHANISMS AND KINETICS OF CATALYTIC REACTIONS 1. INTRODUCTION The hydrolysis of phosphate esters in microemulsion
Study of liquid-solid catalytic reaction of epichlorohydrin with sodium butyrate in the presence of tetrabutylammonium bromide
NASA Astrophysics Data System (ADS)
Huang, Qiang; Meng, Qingyi; Ban, Chunlan; Zhang, Rui; Gao, Yingyu
The liquid-solid catalytic reaction of epichlorohydrin and sodium butyrate with tetrabutylammonium bromide as a phase transfer catalyst was studied in this paper. The shrinking core model was applied. The analysis of the reaction based on the kinetic model showed a reaction-controlled regime at temperatures varying from 90 to 100°C. The exterior diffusivity was removed between 300 and 400 rpm. The internal diffusivity was removed when the particle size was 2 × 10-4 m. Reaction rate constants were calculated at different temperatures. The correlation was obtained when the proposed kinetic model was applied to all the experimental data for predictive evaluations and the activation energy was 37.01 kJ mol-1.
Study on Reaction Products in Plasma-Assisted Selective Catalytic Reduction of NOx
NASA Astrophysics Data System (ADS)
Yoshizawa, Hayato; Tochikubo, Fumiyoshi; Uchida, Satoshi; Watanabe, Tsuneo
Since the gas discharge plasma easily converts NO to NO2, which can be reduced more actively in selective catalytic reduction with hydrocarbons (HC-SCR), the plasma-assisted HC-SCR is an effective method for NOx reduction from diesel engine exhaust gases. In this work, the relation between NOx removal and reaction products is investigated in plasma-assisted HC-SCR in simulated flue gas as parameters of gas composition, plasma specific energy and catalyst temperature. C2H4 is used as a hydrocarbon and commercially available Al2O3 is used as a catalyst. After the plasma treatment of simulated flue gas, HCHO and HCOOH were generated as by-products, while NO was effectively converted to NO2. These by-products were confirmed to be reactive at lower catalyst temperature than C2H4 in HC-SCR. The relation between NOx removal and reaction products suggests that HCHO and HCOOH contribute the effective NOx reduction at low catalyst temperature in plasma-assisted HC-SCR.
Catalytic Wittig and aza-Wittig reactions
Lao, Zhiqi
This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines. PMID:28144327
Catalytic gasification: Isotopic labeling and transient reaction
Saber, J.M.; Falconer, J.L.; Brown, L.F.
Temperature-programmed reaction was used with labeled isotopes (/sup 13/C and /sup 18/O) to study interactions between carbon black and potassium carbonate in pure He and 10% CO/sub 2//90% He atmospheres. Catalytic gasification precursor complexes were observed. Carbon and oxygen-bearing carbon surface groups interacted with the carbonate above 500 K to form surface complexes. Between 500 K and 950 K, and in the presence of gaseous carbon dioxide, the complexes promoted carbon and oxygen exchange between the gas-phase CO/sub 2/ and the surface. Oxygen exchanged between the surface complexes; but carbon did not exchange between the carbonate and the carbon black. As the temperature rose, the complexes decomposed to produce carbon dioxide, and catalytic gasification then began. Elemental potassium formed, and the active catalyst appears to alternate between potassium metal and a potassium-oxygen-carbon complex.
Catalytic reaction in confined flow channel
Van Hassel, Bart A.
A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flow channel.
The Synthesis, Characterization and Catalytic Reaction Studies of Monodisperse Platinum Nanoparticles in Mesoporous Oxide Materials
Rioux, Robert M.
A catalyst design program was implemented in which Pt nanoparticles, either of monodisperse size and/or shape were synthesized, characterized and studied in a number of hydrocarbon conversion reactions. The novel preparation of these materials enables exquisite control over their physical and chemical properties that could be controlled (and therefore rationally tuned) during synthesis. The ability to synthesize rather than prepare catalysts followed by thorough characterization enable accurate structure-function relationships to be elucidated. This thesis emphasizes all three aspects of catalyst design: synthesis, characterization and reactivity studies. The precise control of metal nanoparticle size, surface structure and composition may enable the development of highly active and selective heterogeneous catalysts.
A study on the reaction characteristics of vanadium-impregnated natural manganese oxide in ammonia selective catalytic reduction.
Kim, Sung Su; Lee, Sang Moon; Park, Kwang Hee; Kwon, Dong Wook; Hong, Sung Chang
This study investigated the effect of adding vanadium (V) to natural manganese oxide (NMO) in ammonia (NH3) selective catalytic reduction (SCR). The addition of V to NMO decreased the catalytic activity at low temperatures by blocking the active site. However, the enhancement of catalytic activity was achieved by controlling NH3 oxidation at high temperatures. From the NH3 temperature programmed desorption and oxygen on/off test, it was confirmed that the amount of Lewis acid site and active lattice oxygen of the catalyst affects the catalytic performance at low temperature.
Electric Field-Enhanced Catalytic Conversion of Methane: AN Experimental Study on the Effects of Corona Discharge on Methane Reactions
NASA Astrophysics Data System (ADS)
Marafee, Abdulathim M. J.
The oxidative coupling of methane (OCM) is currently being actively studied for the production of higher hydrocarbons from natural gas. The present study concentrates on the oxidative conversion of methane in a high-pressure (one atmosphere), nonthermal plasma formed by corona discharge. Here, methyl radicals are formed by the reaction of methane with negatively-charged oxygen species created in the corona discharge. The results of methane conversion in the presence of both AC and DC corona discharges revealed that ethane and ethylene product selectivity is affected by electrode polarity, frequency, and oxygen partial pressure in the feed. Higher C_2 yields were obtained with the AC corona. All of the AC corona discharges specified here were initiated at room temperature (i.e., no oven or other heat source used), with temperature increases from 300 to 500^circC due to the exothermic gas discharge and exothermic reaction. A reaction mechanism is presented to explain the observed phenomena. The results suggest that AC and/or DC gas discharge techniques should be further studied for improved economics of methane conversion. The oxidative dehydrogenation of ethane in DC corona discharges was investigated. The atomic oxygen radicals initiated by corona discharges are thought to be active for the OXD of ethane. The selectivity to ethylene is affected by the reaction temperature, the DC applied voltage, voltage polarity, and the C_2H _6/O_2 ratio. The results of this study suggest the corona discharge process to be very efficient and selective in the oxidative dehydrogenation of ethane. The effects of DC corona discharge were examined in the presence of a typical OCM catalyst, Sr/La _2O_3. Experimental investigations have correspondingly been conducted, in which all reactive gases passed through a catalyst bed situated within the corona-induced plasma zone. The methane conversion and C_2 yield increased (with O_2 partial pressure) during the corona-enhanced catalytic
2-methylpentane catalytic reactions on Pt(3%wt)-HNaβ-zeolite. Kinetic studies
NASA Astrophysics Data System (ADS)
Siffert, S.; Garin, F.
The system Pt(2.9 wt%)-HNaβ zeolite is an interesting catalyst for hydrocarbon reforming. Kinetic studies of 2-methylpentane reaction on this catalyst were performed. Apparent activation energies and reaction orders versus respectively temperature and partial pressures of hydrogen and hydrocarbon allowed us to explain the bifunctional behavior of this catalyst and to determine the respective function of the platinum and of the support. The reaction orders versus hydrocarbon do not vary with reaction temperature and are positive (+0.6± 0.1), but the reaction orders versus hydrogen increases when the temperature increases from 0.3 at 160°C to 0 at 200°C. There are two groups of apparent activation energy values differing by about 10 Kcal/mol. The superior values are obtained for higher partial pressures of hydrogen or hydrocarbon (25± 2 Kcal/mol) and the lower ones for lower partial pressures of hydrogen or hydrocarbon 16± 2 (Kcal/mol). The reaction process would be at the metal-support interface. The adsorption step of 2-methylpentane would be a reactive (associative) adsorption step followed by a dissociative step of dehydrogenation leading to the most abundant surface intermediate (MASI). This kinetic process explains the experimental values. Le système Pt(2,9 % en masse)-HNa zéolithe β est un catalyseur intéressant pour le reformage des hydrocarbures. Nous avons effectué des études cinétiques de la réaction du 2-méthylpentane sur ce catalyseur. Les énergies d'activation et les ordres de réaction en fonction respectivement de la température et des pressions partielles d'hydrogène et d'hydrocarbure nous ont permis d'expliquer le caractère bifonctionnel et de déterminer respectivement la fonction du métal et du support. Les ordres de réaction par rapport à l'hydrocarbure ne varient pas avec la température de réaction et sont positifs (+0.6± 0.1), mais les ordres de réaction par rapport à l'hydrogène augmentent quand la température cro
Surface-subsurface model for a dimer-dimer catalytic reaction: a Monte Carlo simulation study
NASA Astrophysics Data System (ADS)
Khan, K. M.; Albano, E. V.
The surface-subsurface model for a dimer-dimer reaction of the type A2 + 2B2→2AB2 has been studied through Monte Carlo simulation via a model based on the lattice gas non-thermal Langmuir-Hinshelwood mechanism, which involves the precursor motion of the B2 molecule. The motion of precursors is considered on the surface as well as in the subsurface. The most interesting feature of this model is that it yields a steady reactive window, which is separated by continuous and discontinuous irreversible phase transitions. The phase diagram is qualitatively similar to the well known Ziff, Gulari and Barshad (ZGB) model. The width of the window depends upon the mobility of precursors. The continuous transition disappears when the mobility of the surface precursors is extended to the third-nearest neighbourhood. The dependence of production rate on partial pressure of B2 dimer is predicted by simple mathematical equations in our model.
Biodiesel Production from Citrillus colocynthis Oil using based Catalytic Reaction and Characterization Studies.
Nehdi, Imededdine A; Sbihi, Hassen M; El Blidi, Lahssen; Rashid, Umer; Al-Resayes, Saud I
In this investigation, an enzyme catalyzed process was optimized to prepare methyl esters from crude Citrullus colocynthis oil (CCO). Novozym 435 was used to synthesize biodiesel by transesterification of CCO with methanol. Use of tert-butanol as a reaction medium eliminated negative effects caused by excess methanol and formation of glycerol byproduct. Several variables affecting the Citrullus colocynthis methyl ester (CCME) yield including lipase quantity, water content, methanol/oil mole ratio, reaction temperature, reaction medium composition, and reaction time were optimized. A CCME yield of 97.8% was achieved using enzyme catalyzed transesterification of CCO under optimal conditions. CCME also exhibited long-term storage stability and fuel properties within biodiesel standards.
Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions
NASA Astrophysics Data System (ADS)
Cuba Torres, Christian Martin
On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.
Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5
Liu, Cong; Evans, Tabitha J.; Cheng, Lei; Nimlos, Mark R.; Mukarakate, Calvin; Robichaud, David J.; Assary, Rajeev S.; Curtiss, Larry A.
These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.
Catalytic Conia-ene and related reactions.
Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter
Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.
Catalytic reaction processes revealed by scanning probe microscopy. [corrected].
Jiang, Peng; Bao, Xinhe; Salmeron, Miquel
at the atomic level. Then the dynamic processes, including surface reconstruction, roughening, sintering, and phase separation, studied by SPM will be discussed. Furthermore, SPM provides valuable insights toward identifying the active sites and understanding the reaction mechanisms. We also illustrate here how both ultrahigh vacuum STM and high pressure STM provide valuable information, expanding the understanding provided by traditional surface science. We conclude with highlighting remarkable recent progress in noncontact atomic force microscopy (NC-AFM) and inelastic electron tunneling spectroscopy (IETS), and their impact on single-chemical-bond level characterization for catalytic reaction processes in the future.
Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study
J Durand; S Senanayake; S Suib; D Mullins
The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.
Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study
Durand, Jason; Senanayake, Sanjaya D; Mullins, David R; Suib, Steven
The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.
[Study on determination of trace nitrite and reaction mechanism by two-wavelength negative absorption-catalytic spectrophotometry].
Zi, Yan-qin; Lu, Hao-miao
A new method was proposed for the determination of trace nitrite by two wavelength negative absorption catalytic spectrophotometry based on the catalysis of nitrite on the oxidation fading reaction of acridine orange by potassium bromate in phosphoricacid medium. The additive value of negative absorbances at two wavelengths was linear to the nitrite concentration in the range of 1.0 x 10(-5)-5.0 x 10(-7) mol x L(1). The method has been used to the determination of nitrite in environment water sample with satisfactory
Study of the Oxygen Evolution Reaction Catalytic Behavior of CoxNi1-xFe2O4 in Alkaline Medium.
Maruthapandian, Viruthasalam; Mathankumar, Mahendran; Saraswathy, Velu; Subramanian, Balasubramanian; Muralidharan, Srinivasan
Catalysts for the oxygen evolution reaction (OER) play an important role in the conversion of solar energy to fuel of earth-abundant water into H2 and O2 through splitting/electrolysis. Heterogeneous electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) exhibit catalytic activity that depends on the electronic properties, oxidation states, and local surface structure. Spinel ferrites (MFe2O4; M = Ni and Co) based materials have been attractive for the catalytic water oxidation due to their well-known stability in alkaline medium, easy synthesis, existence of metal cations with various oxidation states, low cost, and tunable properties by the desired metal substitution. To understand the better catalytic activity of MFe2O4 in detail the role of Ni and Co was studied through MxNi1-xFe2O4 (M = Co; 0 < x < 1), which was prepared by the sol-gel method. The results showed that bare NiFe2O4 has better catalytic activity (η = 381 mV at 10 mA cm(-2) and Tafel slope of 46.4 mV dec(-1)) compared to Co-containing MxNi1-xFe2O4 (η = 450-470 mV at 10 mA cm(-2) and Tafel slope of 50-73 mV dec(-1)) in alkaline medium, and the substitution of Co is found to suppress the catalytic activity of NiFe2O4. The degradation of catalytic activity with an increase in Co content was accounted for in further detailed investigations.
An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations.
Nakagawa, Masaki; Togashi, Yuichi
Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed.
An Analytical Framework for Studying Small-Number Effects in Catalytic Reaction Networks: A Probability Generating Function Approach to Chemical Master Equations
Nakagawa, Masaki; Togashi, Yuichi
Cell activities primarily depend on chemical reactions, especially those mediated by enzymes, and this has led to these activities being modeled as catalytic reaction networks. Although deterministic ordinary differential equations of concentrations (rate equations) have been widely used for modeling purposes in the field of systems biology, it has been pointed out that these catalytic reaction networks may behave in a way that is qualitatively different from such deterministic representation when the number of molecules for certain chemical species in the system is small. Apart from this, representing these phenomena by simple binary (on/off) systems that omit the quantities would also not be feasible. As recent experiments have revealed the existence of rare chemical species in cells, the importance of being able to model potential small-number phenomena is being recognized. However, most preceding studies were based on numerical simulations, and theoretical frameworks to analyze these phenomena have not been sufficiently developed. Motivated by the small-number issue, this work aimed to develop an analytical framework for the chemical master equation describing the distributional behavior of catalytic reaction networks. For simplicity, we considered networks consisting of two-body catalytic reactions. We used the probability generating function method to obtain the steady-state solutions of the chemical master equation without specifying the parameters. We obtained the time evolution equations of the first- and second-order moments of concentrations, and the steady-state analytical solution of the chemical master equation under certain conditions. These results led to the rank conservation law, the connecting state to the winner-takes-all state, and analysis of 2-molecules M-species systems. A possible interpretation of the theoretical conclusion for actual biochemical pathways is also discussed. PMID:27047384
The nature of hot electrons generated by exothermic catalytic reactions
NASA Astrophysics Data System (ADS)
Nedrygailov, Ievgen I.; Park, Jeong Young
We review recent progress in studies of the nature of hot electrons generated in metal nanoparticles and thin films on oxide supports and their role in heterogeneous catalysis. We show that the creation of hot electrons and their transport across the metal-oxide interface is an inherent component of energy dissipation accompanying catalytic and photocatalytic surface reactions. The intensity of hot electron flow is well correlated with turnover rates of corresponding reactions. We also show that controlling the flow of hot electrons crossing the interface can lead to the control of chemical reaction rates. Finally, we discuss perspectives of hot-electron-mediated surface chemistry that promise the capability to drive catalytic reactions with enhanced efficiency and selectivity through electron-mediated, non-thermal processes.
Reaction rate oscillations during catalytic CO oxidation: A brief overview
NASA Technical Reports Server (NTRS)
Tsotsis, T. T.; Sane, R. C.
It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.
Reaction rate oscillations during catalytic CO oxidation: A brief overview
NASA Astrophysics Data System (ADS)
Tsotsis, T. T.; Sane, R. C.
It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.
The doping effect on the catalytic activity of graphene for oxygen evolution reaction in a lithium-air battery: a first-principles study.
Ren, Xiaodong; Wang, Beizhou; Zhu, Jinzhen; Liu, Jianjun; Zhang, Wenqing; Wen, Zhaoyin
A lithium-air battery as an energy storage technology can be used in electric vehicles due to its large energy density. However, its poor rate capability, low power density and large overpotential problems limit its practical usage. In this paper, the first-principles thermodynamic calculations were performed to study the catalytic activity of X-doped graphene (X = B, N, Al, Si, and P) materials as potential cathodes to enhance charge reactions in a lithium-air battery. Among these materials, P-doped graphene exhibits the highest catalytic activity in reducing the charge voltage by 0.25 V, while B-doped graphene has the highest catalytic activity in decreasing the oxygen evolution barrier by 0.12 eV. By combining these two catalytic effects, B,P-codoped graphene was demonstrated to have an enhanced catalytic activity in reducing the O2 evolution barrier by 0.70 eV and the charge voltage by 0.13 V. B-doped graphene interacts with Li2O2 by Li-sited adsorption in which the electron-withdrawing center can enhance charge transfer from Li2O2 to the substrate, facilitating reduction of O2 evolution barrier. In contrast, X-doped graphene (X = N, Al, Si, and P) prefers O-sited adsorption toward Li2O2, forming a X-O2(2-)···Li(+) interface structure between X-O2(2-) and the rich Li(+) layer. The active structure of X-O2(2-) can weaken the surrounding Li-O2 bonds and significantly reduce Li(+) desorption energy at the interface. Our investigation is helpful in developing a novel catalyst to enhance oxygen evolution reaction (OER) in Li-air batteries.
Atmospheric pressure microwave assisted heterogeneous catalytic reactions.
Chemat-Djenni, Zoubida; Hamada, Boudjema; Chemat, Farid
The purpose of the study was to investigate microwave selective heating phenomena and their impact on heterogeneous chemical reactions. We also present a tool which will help microwave chemists to answer to such questions as "My reaction yields 90% after 7 days at reflux; is it possible to obtain the same yield after a few minutes under microwaves?" and to have an approximation of their reactions when conducted under microwaves with different heterogeneous procedures. This model predicting reaction kinetics and yields under microwave heating is based on the Arrhenius equation, in agreement with experimental data and procedures.
[In situ diffuse reflectance FTIR spectroscopy study of the selective catalytic reduction reaction of NO over Ag/SAPO-34 catalysis].
Zhang, Ping; Wang, Le-fu; Xu, Jian-chang
An in situ diffuse reflectance FTIR spectroscopy (DRIFTS) study of the selective catalytic reduction (SCR) of NO with propene in the presence of excess O2 was carried out over Ag/SAPO-34 catalyst. The SCR reaction was investigated at temperatures from 573 to 773 K, and the role of oxygen in the NO reduction process was determined by comparing experiments using an initial reaction mixture containing oxygen and without oxygen. The results show that both NO and propene are easily activated in oxygen. Furthermore, the presence of oxygen is necessary to form organo-NOx adsorbed species. Based on these experiments, a reaction mechanism is proposed that NO, propene and oxygen react to form organo-nitro and organo-nitrito adsorbed species as key intermediates, and then these intermediates decompose to nitrogen.
Visible Light Mediated Photoredox Catalytic Arylation Reactions.
Ghosh, Indrajit; Marzo, Leyre; Das, Amrita; Shaikh, Rizwan; König, Burkhard
anion of the organic dye perylenediimide is excited by a second photon allowing the one electron reduction of acceptor substituted aryl chlorides. The radical anion of the aryl halide fragments under the loss of a halide ion and the aryl radical undergoes C-H arylation with biologically important pyrrole derivatives or adds to a double bond. Rhodamine 6G as an organic photocatalyst allows an even higher degree of control of the reaction. The dye is photoreduced in the presence of an amine donor under irradiation with green light (e.g., 530 nm), yielding its radical anion, which is a mild reducing reagent. The hypsochromic shift of the absorption of the rhodamine 6G radical anion toward blue region of the visible light spectrum allows its selective excitation using blue light (e.g., 455 nm). The excited radical anion is highly reducing and able to activate even bromoanisole for C-H arylation reactions, although only in moderate yield. Photoredox catalytic C-H arylation reactions are valuable alternatives to metal catalyzed reactions. They have an excellent functional group tolerance, could potentially avoid metal containing catalysts, and use visible light as a traceless reagent for the activation of arylating reagents.
Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study.
Han, You; Sun, Mengxia; Li, Wei; Zhang, Jinli
The catalytic mechanism of Ru-based catalysts in the acetylene hydrochlorination reaction has been investigated via the density functional theory (DFT) method. To study the effect of the chlorine coordination number on the catalytic mechanism, Ru3Cl9, Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 clusters were chosen as the catalytic models. Our results show that the energy barrier for acetylene hydrochlorination on Ru3Cl9 was as high as 1.51 eV at 458 K. When the chlorine coordination number decreased, the energy barriers on Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 were 1.29, 0.89, 1.01 and 1.42 eV, respectively. On Ru3Cl9, the H and Cl atoms of HCl were simultaneously added to C2H2 to form C2H3Cl, while the reaction was divided into two steps on Ru3Cl7, Ru3Cl3 and Ru3 clusters. The first step was the addition of H atom of HCl to C2H2 to form C2H3˙, and the second step was the addition of Cl atom to C2H3˙ to form C2H3Cl. The step involving the addition of Cl was the rate-controlling step during the whole reaction. On Ru5Cl7 cluster, there was an additional step before the steps involving the addition of H and Cl: the transfer of H atom from HCl to Ru atom. This step was the rate-controlling step during the reaction of acetylene hydrochlorination on Ru5Cl7 and its energy barrier was the lowest among all the above-mentioned catalytic models. Therefore, the Ru5Cl7 cluster played the most predominant role in acetylene hydrochlorination with the largest reaction rate constant kTST of 10(3).
Quantum mechanical/molecular mechanical study of catalytic mechanism and role of key residues in methylation reactions catalyzed by dimethylxanthine methyltransferase in caffeine biosynthesis.
Yue, Yufei; Guo, Hong
The caffeine biosynthetic pathway is of considerable importance for the beverage and pharmaceutical industries which produces two blockbuster products: theobromine and caffeine. The major biochemistry in caffeine biosynthesis starts from the initial substrate of xanthosine and ends with the final product caffeine, with theobromine serving as an intermediate. The key enzyme, S-adenosyl-l-methionine (SAM) dependent 3,7-dimethyl-xanthine methyltransferase (DXMT), catalyzes two important methyl transfer steps in caffeine biosynthesis: (1) methylation of N3 of 7-methylxanthine (7mX) to form theobromine (Tb); (2) methylation of N1 of theobromine to form caffeine (Cf). Although DXMT has been structurally characterized recently, our understanding of the detailed catalytic mechanism and role of key catalytic residues is still lacking. In this work, the quantum mechanical/molecular mechanical (QM/MM) MD and free energy simulations are performed to elucidate the catalytic mechanism of the enzyme-catalyzed reactions and to explain experimental observations concerning the activity of this enzyme. The roles of certain active-site residues are studied, and the results of computer simulation seem to suggest that a histidine residue (His160) at the active site of DXMT may act as a general base/acid catalyst during the methyl transfer process.
Studies on Anion Promoted Titania.1: Preparation, Characterization, and Catalytic Activity toward Alcohol and Cumene Conversion Reactions of Phosphated Titania.
Parida; Acharya; Samantaray; Mishra
Phosphate impregnated titania samples with varying amount of phosphate have been prepared by solid-solid kneading as well as aqueous impregnation method. All the samples are characterized by XRD, TG-DTA, and N(2) adsorption-desorption isotherm. Surface area is found to increase with the increase in phosphate content up to 7.5 wt% loading and thereafter decreases. The average pore diameter and crystallite size of titania decreases with the addition of phosphate. However, total acidity (determined by base adsorption method) and the catalytic activity increases with the increase in phosphate content up to 10 wt%. Phosphated samples prepared using phosphoric acid as the source of phosphate exhibit higher acidity compared to the samples prepared using (NH(4))(3)PO(4). However, the sample prepared from (NH(4))(3)PO(4) shows the presence of both acid and basic sites. Though from the cumene conversion study it is understood that phosphated samples contain both Lewis and Brønsted acid sites, the latter predominates over the former. Copyright 1999 Academic Press.
A non-thermal lattice gas model for a dimer trimer reaction on a catalytic surface: A computer simulation study
NASA Astrophysics Data System (ADS)
Ahmad, Waqar; Parvez, M.; Baloach, Musa Kaleem; Qaisrani, A. U.; Khalid, M.
The kinetics of an irreversible dimer-trimer reaction of the type 3A 2 + 2B 3 → 6AB have been studied using a non-thermal (precursor mechanism) model on a square as well as on a hexagonal lattice surface by Monte Carlo simulation. When the range of the precursors (A atoms) is increased, the model gives production rates (reactive window widths) that are quite large as compared with those for thermal (Langmuir-Hanshelwood mechanism) model. The phase diagrams qualitatively resemble with the standard ZGB model except that the continuous transition point is eliminated when the range of the precursors is extended up to the third nearest neighbourhood. The diffusion of A atoms on the surface as well as their desorption from the surface with a certain probability is also considered to see their effects on the reaction mechanism.
Determination of Catalytic Coefficient for a First-Order Reaction
ERIC Educational Resources Information Center
Fraga, E. R.; And Others
Describes an undergraduate physical chemistry experiment in which the acid catalyzed hydrolysis of sucrose is used to determine the catalytic coefficient of the hydronium ion, the catalyst in this reaction. (MLH)
Catalytic Asymmetric 1,4-Addition Reactions of Simple Alkylnitriles.
Yamashita, Yasuhiro; Sato, Io; Suzuki, Hirotsugu; Kobayashi, Shū
The development of catalytic asymmetric carbon-carbon bond-forming reactions of alkylnitriles that do not have an activating group at the α-position, under proton-transfer conditions, is a challenging research topic. Here, we report catalytic asymmetric direct-type 1,4-addition reactions of alkylnitriles with α,β-unsaturated amides by using a catalytic amount of potassium hexamethyldisilazide (KHMDS) with a chiral macro crown ether. The desired reactions proceeded in high yields with good diastereo- and enantioselectivities. To our knowledge, this is the first example of catalytic asymmetric direct-type 1,4-addition reaction of alkylnitriles without any activating group at the α-position.
Catalytic reactions in heavy-ion collisions
NASA Astrophysics Data System (ADS)
Kolomeitsev, E. E.; Tomášik, B.
We discuss a new type of reactions of a ϕ-meson production on hyperons, πY → ϕY and antikaons -KN → ϕY. These reactions are not suppressed according to Okubo-Zweig-Iizuka rule and can be a new efficient source of ϕ mesons in a nucleus-nucleus collision. We discuss how these reactions can affect the centrality dependence and the rapidity distributions of the ϕ yield.
Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures
NASA Astrophysics Data System (ADS)
Hashemian, Mohammad Amin
Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional
X-ray, NMR, and Mutational Studies of the Catalytic Cycle of the GDP-Mannose Mannosyl Hydrolase Reaction
Gabelli,S.; Azurmendi, H.; Bianchet, M.; Amzel, L.; Mildva, A.
GDP-mannose hydrolase catalyzes the hydrolysis with inversion of GDP-{alpha}-D-hexose to GDP and {beta}-D-hexose by nucleophilic substitution by water at C1 of the sugar. Two new crystal structures (free enzyme and enzyme-substrate complex), NMR, and site-directed mutagenesis data, combined with the structure of the enzyme-product complex reported earlier, suggest a four-stage catalytic cycle. An important loop (L6, residues 119-125) contains a ligand to the essential Mg{sup 2+} (Gln-123), the catalytic base (His-124), and three anionic residues. This loop is not ordered in the X-ray structure of the free enzyme due to dynamic disorder, as indicated by the two-dimensional 1H-15N HMQC spectrum, which shows selective exchange broadening of the imidazole nitrogen resonances of His-124 (k{sub ex} = 6.6 x 10{sup 4} s{sup -1}). The structure of the enzyme-Mg{sup 2+}-GDP-mannose substrate complex of the less active Y103F mutant shows loop L6 in an open conformation, while the structure of the enzyme-Mg{sup 2+}-GDP product complex showed loop L6 in a closed, 'active' conformation. 1H-15N HMQC spectra show the imidazole N of His-124 to be unprotonated, appropriate for general base catalysis. Substituting Mg{sup 2+} with the more electrophilic metal ions Mn{sup 2+} or Co{sup 2+} decreases the pK{sub a} in the pH versus k{sub cat} rate profiles, showing that deprotonation of a metal-bound water is partially rate-limiting. The H124Q mutation, which decreases k{sub cat} 103.4-fold and largely abolishes its pH dependence, is rescued by the Y103F mutation, which increases k{sub cat} 23-fold and restores its pH dependence. The structural basis of the rescue is the fact that the Y103F mutation shifts the conformational equilibrium to the open form moving loop L6 out of the active site, thus permitting direct access of the specific base hydroxide from the solvent. In the proposed dissociative transition state, which occurs in the closed, active conformation of the enzyme, the
Catalytic asymmetric umpolung reactions of imines.
Wu, Yongwei; Hu, Lin; Li, Zhe; Deng, Li
The carbon-nitrogen double bonds in imines are fundamentally important functional groups in organic chemistry. This is largely due to the fact that imines act as electrophiles towards carbon nucleophiles in reactions that form carbon-carbon bonds, thereby serving as one of the most widely used precursors for the formation of amines in both synthetic and biosynthetic settings. If the carbon atom of the imine could be rendered electron-rich, the imine could react as a nucleophile instead of as an electrophile. Such a reversal in the electronic characteristics of the imine functionality would facilitate the development of new chemical transformations that convert imines into amines via carbon-carbon bond-forming reactions with carbon electrophiles, thereby creating new opportunities for the efficient synthesis of amines. The development of asymmetric umpolung reactions of imines (in which the imines act as nucleophiles) remains uncharted territory, in spite of the far-reaching impact such reactions would have in organic synthesis. Here we report the discovery and development of new chiral phase-transfer catalysts that promote the highly efficient asymmetric umpolung reactions of imines with the carbon electrophile enals. These catalysts mediate the deprotonation of imines and direct the 2-azaallyl anions thus formed to react with enals in a highly chemoselective, regioselective, diastereoselective and enantioselective fashion. The reaction tolerates a broad range of imines and enals, and can be carried out in high yield with as little as 0.01 mole per cent catalyst with a moisture- and air-tolerant operational protocol. These umpolung reactions provide a conceptually new and practical approach to chiral amino compounds.
Catalytic asymmetric umpolung reactions of imines
NASA Astrophysics Data System (ADS)
Wu, Yongwei; Hu, Lin; Li, Zhe; Deng, Li
The carbon-nitrogen double bonds in imines are fundamentally important functional groups in organic chemistry. This is largely due to the fact that imines act as electrophiles towards carbon nucleophiles in reactions that form carbon-carbon bonds, thereby serving as one of the most widely used precursors for the formation of amines in both synthetic and biosynthetic settings. If the carbon atom of the imine could be rendered electron-rich, the imine could react as a nucleophile instead of as an electrophile. Such a reversal in the electronic characteristics of the imine functionality would facilitate the development of new chemical transformations that convert imines into amines via carbon-carbon bond-forming reactions with carbon electrophiles, thereby creating new opportunities for the efficient synthesis of amines. The development of asymmetric umpolung reactions of imines (in which the imines act as nucleophiles) remains uncharted territory, in spite of the far-reaching impact such reactions would have in organic synthesis. Here we report the discovery and development of new chiral phase-transfer catalysts that promote the highly efficient asymmetric umpolung reactions of imines with the carbon electrophile enals. These catalysts mediate the deprotonation of imines and direct the 2-azaallyl anions thus formed to react with enals in a highly chemoselective, regioselective, diastereoselective and enantioselective fashion. The reaction tolerates a broad range of imines and enals, and can be carried out in high yield with as little as 0.01 mole per cent catalyst with a moisture- and air-tolerant operational protocol. These umpolung reactions provide a conceptually new and practical approach to chiral amino compounds.
New insights in understanding plasma-catalysis reaction pathways: study of the catalytic ozonation of an acetaldehyde saturated Ag/TiO2/SiO2 catalyst
NASA Astrophysics Data System (ADS)
Sauce, Sonia; Vega-González, Arlette; Jia, Zixian; Touchard, Sylvain; Hassouni, Khaled; Kanaev, Andrei; Duten, Xavier
This paper is a preliminary study intended to straighten out the role of reactive oxygen species in the activation mechanisms occurring in a plasma driven catalysis process for acetaldehyde decomposition. For this purpose, the interaction between the surface, the pollutant and one of the main oxidative species generated by non-thermal plasma, namely ozone, was studied. Acetaldehyde catalytic ozonation over a nanostructured Ag/TiO2/SiO2 catalyst is carried out at room temperature and atmospheric pressure, and followed by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS). For this, the catalyst is firstly saturated with acetaldehyde. At the end of the saturation, acetaldehyde and crotonaldehyde, its condensation product, are identified as the major adsorbed species. In a second step, the surface ozonation is carried out and three additional intermediates are identified, namely, acetone, formic acid and acetic acid. Gaseous CO, CO2, methyl formate and methyl acetate are detected at the DRIFTS outlet, evidencing the partial mineralization of the adsorbed species. A global reaction scheme is proposed for explaining the formation of those adsorbed intermediates and gaseous products. This proposed heterogeneous ozone induced chemistry has to be taken into account when associating non-thermal plasma in air to a catalyst. Contribution to the topical issue "The 14th International Symposium on High Pressure Low Temperature Plasma Chemistry (HAKONE XIV)", edited by Nicolas Gherardi, Ronny Brandenburg and Lars Stollenwark
Expression studies of catalytic antibodies
Ulrich, H.D.; Patten, P.A.; Yang, P.L.
We have examined the positive influence of human constant regions on the folding and bacterial expression of active soluble mouse immunoglobulin variable domains derived form a number of catalytic antibodies. Expression yields of eight hybridoma-and myeloma-derived chimeric Fab fragments are compared in both shake flasks and high-density fermentation. In addition the usefulness of this system for the generation of in vivo expression libraries is examined by constructing and expressing combinations of heavy and light chain variable regions that were not selected as a pair during an immune response. A mutagenesis study of one of the recombinant catalytic Fab fragments reveals that single amino acid substitutions can have dramatic effects on the expression yield. This system should be generally applicable to the production of Fab fragments of catalytic and other hybridoma-derived antibodies for crystallographic and structure-function studies. 41 refs., 4 figs., 1 tab.
Catalytic asymmetric dearomatization (CADA) reactions of phenol and aniline derivatives.
Wu, Wen-Ting; Zhang, Liming; You, Shu-Li
Phenols are widely used as starting materials in both industrial and academic society. Dearomatization reactions of phenols provide an efficient way to construct highly functionalized cyclohexadienones. The main challenge to make them asymmetric by catalytic methods is to control the selectivity while overcoming the loss of aromaticity. In this tutorial review, an up to date summary of recent progress in CADA reactions of phenol and aniline derivatives is presented.
Catalytic imine-imine cross-coupling reactions.
Matsumoto, Masatoshi; Harada, Masashi; Yamashita, Yasuhiro; Kobayashi, Shū
We report here efficient catalytic imine-imine cross-coupling reactions based on an umpolung strategy; an imine bearing a 9-fluorenyl moiety on its nitrogen atom, which acted as a nucleophile, reacted with another imine to afford an imine-imine cross-coupling adduct in high yield. Furthermore, a chiral guanidine acted as a chiral catalyst for these coupling reactions, and optically active 1,2-diamines were obtained in high yields with high enantioselectivities.
A combined experimental and computational study of the catalytic dehydration of glycerol on microporous zeolites: an investigation of the reaction mechanism and acrolein selectivity.
Lin, Xufeng; Lv, Yanhong; Qu, Yuanyuan; Zhang, Guodong; Xi, Yanyan; Phillips, David L; Liu, Chenguang
The catalytic activity and the acrolein selectivity for liquid phase glycerol dehydration on β zeolites (HNa-β-k) were found to be dependent on the reaction temperature as well as on the amount of acid sites on the zeolites. An increase in the reaction temperature favors the acrolein selectivity. The acrolein selectivity increases with the Na(+)/H(+) ratio and the glycerol conversion decreases with it so that a maximum acrolein yield is obtained when a certain amount of acidic sites are replaced by non-active Na(+) sites. The computational results indicate that 3-hydoxylpropanal (HPA) is an important intermediate that determines the final product selectivity. The relative rates of the different reaction pathways for HAP can be affected by the amount of water molecules involved in its homogeneous reaction. Based on the reaction mechanism proposed, it was hypothesized that smaller pores reduce activity but increase selectivity to acrolein, and results of the H-MFI zeolite were consistent with this hypothesis. Our work provides important insight into the overall landscape of the reaction mechanism and can be used to help design reaction systems that have good acrolein selectivity for the liquid phase glycerol dehydration reactions.
Fuel-rich, catalytic reaction experimental results
NASA Technical Reports Server (NTRS)
Rollbuhler, R. James
Future aeropropulsion gas turbine combustion requirements call for operating at very high inlet temperatures, pressures, and large temperature rises. At the same time, the combustion process is to have minimum pollution effects on the environment. Aircraft gas turbine engines utilize liquid hydrocarbon fuels which are difficult to uniformly atomize and mix with combustion air. An approach for minimizing fuel related problems is to transform the liquid fuel into gaseous form prior to the completion of the combustion process. Experimentally obtained results are presented for vaporizing and partially oxidizing a liquid hydrocarbon fuel into burnable gaseous components. The presented experimental data show that 1200 to 1300 K reaction product gas, rich in hydrogen, carbon monoxide, and light-end hydrocarbons, is formed when flowing 0.3 to 0.6 fuel to air mixes through a catalyst reactor. The reaction temperatures are kept low enough that nitrogen oxides and carbon particles (soot) do not form. Results are reported for tests using different catalyst types and configurations, mass flowrates, input temperatures, and fuel to air ratios.
Catalytic ignition model in a monolithic reactor with in-depth reaction
NASA Technical Reports Server (NTRS)
Tien, Ta-Ching; Tien, James S.
Two transient models have been developed to study the catalytic ignition in a monolithic catalytic reactor. The special feature in these models is the inclusion of thermal and species structures in the porous catalytic layer. There are many time scales involved in the catalytic ignition problem, and these two models are developed with different time scales. In the full transient model, the equations are non-dimensionalized by the shortest time scale (mass diffusion across the catalytic layer). It is therefore accurate but is computationally costly. In the energy-integral model, only the slowest process (solid heat-up) is taken as nonsteady. It is approximate but computationally efficient. In the computations performed, the catalyst is platinum and the reactants are rich mixtures of hydrogen and oxygen. One-step global chemical reaction rates are used for both gas-phase homogeneous reaction and catalytic heterogeneous reaction. The computed results reveal the transient ignition processes in detail, including the structure variation with time in the reactive catalytic layer. An ignition map using reactor length and catalyst loading is constructed. The comparison of computed results between the two transient models verifies the applicability of the energy-integral model when the time is greater than the second largest time scale of the system. It also suggests that a proper combined use of the two models can catch all the transient phenomena while minimizing the computational cost.
Manual control of catalytic reactions: Reactions by an apoenzyme gel and a cofactor gel
NASA Astrophysics Data System (ADS)
Kobayashi, Yuichiro; Takashima, Yoshinori; Hashidzume, Akihito; Yamaguchi, Hiroyasu; Harada, Akira
Enzymes play a vital role in catalysing almost all chemical reactions that occur in biological systems. Some enzymes must form complexes with non-protein molecules called cofactors to express catalytic activities. Although the control of catalytic reactions via apoenzyme-cofactor complexes has attracted significant attention, the reports have been limited to the microscale. Here, we report a system to express catalytic activity by adhesion of an apoenzyme gel and a cofactor gel. The apoenzyme and cofactor gels act as catalysts when they form a gel assembly, but they lose catalytic ability upon manual dissociation. We successfully construct a system with switchable catalytic activity via adhesion and separation of the apoenzyme gel with the cofactor gel. We expect that this methodology can be applied to regulate the functional activities of enzymes that bear cofactors in their active sites, such as the oxygen transport of haemoglobin or myoglobin and the electron transport of cytochromes.
Acid-base bifunctional catalytic surfaces for nucleophilic addition reactions.
Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro
This article illustrates the modification of oxide surfaces with organic amine functional groups to create acid-base bifunctional catalysts, summarizing our previous reports and also presenting new data. Immobilization of organic amines as bases on inorganic solid-acid surfaces afforded highly active acid-base bifunctional catalysts, which enabled various organic transformations including C--C coupling reactions, though these reactions did not proceed with either the homogeneous amine precursors or the acidic supports alone. Spectroscopic characterization, such as by solid-state MAS NMR and FTIR, revealed not only the interactions between acidic and basic sites but also bifunctional catalytic reaction mechanisms.
Catalytic Ignition and Upstream Reaction Propagation in Monolith Reactors
NASA Technical Reports Server (NTRS)
Struk, Peter M.; Dietrich, Daniel L.; Miller, Fletcher J.; T'ien, James S.
Using numerical simulations, this work demonstrates a concept called back-end ignition for lighting-off and pre-heating a catalytic monolith in a power generation system. In this concept, a downstream heat source (e.g. a flame) or resistive heating in the downstream portion of the monolith initiates a localized catalytic reaction which subsequently propagates upstream and heats the entire monolith. The simulations used a transient numerical model of a single catalytic channel which characterizes the behavior of the entire monolith. The model treats both the gas and solid phases and includes detailed homogeneous and heterogeneous reactions. An important parameter in the model for back-end ignition is upstream heat conduction along the solid. The simulations used both dry and wet CO chemistry as a model fuel for the proof-of-concept calculations; the presence of water vapor can trigger homogenous reactions, provided that gas-phase temperatures are adequately high and there is sufficient fuel remaining after surface reactions. With sufficiently high inlet equivalence ratio, back-end ignition occurs using the thermophysical properties of both a ceramic and metal monolith (coated with platinum in both cases), with the heat-up times significantly faster for the metal monolith. For lower equivalence ratios, back-end ignition occurs without upstream propagation. Once light-off and propagation occur, the inlet equivalence ratio could be reduced significantly while still maintaining an ignited monolith as demonstrated by calculations using complete monolith heating.
Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts.
Cao, Shaowen; Tao, Franklin Feng; Tang, Yu; Li, Yuting; Yu, Jiaguo
Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liquid interfaces with a purpose of establishing correlations of size- and shape-dependent chemical and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a molecular level.
Polymer and Membrane Design for Low Temperature Catalytic Reactions.
Villalobos, Luis Francisco; Xie, Yihui; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor
Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed.
Catalytic Ignition and Upstream Reaction Propagation in a Platinum Tube
NASA Technical Reports Server (NTRS)
Struk, P. M.; Dietrich, D. L.; Mellish, B. P.; Miller, F. J.; T'ien, J. S.
A challenge for catalytic combustion in monolithic reactors at elevated temperatures is the start-up or "light-off" from a cold initial condition. In this work, we demonstrate a concept called "back-end catalytic ignition that potentially can be utilized in the light-off of catalytic monoliths. An external downstream flame or Joule heating raises the temperature of a small portion of the catalyst near the outlet initiating a localized catalytic reaction that propagates upstream heating the entire channel. This work uses a transient numerical model to demonstrate "back-end" ignition within a single channel which can characterize the overall performance of a monolith. The paper presents comparisons to an experiment using a single non-adiabatic channel but the concept can be extended to the adiabatic monolith case. In the model, the time scales associated with solid heat-up are typically several orders of magnitude larger than the gas-phase and chemical kinetic time-scales. Therefore, the model assumes a quasi-steady gas-phase with respect to a transient solid. The gas phase is one-dimensional. Appropriate correlations, however, account for heat and mass transfer in a direction perpendicular to the flow. The thermally-thin solid includes axial conduction. The gas phase, however, does not include axial conduction due to the high Peclet number flows. The model includes both detailed gas-phase and catalytic surface reactions. The experiment utilizes a pure platinum circular channel oriented horizontally though which a CO/O2 mixture (equivalence ratios ranging from 0.6 to 0.9) flows at 2 m/s.
Elementary steps of the catalytic NO{sub x} reduction with NH{sub 3}: Cluster studies on reaction paths and energetics at vanadium oxide substrate
Gruber, M.; Hermann, K.
We consider different reaction scenarios of the selective catalytic reduction (SCR) of NO in the presence of ammonia at perfect as well as reduced vanadium oxide surfaces modeled by V{sub 2}O{sub 5}(010) without and with oxygen vacancies. Geometric and energetic details as well as reaction paths are evaluated using extended cluster models together with density-functional theory. Based on earlier work of adsorption, diffusion, and reaction of the different surface species participating in the SCR we confirm that at Brønsted acid sites (i.e., OH groups) of the perfect oxide surface nitrosamide, NH{sub 2}NO, forms a stable intermediate. Here adsorption of NH{sub 3} results in NH{sub 4} surface species which reacts with gas phase NO to produce the intermediate. Nitrosamide is also found as intermediate of the SCR near Lewis acid sites of the reduced oxide surface (i.e., near oxygen vacancies). However, here the adsorbed NH{sub 3} species is dehydrogenated to surface NH{sub 2} before it reacts with gas phase NO to produce the intermediate. The calculations suggest that reaction barriers for the SCR are overall higher near Brønsted acid sites of the perfect surface compared with Lewis acid sites of the reduced surface, examined for the first time in this work. The theoretical results are consistent with experimental findings and confirm the importance of surface reduction for the SCR process.
Elementary steps of the catalytic NOx reduction with NH3: Cluster studies on reaction paths and energetics at vanadium oxide substrate
NASA Astrophysics Data System (ADS)
Gruber, M.; Hermann, K.
We consider different reaction scenarios of the selective catalytic reduction (SCR) of NO in the presence of ammonia at perfect as well as reduced vanadium oxide surfaces modeled by V2O5(010) without and with oxygen vacancies. Geometric and energetic details as well as reaction paths are evaluated using extended cluster models together with density-functional theory. Based on earlier work of adsorption, diffusion, and reaction of the different surface species participating in the SCR we confirm that at Brønsted acid sites (i.e., OH groups) of the perfect oxide surface nitrosamide, NH2NO, forms a stable intermediate. Here adsorption of NH3 results in NH4 surface species which reacts with gas phase NO to produce the intermediate. Nitrosamide is also found as intermediate of the SCR near Lewis acid sites of the reduced oxide surface (i.e., near oxygen vacancies). However, here the adsorbed NH3 species is dehydrogenated to surface NH2 before it reacts with gas phase NO to produce the intermediate. The calculations suggest that reaction barriers for the SCR are overall higher near Brønsted acid sites of the perfect surface compared with Lewis acid sites of the reduced surface, examined for the first time in this work. The theoretical results are consistent with experimental findings and confirm the importance of surface reduction for the SCR process.
Growth states of catalytic reaction networks exhibiting energy metabolism
NASA Astrophysics Data System (ADS)
Kondo, Yohei; Kaneko, Kunihiko
All cells derive nutrition by absorbing some chemical and energy resources from the environment; these resources are used by the cells to reproduce the chemicals within them, which in turn leads to an increase in their volume. In this study we introduce a protocell model exhibiting catalytic reaction dynamics, energy metabolism, and cell growth. Results of extensive simulations of this model show the existence of four phases with regard to the rates of both the influx of resources and cell growth. These phases include an active phase with high influx and high growth rates, an inefficient phase with high influx but low growth rates, a quasistatic phase with low influx and low growth rates, and a death phase with negative growth rate. A mean field model well explains the transition among these phases as bifurcations. The statistical distribution of the active phase is characterized by a power law, and that of the inefficient phase is characterized by a nearly equilibrium distribution. We also discuss the relevance of the results of this study to distinct states in the existing cells.
A density functional study on the effect of the zeolite cavity on its catalytic activity: The dehydrogenation and cracking reactions of isobutane over HZSM-5 and HY zeolites
NASA Astrophysics Data System (ADS)
Milas, Ivan; Chaer Nascimento, Marco Antonio
The dehydrogenation and cracking reactions of isobutane over HZMS-5 and HY were studied at the DFT level of calculation to verify the influence of the cavity on the energetics and mechanism of the reactions. The zeolites were represented by the 20T and 32T clusters, respectively. The results indicate that the reactions follow the same mechanism in both zeolites but the activation energies are reduced by ˜10 kcal/mol relative to the values with smaller clusters. Activation energies for the dehydrogenation reactions were similar in both zeolites, but for the cracking reaction in HY, the activation energy is ˜5 kcal/mol higher than in HZSM-5.
Thermodynamics behind carbon nanotube growth via endothermic catalytic decomposition reaction.
Harutyunyan, Avetik R; Kuznetsov, Oleg A; Brooks, Christopher J; Mora, Elena; Chen, Gugang
Carbon filaments can be grown using hydrocarbons with either exothermic or endothermic catalytic decomposition enthalpies. By in situ monitoring the evolution of the reaction enthalpy during nanotube synthesis via methane gas, we found that although the decomposition reaction of methane is endothermic an exothermic process is superimposed which accompanies the nanotube growth. Analysis shows that the main contributor in this liberated heat is the radiative heat transfer from the surroundings, along with dehydrogenation reaction of in situ formed secondary hydrocarbons on the catalyst surface and the carbon hydrogenation/oxidation processes. This finding implies that nanotube growth process enthalpy is exothermic, and particularly, it extends the commonly accepted temperature gradient driven growth mechanism to the growth via hydrocarbons with endothermic decomposition enthalpy.
Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters.
Yamada, Akira; Miyajima, Ken; Mafuné, Fumitaka
Gas phase catalytic reactions involving the reduction of N(2)O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rh(n) (n = 10-28), using mass spectrometry. Sequential oxygen transfer reactions, Rh(n)O(m-1) + N(2)O → Rh(n)O(m) + N(2) (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, Rh(n)O(m) + CO → Rh(n)O(m-1) + CO(2) (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N(2)O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around Rh(n)O(m) (m ≥ 4) than around bare Rh(n). Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalytic CO oxidation reaction on a rhodium surface.
Reaction-driven surface restructuring and selectivity control in allylic alcohol catalytic aerobic oxidation over Pd.
Lee, Adam F; Ellis, Christine V; Naughton, James N; Newton, Mark A; Parlett, Christopher M A; Wilson, Karen
Synchronous, time-resolved DRIFTS/MS/XAS cycling studies of the vapor-phase selective aerobic oxidation of crotyl alcohol over nanoparticulate Pd have revealed surface oxide as the desired catalytically active phase, with dynamic, reaction-induced Pd redox processes controlling selective versus combustion pathways.
Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions**
Yu, Zhiyong; Ely, Robert J.
The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides a forum for the inspiration of new reaction development. In this manuscript, we present a synthesis of discodermolide that employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for chiral enolate alkylation. In addition, this synthesis of discodermolide provides the first examples of diene 1,4-diboration and borylative diene-aldehyde couplings in complex molecule synthesis. PMID:25045037
On the role of DNA in DNA-based catalytic enantioselective conjugate addition reactions.
Dijk, Ewold W; Boersma, Arnold J; Feringa, Ben L; Roelfes, Gerard
A kinetic study of DNA-based catalytic enantioselective Friedel-Crafts alkylation and Michael addition reactions showed that DNA affects the rate of these reactions significantly. Whereas in the presence of DNA, a large acceleration was found for the Friedel-Crafts alkylation and a modest acceleration in the Michael addition of dimethyl malonate, a deceleration was observed when using nitromethane as nucleophile. Also, the enantioselectivities proved to be dependent on the DNA sequence. In comparison with the previously reported Diels-Alder reaction, the results presented here suggest that DNA plays a similar role in both cycloaddition and conjugate addition reactions.
Hydrogen production from methane through catalytic partial oxidation reactions
NASA Astrophysics Data System (ADS)
Freni, S.; Calogero, G.; Cavallaro, S.
This paper reviews recent developments in syn-gas production processes used for partial methane oxidation with and/or without steam. In particular, we examined different process charts (fixed bed, fluidised bed, membrane, etc.), kinds of catalysts (powders, foams, monoliths, etc.) and catalytically active phases (Ni, Pt, Rh, etc.). The explanation of the various suggested technical solutions accounted for the reaction mechanism that may selectively lead to calibrated mixtures of CO and H 2 or to the unwanted formation of products of total oxidation (CO 2 and H 2O) and pyrolysis (coke). Moreover, the new classes of catalysts allow the use of small reactors to treat large amounts of methane (monoliths) or separate hydrogen in situ from the other reaction products (membrane). This leads to higher conversions and selectivity than could have been expected thermodynamically. Although catalysts based on Rh are extremely expensive, they can be used to minimise H 2O formation by maximising H 2 yield.
Catalytic test reactions for the evaluation of hierarchical zeolites.
Hartmann, Martin; Machoke, Albert Gonche; Schwieger, Wilhelm
Hierarchical zeolites have received increasing attention in the last decade due to their outstanding catalytic performance. Several types of hierarchical zeolites can be prepared by a large number of different techniques. Hierarchical zeolites combine the intrinsic catalytic properties of conventional zeolites and the facilitated access and transport in the additional meso- or macropore system. In this tutorial review, we discuss several test reactions that have been explored to show the benefit of the hierarchical pore system with respect to their suitability to prove the positive effects of hierarchical porous zeolites. It is important to note that positive effects on activity, stability and less frequently selectivity observed for hierarchically structured catalysts not necessarily are only a consequence of the additional meso- or macropores but also the number, strength and location of active sites as well as defects and impurities. With regard to these aspects, the test reaction has to be chosen carefully and potential changes in the chemistry of the catalyst have to be considered as well. In addition to the determination of conversion, yield and selectivity, we will show that the calculation of the activation energy and the determination of the Thiele modulus and the effectiveness factor are good indicators of the presence or absence of diffusion limitations in hierarchical zeolites compared to their parent materials.
Atomically resolved studies of reactions at industrial settings - novel design of an ultra high pressure, high temperature scanning tunneling microscope system for probing catalytic conversions
NASA Astrophysics Data System (ADS)
Tang, David; Somorjai, Gabor
In order to observe heterogeneous catalytic reactions that occur well above ambient pressure and temperature, a modified version of the Pan-style STM motor has been designed and constructed in-house. The new design features a much reduced size and a rigid coupling to the sample, and has been tested to show much higher resonant frequency than conventional Beetle-style STM designs, providing the ability to image faster and yielding lower susceptibility to noise. A small flow reactor cell (˜10 mL) has been constructed to house the new STM, whose samples and tips are accessible through a bayonet-sealed access port by the use of a wobble stick and a transfer arm. The reactor cell can be placed inside an UHV system to allow cleaning and characterization of sample before and after experiments, as well as continuous monitoring by mass spectrometry or gas chromatography through a leak valve. The new system also allows in vacuo sample and tip exchange without exposing the system to impurities in air. As such, the new ultrahigh pressure scanning tunneling microscope is designed to allow successive STM experiments performed with precise control of temperatures between 300 K and 600 K and pressures between <10-9 torr and 30 bars.
Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.
Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng
The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.
Study of the oxidative half-reaction catalyzed by a non-heme ferrous catalytic center by means of structural and computational methodologies
NASA Astrophysics Data System (ADS)
Cicero, Giancarlo; Carbonera, Chiara; Valegård, Karin; Hajdu, Janos; Andersson, Inger; Ranghino, Graziella
Deacetoxycephalosporin C synthase (DAOCS) is a mononuclear ferrous enzyme that catalyzes the expansion of the five-membered thiazolidine ring of the penicillin nucleus into the six-membered dihydrothiazine ring of the cephalosporins. In the first half-reaction with dioxygen and 2-oxoglutarate, a reactive iron-oxygen species is produced that can subsequently react with the penicillin substrate to yield the cephalosporin. We describe quantum mechanical calculations of the first part of the reaction based on the high-resolution structures of the active site of DAOCS and its complexes with ligands. These studies are aimed at understanding how the reactive species can be produced and contained in the active site of the enzyme. The results demonstrate the priming of the active site by the co-substrate for oxygen binding and hint to the presence of a stable iron-peroxo intermediate in equilibrium with a more reactive ferryl species and the formation of CO2 as a leaving group by decarboxylation of 2-oxoglutarate. A conclusion from these studies is that substitution of CO2 by the penicillin substrate triggers the oxidation reaction in a booby-trap-like mechanism.
Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction
Ju, Hua; Li, Zhihu; Xu, Yanhui
Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.
New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.
Zaera, Francisco
Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are
Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.
Collins, Gillian; Holmes, Justin D
Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs.
Catalytic Reaction Synthesis for the Partial Oxidation of Methane to Formaldehyde.
NASA Astrophysics Data System (ADS)
Cardenas-Galindo, Maria-Guadalupe
Catalytic reaction synthesis for the partial oxidation of methane to formaldehyde has been studied by combining microkinetic analysis with molecular orbital calculations. This strategy is used to establish microscopic correlations between the structure and composition of the active site and the kinetic parameters of the reaction mechanism. Using atom clusters to represent the active site of transition metal oxide catalysts, the relationship was probed between coordination number, oxidation state, and ionization potential of the active cation and the reaction steps of methane activation and surface reactions leading to formaldehyde formation. The analysis suggests that in transition metal oxide catalysts, the d-band orbitals of the metal cation should be empty, since otherwise CO_2 formation from CO oxidation will be excessive. Furthermore, the transition metal oxide d-band must be located at sufficiently low energy that it may accept electrons during methane activation. Oxygen O- species, representing vacancies in the 2p cluster band, will favor methane activation. However, clusters with fully occupied 2p bands (O^ {2-}^ecies) will favor formaldehyde production. Such inferences illustrate how experimental and theoretical information already incorporated into an existing microkinetic model for the reaction over V _2O_5 and MoO _3 catalysts can be extended to describe the reaction over new materials in the search for more active and selective catalysts. Using parameters estimated from the molecular orbital calculations, microkinetic reaction simulations were also shown to be useful to identify reactor operating conditions that may favor the production of formaldehyde. The simulation can be used to identify key experiments necessary to test the performance of postulated catalytic materials. The economic evaluation of the process design sets important target goals for methane conversion and formaldehyde selectivity that a catalytic material must satisfy to create a new
Effects of copper catalytic reactions on the development of supersonic hydrogen flames
Chang, S.L.; Lottes, S.A.; Berry, G.F.
Copper species are present in hydrogen flames in arc heated supersonic ramjet testing facilities. Homogeneous and heterogeneous copper catalytic reactions may affect the flame development by enhancing the recombination of hydrogen atoms. Computer simulation is used to investigate the effects of the catalytic reactions on the reaction and ignition times of the flames. The simulation uses a modified general chemical kinetics computer program to simulate the development of copper-contaminated hydrogen flames under scramjet testing conditions. Reaction times of hydrogen flames are found to be reduced due to the copper catalytic effects, but ignition times are much less sensitive to such effects. The reduction of reaction time depends on copper concentration, particle size (if copper is in the condensed phase), and Mach number (or initial temperature and pressure). As copper concentration increases or the particle size decreases, reaction time decreases. As Mach number increases (or pressure and temperature decrease), the copper catalytic effects are greater.
Study on the Catalytic Activity of Noble Metal Nanoparticles on Reduced Graphene Oxide for Oxygen Evolution Reactions in Lithium-Air Batteries.
Jeong, Yo Sub; Park, Jin-Bum; Jung, Hun-Gi; Kim, Jooho; Luo, Xiangyi; Lu, Jun; Curtiss, Larry; Amine, Khalil; Sun, Yang-Kook; Scrosati, Bruno; Lee, Yun Jung
Among many challenges present in Li-air batteries, one of the main reasons of low efficiency is the high charge overpotential due to the slow oxygen evolution reaction (OER). Here, we present systematic evaluation of Pt, Pd, and Ru nanoparticles supported on rGO as OER electrocatalysts in Li-air cell cathodes with LiCF3SO3-tetra(ethylene glycol) dimethyl ether (TEGDME) salt-electrolyte system. All of the noble metals explored could lower the charge overpotentials, and among them, Ru-rGO hybrids exhibited the most stable cycling performance and the lowest charge overpotentials. Role of Ru nanoparticles in boosting oxidation kinetics of the discharge products were investigated. Apparent behavior of Ru nanoparticles was different from the conventional electrocatalysts that lower activation barrier through electron transfer, because the major contribution of Ru nanoparticles in lowering charge overpotential is to control the nature of the discharge products. Ru nanoparticles facilitated thin film-like or nanoparticulate Li2O2 formation during oxygen reduction reaction (ORR), which decomposes at lower potentials during charge, although the conventional role as electrocatalysts during OER cannot be ruled out. Pt-and Pd-rGO hybrids showed fluctuating potential profiles during the cycling. Although Pt- and Pd-rGO decomposed the electrolyte after electrochemical cycling, no electrolyte instability was observed with Ru-rGO hybrids. This study provides the possibility of screening selective electrocatalysts for Li-air cells while maintaining electrolyte stability.
Cyclosophorohexadecaose and succinoglycan monomers as catalytic carbohydrates for the Strecker reaction.
Lee, Sanghoo; Cho, Eunae; Kwon, Chanho; Jung, Seunho
Some microbial carbohydrates have been used as catalysts for the multicomponent Strecker reaction using trimethylsilyl cyanide (TMSCN). Alpha-Cyclosophorohexadecaose (alpha-C16) derived from Xanthomonas species and succinoglycan monomers derived from Rhizobium species acted as catalytic carbohydrates in the mixture solutions of methanol and water. Malonaldehyde bis(phenylimine) as a substrate was completely converted (yield: 100%) into its product to 100% by both alpha-C16 and the succinoglycan monomer (M2), having acetyl, pyruvyl, and succinyl groups as substituents after 1h. The catalytic abilities of the carbohydrates were dependent on the inherent structures of the substrates used in this study, where substrate 1 having a symmetrical structure rather than the others was favorably reacted with the alpha-C16 and M2. Through this study, we suggest that the microbial carbohydrates used in this study could be expected to be environmentally-benign catalysts for the synthesis of alpha-aminonitriles.
Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.
Habershon, Scott
In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.
Catalytic reactor for promoting a chemical reaction on a fluid passing therethrough
NASA Technical Reports Server (NTRS)
Roychoudhury, Subir (Inventor); Pfefferle, William C. (Inventor)
A catalytic reactor with an auxiliary heating structure for raising the temperature of a fluid passing therethrough whereby the catalytic reaction is promoted. The invention is a apparatus employing multiple electrical heating elements electrically isolated from one another by insulators that are an integral part of the flow path. The invention provides step heating of a fluid as the fluid passes through the reactor.
Reaction kinetics of waste sulfuric acid using H2O2 catalytic oxidation.
Wang, Jiade; Hong, Binxun; Tong, Xinyang; Qiu, Shufeng
The process of recovering waste sulfuric acids using H2O2 catalytic oxidation is studied in this paper. Activated carbon was used as catalyst. Main operating parameters, such as temperature, feed rate of H2O2, and catalyst dosage, have effects on the removal of impurities from waste sulfuric acids. The reaction kinetics of H2O2 catalytic oxidation on impurities are discussed. At a temperature of 90°C, H2O2 feeding rate of 50 g (kg waste acid)(-1) per hour, and catalyst dosage of 0.2 wt% (waste acid weight), the removal efficiencies of COD and chrominance were both more than 99%, the recovery ratio of sulfuric acid was more than 95%, and the utilization ratio of H2O2 was 88.57%.
Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides
Ekerdt, J.G.
This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.
Catalytic enantioselective Friedel-Crafts/Michael addition reactions of indoles to ethenetricarboxylates.
Yamazaki, Shoko; Iwata, Yuko
[reaction: see text] The Friedel-Crafts reaction is an important reaction for the formation of new C-C bonds. Recently, catalytic enantioselective Friedel-Crafts reaction of alkylidene malonates has been reported. However, the substituents in alkylidene malonates are limited. To explore new substituents such as carboxyl and carbonyl groups, catalytic enantioselective Friedel-Crafts reactions of reactive ethenetricarboxylates and acyl-substituted methylenemalonates 1 were investigated. The reaction of 1 with indoles in the presence of catalytic amounts of chiral bisoxazoline copper(II) complex (10%) in THF at room temperature gave alkylated products in high yields and up to 95% ee. The enantioselectivity can be explained by the secondary orbital interaction on approach of indole to the less hindered side of the 1-Cu(II)-ligand complex.
Study on surface properties of gamma-alumina catalytic membrane
Mengchenu Lu; Guoxing Xiong; Bauser, H.
In recent years, preparation and separation applications of gamma-alumina membranes have been extensively studied. In catalysis research field, this membrane can be used not only as a separating medium but also as a catalyst or catalyst support. In this paper, a gamma-alumina catalytic membrane was prepared by a sol-gel technique, then special attention was paid to its surface properties related to catalysis, its surface acidity, hydroxyl, microstructure and pore properties was studied by IR with pyridine adsorption, XRD and N{sub 2} adsorption at low temperature, 1-butanol dehydration as a probe reaction was used to study its reaction property.
Electrical polymerization of a tetrazole polymer-modified electrode and its catalytic reaction toward dopamine
NASA Astrophysics Data System (ADS)
Hsieh, Mu-Tao; Whang, Thou-Jen
A conducting polymer-modified electrode was proposed in this article, which was fabricated by electropolymerization of 5-amino-1H-tetrazole (ATet) on a glassy carbon electrode. Electrochemical studies such as differential pulse voltammetry and chronoamperometry were performed for the evaluation of the rate constant of the catalytic reaction, the diffusion coefficient of the analyte dopamine, and the linear dynamic range of the analyte determination. The film modified electrode has superior resolving power in quantitative determination from the mixture of analytes and it was found to be an efficient functionalized electrode for its sensitivity and selectivity toward the analyte of interest.
Catalytic reaction of cytokinin dehydrogenase: preference for quinones as electron acceptors.
Frébortová, Jitka; Fraaije, Marco W; Galuszka, Petr; Sebela, Marek; Pec, Pavel; Hrbác, Jan; Novák, Ondrej; Bilyeu, Kristin D; English, James T; Frébort, Ivo
The catalytic reaction of cytokinin oxidase/dehydrogenase (EC 220.127.116.11) was studied in detail using the recombinant flavoenzyme from maize. Determination of the redox potential of the covalently linked flavin cofactor revealed a relatively high potential dictating the type of electron acceptor that can be used by the enzyme. Using 2,6-dichlorophenol indophenol, 2,3-dimethoxy-5-methyl-1,4-benzoquinone or 1,4-naphthoquinone as electron acceptor, turnover rates with N6-(2-isopentenyl)adenine of approx. 150 s(-1) could be obtained. This suggests that the natural electron acceptor of the enzyme is quite probably a p-quinone or similar compound. By using the stopped-flow technique, it was found that the enzyme is rapidly reduced by N6-(2-isopentenyl)adenine (k(red)=950 s(-1)). Re-oxidation of the reduced enzyme by molecular oxygen is too slow to be of physiological relevance, confirming its classification as a dehydrogenase. Furthermore, it was established for the first time that the enzyme is capable of degrading aromatic cytokinins, although at low reaction rates. As a result, the enzyme displays a dual catalytic mode for oxidative degradation of cytokinins: a low-rate and low-substrate specificity reaction with oxygen as the electron acceptor, and high activity and strict specificity for isopentenyladenine and analogous cytokinins with some specific electron acceptors. PMID:14965342
A computational study of detoxification of lewisite warfare agents by British anti-lewisite: catalytic effects of water and ammonia on reaction mechanism and kinetics.
Sahu, Chandan; Pakhira, Srimanta; Sen, Kaushik; Das, Abhijit K
trans-2-Chlorovinyldichloroarsine (lewisite, L agent, Lew-I) acts as a blistering agents. British anti-lewisite (BAL, 2,3-dimercaptopropanol) has long been used as an L-agent antidote. The main reaction channels for the detoxification proceed via breaking of As-Cl bonds and formation of As-S bonds, producing stable, nontoxic ring product [(2-methyl-1,3,2-dithiarsolan-4-yl)methanol]. M06-2X/GENECP calculations have been carried out to establish the enhanced rate of detoxification mechanism in the presence of NH3 and H2O catalysts in both gas and solvent phases, which has been modeled by use of the polarized continuum model (PCM). In addition, natural bond orbital (NBO) and atoms in molecules (AIM) analysis have been performed to characterize the intermolecular hydrogen bonding in the transition states. Transition-state theory (TST) calculation establishes that the rates of NH3-catalyzed (2.88 × 10(-11) s(-1)) and H2O-catalyzed (2.42 × 10(-11) s(-1)) reactions are reasonably faster than the uncatalyzed detoxification (5.44 × 10(-13) s(-1)). The results obtained by these techniques give new insight into the mechanism of the detoxification process, identification and thermodynamic characterization of the relevant stationary species, the proposal of alternative paths on modeled potential energy surfaces for uncatalyzed reaction, and the rationalization of the mechanistic role played by catalysts and solvents.
First principles molecular dynamics study of catalytic reactions of biological macromolecular systems: toward analyses with QM/MM hybrid molecular simulations.
Boero, Mauro; Park, Jung Mee; Hagiwara, Yohsuke; Tateno, Masaru
First principles molecular dynamics simulations performed on a fully solvated RNA model structure allowed us to investigate the mechanism for enzymatic cleavage reactions, in vitro, of RNA enzymes (ribozymes). The concerted action of two metal catalysts turns out to be the most efficient way to promote, on the one hand, the proton abstraction from 2(')-OH that triggers the nucleophilic attack and, on the other hand, the cleavage of the P-O(5(')) bond. In fact, the elimination of one of the two metal cations leads to an increase in the activation energy of the reaction. The simulated pathway shows that an OH(-) in the coordination shell of the Mg(2+) close to O(2(')) promotes the initial proton abstraction and prevents its transfer to the ribozyme. This suggests that, in a real ribozyme, the double-metal-ion reaction mechanism is preferred with respect to single-metal-ion mechanisms either in the presence or in absence of the OH(-) anion. Finally, an insight into the importance of hybrid quantum mechanics/molecular mechanics (QM/MM) schemes is discussed in view of the modelling of a realistic system carrying all the features of a true ribozyme.
Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, April 1, 1994--June 30, 1994
Iglesia, E.; Perry, D.L.; Heinemann, H.
Catalytic gasification work has been completed and no other work is planned in the general area of catalytic gasification of coals and chars has operated without a post-doctoral fellow because of budget limitations during the first two quarters of FY1994. Dr. S. Sundararajan joined the group in April 1994 and will be assigned to the project throughout the remaining of the fiscal year. Results published by Hamakawa, et al. in The Journal of the Electrochemical Society have confirmed the concept of methane coupling via a membrane reactor. These findings confirm our previous conclusion that thinner membranes and increased surface activity for C-H bond activation at low temperatures are required in order to reach commercially attractive rates of reaction. The initial analysis of a theoretical model comparing the membrane and cyclic processes has been completed. The results indicate that perovskite membranes on the order of 50 microns will be needed for the membrane operation to be superior to a cyclic one. Two techniques, laser ablation and spin-coating/sol-gel chemistry are being tried to prepare the thin membranes described above. Studies of the magnetochemical properties of the calcium-nickel-potassium oxide powdered catalysts have been concluded and a manuscript describing the work has been completed. Synchrotron x-ray fluorescence microprobe data for calcium-nickel-potassium films have been analyzed and an abstract of the results has been submitted for presentation at the Fall Meeting of the Materials Research Society. Initial films of strontium-zirconium oxide, using yttria-stabilized zirconia as a buffer layer, have been fabricated using pulsed laser deposition. X-ray diffraction data have been obtained for several of the strontium-zirconium-yttrium oxide films.
Stoichiometric Reactions of Acylnickel(II) Complexes with Electrophiles and the Catalytic Synthesis of Ketones
Acylnickel(II) complexes feature prominently in cross-electrophile coupling (XEC) reactions that form ketones, yet their reactivity has not been systematically investigated. We present here our studies on the reactivity of acylnickel(II) complexes with a series of carbon electrophiles. Bromobenzene, α-chloroethylbenzene, bromooctane, and iodooctane were reacted with (dtbbpy)NiII(C(O)C5H11)(Br) (1b) and (dtbbpy)NiII(C(O)tolyl)(Br) (1c) to form a variety of organic products. While reactions with bromobenzene formed complex mixtures of ketones, reactions with α-chloroethylbenzene were highly selective for the cross-ketone product. Reactions with iodooctane and bromooctane also produced the cross-ketone product, but in intermediate yield and selectivity. In most cases the presence or absence of a chemical reductant (zinc) had only a small effect on the selectivity of the reaction. The coupling of 1c with iodooctane (60% yield) was translated into a catalytic reaction, the carbonylative coupling of bromoarenes with primary bromoalkanes (six examples, 60% average yield). PMID:25364092
Phosphoryl transfer reaction snapshots in crystals: Insights into the mechanism of protein kinase a catalytic subunit
Das, Amit; Gerlits, Oksana O.; Heller, William T.; ...
To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, themore » thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. As a result, the present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.« less
Phosphoryl transfer reaction snapshots in crystals: Insights into the mechanism of protein kinase a catalytic subunit
Das, Amit; Gerlits, Oksana O.; Heller, William T.; Kovalevskyi, Andrii Y.; Langan, Paul; Tian, Jianhui
To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca2+ ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, the thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca2+ cations with Mg2+ ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. As a result, the present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.
Phosphoryl Transfer Reaction Snapshots in Crystals: INSIGHTS INTO THE MECHANISM OF PROTEIN KINASE A CATALYTIC SUBUNIT.
Gerlits, Oksana; Tian, Jianhui; Das, Amit; Langan, Paul; Heller, William T; Kovalevsky, Andrey
To study the catalytic mechanism of phosphorylation catalyzed by cAMP-dependent protein kinase (PKA) a structure of the enzyme-substrate complex representing the Michaelis complex is of specific interest as it can shed light on the structure of the transition state. However, all previous crystal structures of the Michaelis complex mimics of the PKA catalytic subunit (PKAc) were obtained with either peptide inhibitors or ATP analogs. Here we utilized Ca(2+) ions and sulfur in place of the nucleophilic oxygen in a 20-residue pseudo-substrate peptide (CP20) and ATP to produce a close mimic of the Michaelis complex. In the ternary reactant complex, the thiol group of Cys-21 of the peptide is facing Asp-166 and the sulfur atom is positioned for an in-line phosphoryl transfer. Replacement of Ca(2+) cations with Mg(2+) ions resulted in a complex with trapped products of ATP hydrolysis: phosphate ion and ADP. The present structural results in combination with the previously reported structures of the transition state mimic and phosphorylated product complexes complete the snapshots of the phosphoryl transfer reaction by PKAc, providing us with the most thorough picture of the catalytic mechanism to date.
Basic character of rare earth metal alkoxides. Utilization in catalytic C-C bond-forming reactions and catalytic asymmetric nitroaldol reactions
Sasai, H.; Suzuki, T.; Arai, S.
In a recent paper, the authors reported that Zr(O-t-Bu){sub 4} was an efficient and convenient basic reagent in organic synthesis. However, all reactions examined were performed with stoichiometric quantities of the reagent. The authors envisioned that rare earth metal alkoxides would be stronger bases than group 4 metal alkoxides due to the lower ionization potential (ca. 5.4-6.4 eV) and the lower electronegativity (1.1-1.3) of rare earth elements; thus, the catalytic use of rare earth metal alkoxides in organic synthesis was expected. Although a variety of rare earth metal alkoxides have been prepared for the last three decades, to the authors knowledge, there have been few reports concerning the basicity of rare earth metal alkoxides. Herein, the authors report several carbon-carbon bond-forming reactions catalyzed by rare earth metal alkoxides and their application to a catalytic asymmetric nitroaldol reaction.
Catalytic effect of magnetic nanoparticles over the H2O2 decomposition reaction.
Andrade, A L; Souza, D M; Pereira, M C; Fabris, J D; Domingues, R Z
This paper compares the rate of decomposition of hydrogen peroxide when controlled nano-sized magnetite powders are used as catalysts. Two different nano-sized powders and a Fe0/Fe3O4 composite have been used. The nanoparticle samples were synthesized by: (i) a chemical reduction-precipitation method and, (ii) by reduction under H2 atmosphere at 250 degrees C, of a hematite sample previously prepared. The composite, Fe0/Fe3O4, was prepared by thermal controlled reduction of nanoparticles of Fe2O3 obtained from hematite under H2 at 300 degrees C. The samples were characterized by Fourier-transform infrared, X-ray diffraction, and Mössbauer spectroscopy at room temperature, and surface area. The catalytic effect was studied in the decomposition reaction of H2O2 by measuring the formation of gaseous O2. The results showed the presence of pure Fe3O4 for nano magnetite samples and Fe0 and Fe3O4 for the composite sample. The average particle sizes of the magnetite, calculated from reflection 311 by using Scherrer equation were about 33 and 10 nm for the samples obtained by hematite reduction and reduction-precipitation, respectively. Kinetic studies of the decomposition of peroxide showed a higher decomposition rate for the hydrogen peroxide reaction when nanoparticles prepared by reduction-precipitation method were used as catalysts. The high catalytic activity associated to nanoparticles is discussed in terms of the high surface area of these samples.
Pt loaded carbon aerogel catalyst for catalytic exchange reactions between water and hydrogen gas
NASA Astrophysics Data System (ADS)
Singh, Rashmi; Singh, Ashish; Kohli, D. K.; Singh, M. K.; Gupta, P. K.
We report development and characterization of platinum doped carbon aerogel catalyst for catalytic exchange reactions between water and hydrogen gas. The carbon aerogel with uniformly dispersed platinum nanoparticles was prepared by adding platinum precursor during the sol-gel process. Thereafter colloidal PTFE was mixed with the platinum doped carbon aerogel powder and coated on Dixon rings to obtain hydrophobic catalyst with required mechanical strength. Detailed studies have been carried out to observe the effect of physical characteristics of the catalyst powder (surface area and pore size of aerogels, Pt cluster size and its valence state etc) and the different coating parameters (PTFE to Pt-CA ratio and Pt loading on Dixon ring) on volume transfer rate (Ky.a) for H/D reaction. Ky.a values of ˜0.8 m3 (STP).s-1. m-3 were obtained for Pt loading of 7% and Pt cluster size of 3 nm at atmospheric pressure.
Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling
Garcia, Andres; Wang, Jing; Windus, Theresa L.; ...
Statistical mechanical modeling is developed to describe a catalytic conversion reaction A → Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Hence, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A.
Catalytic conversion of bio-oil to oxygen-containing fuels by simultaneous reactions with 1-butanol and 1-octene over solid acids: Model compound studies and reaction pathways.
Zhang, Zhi-Jun; Sui, Shu-Juan; Tan, Shun; Wang, Qing-Wen; Pittman, Charles U
Upgrading bio-oil by addition reactions across olefins represents a route to refine bio-oil to combustible and stable oxygen-containing fuels. Development and application of highly active strong solid acid catalysts with good hydrothermal stability has become a key determinant for success, because bio-oil's complexity includes large amounts of water. Temperatures of 120°C or more are needed for satisfactory kinetics. Batch upgrading of a model bio-oil (phenol/water/acetic acid/acetaldehyde/hydroxyacetone/d-glucose/2-hydroxymethylfuran) over five water-tolerant solid acid catalysts (Dowex50WX2, Amberlyst15, Amberlyst36, silica sulfuric acid (SSA) and Cs(2.5)H(0.5)PW(12)O(40) supported on K-10 clay (Cs(2.5)/K-10, 30wt.%)) with 1-octene/1-butanol were studied at 120°C/3h. SSA, , exhibited the highest water tolerance and activity. Upgrading using olefin/1-butanol is complex, involving many simultaneous competing esterification, etherification, olefin hydration, phenol alkylation, aldol condensation, sugar dehydration etc. reactions.
Rapid-reaction kinetic characterization of the pathway of streptokinase-plasmin catalytic complex formation.
Verhamme, Ingrid M; Bock, Paul E
Binding of the fibrinolytic proteinase plasmin (Pm) to streptokinase (SK) in a tight stoichiometric complex transforms Pm into a potent proteolytic activator of plasminogen. SK binding to the catalytic domain of Pm, with a dissociation constant of 12 pm, is assisted by SK Lys(414) binding to a Pm kringle, which accounts for a 11-20-fold affinity decrease when Pm lysine binding sites are blocked by 6-aminohexanoic acid (6-AHA) or benzamidine. The pathway of SK.Pm catalytic complex formation was characterized by stopped-flow kinetics of SK and the Lys(414) deletion mutant (SKDeltaK414) binding to Pm labeled at the active site with 5-fluorescein ([5F]FFR-Pm) and the reverse reactions by competitive displacement of [5F]FFR-Pm with active site-blocked Pm. The rate constants for the biexponential fluorescence quenching caused by SK and SKDeltaK414 binding to [5F]FFR-Pm were saturable as a function of SK concentration, reporting encounter complex affinities of 62-110 nm in the absence of lysine analogs and 4900-6500 and 1430-2200 nm in the presence of 6-AHA and benzamidine, respectively. The encounter complex with SKDeltaK414 was approximately 10-fold weaker in the absence of lysine analogs but indistinguishable from that of native SK in the presence of 6-AHA and benzamidine. The studies delineate for the first time the sequence of molecular events in the formation of the SK.Pm catalytic complex and its regulation by kringle ligands. Analysis of the forward and reverse reactions supports a binding mechanism in which SK Lys(414) binding to a Pm kringle accompanies near-diffusion-limited encounter complex formation followed by two slower, tightening conformational changes.
Process of forming catalytic surfaces for wet oxidation reactions
NASA Technical Reports Server (NTRS)
Jagow, R. B. (Inventor)
A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.
Catalytic studies on a novel synthesis of methanol
Palekar, V.M.; Tierney, J.W.; Wender, I.
Catalytic studies on a new method for methanol synthesis from CO and H{sub 2} in a slurry reactor are described. This reaction proceeds through the carbonylation of methanol to methyl formate in the liquid phase followed by hydrogenolysis of methyl formate to two molecules of methanol; the net result is the reaction of CO with H{sub 2} to give methanol. Moderate temperatures and pressures (100--160{degrees}C, 50--65 atm) are used. Reaction rates using mixed catalysts comprised of an alkali methoxide and Cu-chromite are presented. It seems likely that Cu-chromite maintains the activity of the alkali methoxide catalyst. A mixed catalyst comprised of potassium methoxide and Cu-chromite was found to be the most active under the reaction conditions used. Evidence is provided for an interaction between the alkali methoxide and Cu-chromite. 27 refs., 6 figs., 2 tabs.
Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction
Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping
A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.
Self-organized criticality of a catalytic reaction network under flow.
Awazu, Akinori; Kaneko, Kunihiko
Self-organized critical behavior in a catalytic reaction network system induced by smallness in the molecule number is reported. The system under a flow of chemicals is shown to undergo a transition from a stationary to an intermittent reaction phase when the flow rate is decreased. In the intermittent reaction phase, two temporal regimes with active and halted reactions alternate. The number frequency of reaction events at each active regime and its duration time are shown to obey a universal power law with the exponents 4/3 and 3/2, respectively, independently of the parameters and network structure. These power laws are explained by a one-dimensional random-walk representation of the number of catalytically active chemicals. Possible relevance of the result to reaction dynamics in artificial and biological cells is briefly discussed.
A Phosphoenzyme Mimic, Overlapping Catalytic Sites and Reaction Coordinate Motion for Human NAMPT
Burgos, E.; Ho, M; Almo, S; Schramm, V
Nicotinamide phosphoribosyltransferase (NAMPT) is highly evolved to capture nicotinamide (NAM) and replenish the nicotinamide adenine dinucleotide (NAD+) pool during ADP-ribosylation and transferase reactions. ATP-phosphorylation of an active-site histidine causes catalytic activation, increasing NAM affinity by 160,000. Crystal structures of NAMPT with catalytic site ligands identify the phosphorylation site, establish its role in catalysis, demonstrate unique overlapping ATP and phosphoribosyltransferase sites, and establish reaction coordinate motion. NAMPT structures with beryllium fluoride indicate a covalent H247-BeF3- as the phosphohistidine mimic. Activation of NAMPT by H247-phosphorylation causes stabilization of the enzyme-phosphoribosylpyrophosphate complex, permitting efficient capture of NAM. Reactant and product structures establish reaction coordinate motion for NAMPT to be migration of the ribosyl anomeric carbon from the pyrophosphate leaving group to the nicotinamide-N1 while the 5-phosphoryl group, the pyrophosphate moiety, and the nicotinamide ring remain fixed in the catalytic site.
A phosphoenzyme mimic, overlapping catalytic sites and reaction coordinate motion for human NAMPT
Burgos, Emmanuel S.; Ho, Meng-Chiao; Almo, Steven C.; Schramm, Vern L.
Nicotinamide phosphoribosyltransferase (NAMPT) is highly evolved to capture nicotinamide (NAM) and replenish the nicotinamide adenine dinucleotide (NAD+) pool during ADP-ribosylation and transferase reactions. ATP-phosphorylation of an active-site histidine causes catalytic activation, increasing NAM affinity by 160,000. Crystal structures of NAMPT with catalytic site ligands identify the phosphorylation site, establish its role in catalysis, demonstrate unique overlapping ATP and phosphoribosyltransferase sites, and establish reaction coordinate motion. NAMPT structures with beryllium fluoride indicate a covalent H247-BeF3− as the phosphohistidine mimic. Activation of NAMPT by H247-phosphorylation causes stabilization of the enzyme-phosphoribosylpyrophosphate complex, permitting efficient capture of NAM. Reactant and product structures establish reaction coordinate motion for NAMPT to be migration of the ribosyl anomeric carbon from the pyrophosphate leaving group to the nicotinamide-N1 while the 5-phosphoryl group, the pyrophosphate moiety, and the nicotinamide ring remain fixed in the catalytic site. PMID:19666527
Catalytic asymmetric direct-type 1,4-addition reactions of simple amides.
Suzuki, Hirotsugu; Sato, Io; Yamashita, Yasuhiro; Kobayashi, Shū
The development of catalytic asymmetric direct-type reactions of less acidic carbonyl compounds such as amides and esters has been a challenging theme in organic chemistry for decades. Here we describe the asymmetric direct 1,4-addition reactions of simple amides with α,β-unsaturated carbonyl compounds using a catalytic amount of a novel chiral catalyst consisting of a potassium base and a macrocyclic chiral crown ether. The desired 1,5-dicarbonyl compounds were obtained in high yields with excellent diastereo- and enantioselectivities. This is the first example of a highly enantioselective catalytic direct-type reaction of simple amides. In addition, the structure of the chiral potassium catalyst has been investigated by X-ray crystallographic, dynamic (1)H NMR, and MALDI-TOF MS analyses.
A study on naphtha catalytic reforming reactor simulation and analysis.
Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei
A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.
A study on naphtha catalytic reforming reactor simulation and analysis
Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei
A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data. PMID:15909350
Sum frequency generation and catalytic reaction studies of the removal of the organic capping agents from Pt nanoparticles by UV-ozone treatment
Aliaga, Cesar; Park, Jeong Y.; Yamada, Yusuke; Lee, Hyun Sook; Tsung, Chia-Kuang; Yang, Peidong; Somorjai, Gabor A.
We report the structure of the organic capping layers of platinum colloid nanoparticles and their removal by UV-ozone exposure. Sum frequency generation vibrational spectroscopy (SFGVS) studies identify the carbon-hydrogen stretching modes on poly(vinylpyrrolidone) (PVP) and tetradecyl tributylammonium bromide (TTAB)-capped platinum nanoparticles. We found that the UV-ozone treatment technique effectively removes the capping layer on the basis of several analytical measurements including SFGVS, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The overall shape of the nanoparticles was preserved after the removal of capping layers, as confirmed by transmission electron microscopy (TEM). SFGVS of ethylene hydrogenation on the clean platinum nanoparticles demonstrates the existence of ethylidyne and di-{sigma}-bonded species, indicating the similarity between single-crystal and nanoparticle systems.
Metal Vinylidenes as Catalytic Species in Organic Reactions
McClory, Andrew
Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis. PMID:18172846
Two-dimensional reaction free energy surfaces of catalytic reaction: effects of protein conformational dynamics on enzyme catalysis.
Min, Wei; Xie, X Sunney; Bagchi, Biman
We introduce a two-dimensional (2D) multisurface reaction free energy description of the catalytic cycle that explicitly connects the recently observed multi-time-scale conformational dynamics as well as dispersed enzymatic kinetics to the classical Michaelis-Menten equation. A slow conformational motion on a collective enzyme coordinate Q facilitates the catalytic reaction along the intrinsic reaction coordinate X, providing a dynamic realization of Pauling's well-known idea of transition-state stabilization. The catalytic cycle is modeled as transitions between multiple displaced harmonic wells in the XQ space representing different states of the cycle, which is constructed according to the free energy driving force of the cycle. Subsequent to substrate association with the enzyme, the enzyme-substrate complex under strain exhibits a nonequilibrium relaxation toward a new conformation that lowers the activation energy of the reaction, as first proposed by Haldane. The chemical reaction in X is thus enslaved to the down hill slow motion on the Q surface. One consequence of the present theory is that, in spite of the existence of dispersive kinetics, the Michaelis-Menten expression of the catalysis rate remains valid under certain conditions, as observed in recent single-molecule experiments. This dynamic theory builds the relationship between the protein conformational dynamics and the enzymatic reaction kinetics and offers a unified description of enzyme fluctuation-assisted catalysis.
SpaciMS: spatial and temporal operando resolution of reactions within catalytic monoliths
Sa, Jacinto; Fernandes, Daniel; Aiouache, Farid; Goguet, Alexandre; Hardacdre, Christopher; Lundie, David; Naeem, Wasif; Partridge Jr, William P; Stere, Cristina
Monolithic catalysts are widely used as structured catalysts, especially in the abatement of pollutants. Probing what happens inside these monoliths during operation is, therefore, vital for modelling and prediction of the catalyst behavior. SpaciMS is a spatially resolved capillary-inlet mass spectroscopy system allowing for the generation of spatially resolved maps of the reactions within monoliths. In this study SpaciMS results combined with 3D CFD modelling demonstrate that SpaciMS is a highly sensitive and minimally invasive technique that can provide reaction maps as well as catalytic temporal behavior. Herein we illustrate this by examining kinetic oscillations during a CO oxidation reaction over a Pt/Rh on alumina catalyst supported on a cordierite monolith. These oscillations were only observed within the monolith by SpaciMS between 30 and 90% CO conversion. Equivalent experiments performed in a plug-flow reactor using this catalyst in a crushed form over a similar range of reaction conditions did not display any oscillations demonstrating the importance of intra monolith analysis. This work demonstrates that the SpaciMS offers an accurate and comprehensive picture of structured catalysts under operation.
Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones.
Zhang, Junmin; Xing, Chong; Tiwari, Bhoopendra; Chi, Yonggui Robin
We disclose the first catalytic activation of carbohydrates as formaldehyde equivalents to generate acyl anions as one-carbon nucleophilic units for a Stetter reaction. The activation involves N-heterocyclic carbene (NHC)-catalyzed C-C bond cleavage of carbohydrates via a retro-benzoin-type process to generate the acyl anion intermediates. This Stetter reaction constitutes the first success in generating formal formaldehyde-derived acyl anions as one-carbon nucleophiles for non-self-benzoin processes. The renewable nature of carbohydrates, accessible from biomass, further highlights the practical potential of this fundamentally interesting catalytic activation.
Alexander, J.M.; Lacey, R.A.
Research focused on the statistical and dynamical properties of ``hot`` nuclei formed in symmetric heavy-ion reactions. Theses included ``flow`` measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study {sup 40}Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs.
Facilitating ZnO nanostructure growths by making seeds for self-catalytic reactions
Yin Liang; Yu, Choongho
Long and straight single-crystalline ZnO nanowires were successfully synthesized on ZnCl{sub 2}-coated Zn foils in oxygen environment by using simple thermal annealing processes. With relatively low reaction temperatures (410 and 700 Degree-Sign C), nanowires whose lengths and diameters are up to {approx}50 {mu}m and 10-100 nm were obtained. We found that ZnO seeds created from ZnCl{sub 2} played an important role in facilitating the ZnO nanowire growth via self-catalytic reactions. Systematic studies by altering critical synthesis factors that determine shape, length, diameter, and density of the nanowires were performed in order to unveil the growth mechanisms. We also compared the nanowires synthesized from Zn foils with tetrapod ZnO nanostructures synthesized from Zn powders at various temperatures. - Graphical abstract: (Left panel) ZnO seeds from ZnCl{sub 2} after thermal annealing at 500 Degree-Sign C for 5 min, (right panel) dense ZnO nanowires grown from Zn foils with ZnCl{sub 2} coating after thermal annealing at 700 Degree-Sign C for 60 min. Highlights: Black-Right-Pointing-Pointer ZnCl{sub 2} facilitated ZnO nanowire growth by creating ZnO seeds. Black-Right-Pointing-Pointer ZnO nanowires were synthesized via self-catalytic reactions. Black-Right-Pointing-Pointer Long and straight single-crystalline ZnO nanowires were synthesized. Black-Right-Pointing-Pointer Key parameters in thermal annealing processes were identified.
"Ab initio" synthesis of zeolites for preestablished catalytic reactions.
Gallego, Eva María; Portilla, M Teresa; Paris, Cecilia; León-Escamilla, Alejandro; Boronat, Mercedes; Moliner, Manuel; Corma, Avelino
Unlike homogeneous catalysts that are often designed for particular reactions, zeolites are heterogeneous catalysts that are explored and optimized in a heuristic fashion. We present a methodology for synthesizing active and selective zeolites by using organic structure-directing agents that mimic the transition state (TS) of preestablished reactions to be catalyzed. In these zeolites, the pores and cavities could be generated approaching a molecular-recognition pattern. For disproportionation of toluene and isomerization of ethylbenzene into xylenes, the TSs are larger than the reaction products. Zeolite ITQ-27 showed high disproportionation activity, and ITQ-64 showed high selectivity for the desired para and ortho isomers. For the case of a product and TS of similar size, we synthesized a catalyst, MIT-1, for the isomerization of endo-dicyclopentane into adamantane.
Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.
Catlow, C Richard A
Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.
Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions
NASA Astrophysics Data System (ADS)
Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.
Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.
Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, July 1--September 30, 1992
Heinemann, H.; Somorjai, G.A.; Perry, D.L.
Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C{sub 2}, C{sub 3} and C{sub 4} hydrocarbons and Particularly Olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility Of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.
Robustness and modularity properties of a non-covalent DNA catalytic reaction
Zhang, David Yu
The biophysics of nucleic acid hybridization and strand displacement have been used for the rational design of a number of nanoscale structures and functions. Recently, molecular amplification methods have been developed in the form of non-covalent DNA catalytic reactions, in which single-stranded DNA (ssDNA) molecules catalyze the release of ssDNA product molecules from multi-stranded complexes. Here, we characterize the robustness and specificity of one such strand displacement-based catalytic reaction. We show that the designed reaction is simultaneously sensitive to sequence mutations in the catalyst and robust to a variety of impurities and molecular noise. These properties facilitate the incorporation of strand displacement-based DNA components in synthetic chemical and biological reaction networks. PMID:20194118
Modeling the Catalysis of Anti-Cocaine Catalytic Antibody: Competing Reaction Pathways and Free Energy Barriers
Pan, Yongmei; Gao, Daquan; Zhan, Chang-Guo
The competing reaction pathways and the corresponding free energy barriers for cocaine hydrolysis catalyzed by an anti-cocaine catalytic antibody, mAb 15A10, were studied by using a novel computational strategy based on the binding free energy calculations on the antibody binding with cocaine and transition states. The calculated binding free energies were used to evaluate the free energy barrier shift from the cocaine hydrolysis in water to the antibody-catalyzed cocaine hydrolysis for each reaction pathway. The free energy barriers for the antibody-catalyzed cocaine hydrolysis were predicted to be the corresponding free energy barriers for the cocaine hydrolysis in water plus the calculated free energy barrier shifts. The calculated free energy barrier shift of −6.33 kcal/mol from the dominant reaction pathway of the cocaine benzoyl ester hydrolysis in water to the dominant reaction pathway of the antibody-catalyzed cocaine hydrolysis is in good agreement with the experimentally-derived free energy barrier shift of −5.93 kcal/mol. The calculated mutation-caused shifts of the free energy barrier are also reasonably close to the available experimental activity data. The good agreement suggests that the protocol for calculating the free energy barrier shift from the cocaine hydrolysis in water to the antibody-catalyzed cocaine hydrolysis may be used in future rational design of possible high-activity mutants of the antibody as anti-cocaine therapeutics. The general strategy of the free energy barrier shift calculation may also be valuable in studying a variety of chemical reactions catalyzed by other antibodies or proteins through non-covalent bonding interactions with the substrates. PMID:18341277
Utilization of the Recycle Reactor in Determining Kinetics of Gas-Solid Catalytic Reactions.
ERIC Educational Resources Information Center
Paspek, Stephen C.; And Others
Describes a laboratory scale reactor that determines the kinetics of a gas-solid catalytic reaction. The external recycle reactor construction is detailed with accompanying diagrams. Experimental details, application of the reactor to CO oxidation kinetics, interphase gradients, and intraphase gradients are discussed. (CS)
Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane
ERIC Educational Resources Information Center
Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.
Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…
Catalytic Friedel-Crafts Reactions of Highly Electronically Deactivated Benzylic Alcohols.
Vuković, Vuk D; Richmond, Edward; Wolf, Eléna; Moran, Joseph
Highly electronically deactivated benzylic alcohols, including those with a CF3 group adjacent to the OH-bearing carbon, undergo dehydrative Friedel-Crafts reactions upon exposure to catalytic Brønsted acid in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solvent. Titration and kinetic experiments support the involvement of higher order solvent/acid clusters in catalysis.
Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides.
Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu
Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asymmetric catalysis. This methodology is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts.
LETTER TO THE EDITOR: Single-species reactions on a random catalytic chain
NASA Astrophysics Data System (ADS)
Oshanin, G.; Burlatsky, S. F.
We present an exact solution for a catalytically activated annihilation A + A → 0 reaction taking place on a one-dimensional chain in which some segments (placed at random, with mean concentration p) possess special, catalytic properties. An annihilation reaction takes place as soon as any two A particles land from the reservoir onto two vacant sites at the extremities of the catalytic segment, or when any A particle lands onto a vacant site on a catalytic segment while the site at the other extremity of this segment is already occupied by another A particle. We find that the disorder-average pressure P(quen) per site of such a chain is given by P(quen) = P(Lan) + β-1F, where P(Lan) = β-1 ln(1 + z) is the Langmuir adsorption pressure, (z being the activity and β-1 the temperature), while β-1F is the reaction-induced contribution, which can be expressed, under appropriate change of notation, as the Lyapunov exponent for the product of 2 × 2 random matrices, obtained exactly by Derrida and Hilhorst (1983 J. Phys. A: Math. Gen. 16 2641). Explicit asymptotic formulae for the particle mean density and the compressibility are also presented.
High-spatial-resolution mapping of catalytic reactions on single particles
NASA Astrophysics Data System (ADS)
Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan; Bechtel, Hans A.; Martin, Michael C.; Toste, F. Dean; Gross, Elad
The critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has been used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. These observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles—which contain metal atoms with low coordination numbers—are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.
[The surface adsorption and selective catalytic reaction of NO on Cu-ZSM-5 using in situ DRIFTS].
Zhang, Ping; Wang, Le-Fu; Chen, Yong-Heng
The prepared Cu-ZSM-5 catalyst presents higher activity at low temperature during the selective catalytic reduction (SCR) of NO, and the conversion from NO to N2 is 70.6% at 613 K. The in situ diffuse reflectance FTIR spectroscopy (in situ DRIFTS) is an important method for studying surface adsorption of catalyst and mechanism of catalytic reaction, and was used to study the surface adsorbed species and the selective catalytic reduction reaction of NO on Cu-ZSM-5 catalyst in the presence of propene as reductant, with excess O2 and at 298-773 K. Based on the in-situ DRIFTS, a reaction mechanism is proposed that on Cu-ZSM-5, NO is first transformed to a series of NO(x) surface adsorbates, then these species react with the activating species of propene (C(x)H(y) or C(x)H(y)O(x)) to form organo-intermediates, including a process from organo-NH to organo-CN again to organo-NO(x) (organo-nitro or organo-nitrito), and finally these key intermediates react to form nitrogen. The role of Cu is to promote NO(x) content. Propene is easily activated on Cu-ZSM-5 with oxygen, and furthermore, the presence of oxygen is necessary to form organo-NO(x) intermediates.
Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling
Garcia, Andres; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.
Statistical mechanical modeling is developed to describe a catalytic conversion reaction A → Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Hence, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A.
Conformational Substrate Selection Contributes to the Enzymatic Catalytic Reaction Mechanism of Pin1.
Vöhringer-Martinez, Esteban; Dörner, Ciro
Conformational changes in enzymes and their role in their catalytic activity have been thoroughly addressed experimentally and theoretically. There is a vivid discussion in the field of enzyme catalysis on whether conformational changes of the enzyme are coupled to catalysis, or whether transition state stabilization through the preorganized protein and its electrostatic properties govern the catalysis. In this study, an additional contribution to the catalysis of one specific enzyme, Pin1, is proposed, which arises from its conformational selection of the peptide substrate from aqueous solution with the lowest activation barrier. The most stable conformers of the reactant (cis) and product (trans) peptide were identified through molecular dynamics simulations in combination with metadynamics. The cis-trans isomerization reaction was studied with quantum mechanical/molecular mechanical molecular dynamics simulations and density functional theory together with the mean reaction force, which allows us to separate structural and electronic contributions to the activation barrier. Our results show that enzyme Pin1 binds the trans isomer in the conformation of the peptide with the smallest activation barrier and reduces the barrier further through specific substrate-enzyme interactions, as we have shown previously. The activation barrier of the cis peptide is independent of the conformer and remains unchanged in the enzyme.
The reaction mechanism of catalytic oxidation with hydrogen peroxide and ozone in aqueous solution.
Park, J S; Choi, H; Ahn, K H
The sorption and catalytic oxidation of model compounds (pCBA and phenanthrene) and NOM on FeOOH were investigated using hydrogen peroxide and ozone, respectively. After oxidation with ozone, the hydrophobic, transphilic, and hydrophilic NOM fractions were isolated using XAD-8 and -4 resins to analyze the reaction characteristics. The sorption of pCBA was strongly dependent upon the pH, but phenanthrene exhibited a sorption behavior that was independent of the pH. In the case of NOM, the hydrophobic portion showed higher sorption affinity than hydrophilic and transphilic at pH 7.2. The concentrations of model compounds and oxidants were measured during the oxidations and the efficiency was compared for tests done with ozone alone and those using catalytic ozonation. Through the comparison of the sorption and decomposition of the model compounds, along with the effects of bicarbonate addition, mechanisms for catalytic oxidation with hydrogen peroxide or ozone were proposed, respectively.
Polyethersulfone hollow fiber modified with poly(styrenesulfonate) and Pd nanoparticles for catalytic reaction
NASA Astrophysics Data System (ADS)
Emin, C.; Gu, Y.; Remigy, J.-C.; Lahitte, J.-F.
The aim of this work is the synthesis of polymer-stabilized Pd nanoparticles (PdNP) inside a functionalized polymeric porous membrane in order to develop hybrid catalytic membrane reactors and to test them in model metal-catalyzed organic reactions. For this goal, a polymeric membrane support (Polyethersulfone hollow fiber-shaped) was firstly functionalized with an ionogenic polymer (i.e. poly(styrenesulfonate) capable to retain PdNP precursors using an UV photo-grafting method. PdNP were then generated inside the polymeric matrix by chemical reduction of precursor salts (intermatrix synthesis). The catalytic performance of the PdNP catalytic membranes was evaluated using reduction of nitrophenol by sodium borohydride (NaBH4) in water.
Chiral N,N'-dioxides: new ligands and organocatalysts for catalytic asymmetric reactions.
Liu, XiaoHua; Lin, LiLi; Feng, XiaoMing
Homochiral catalysts that can effect asymmetric transformations are invaluable in the production of optically active molecules. Researchers are actively pursuing the design of new ligands and organocatalysts by exploiting concepts derived from the application of bifunctional and C(2)-symmetric catalysts. Many homochiral catalysts containing amines, ethers, alcohols, and phosphines as electron-pair donors have been successfully developed. Amine N-oxides are highly polar substances. Despite their pronounced capacity as electron-pair donors, N-oxides have been underutilized in asymmetric reactions; they have only made a visible impact on the field in the preceding decade. Systematic studies have instead largely focused on pyridine- or quinoline-based scaffolds in organosilicon and coordination chemistry. The application of chiral tertiary amine N-oxides has not been widely pursued because of the difficulty of controlling the chirality at the tetrahedral nitrogen of the N-oxide moiety. In this Account, we outline the design of a new family of C(2)-symmetric N,N'-dioxides from readily available chiral amino acids. We then discuss the application of these chiral amine N-oxides as useful metal ligands and organocatalysts for asymmetric reactions. The high nucleophilicity of the oxygen in N-oxides is ideal for organocatalytic reactions that rely on nucleophilic activation of organosilicon reagents. These catalysts have been successfully applied in the asymmetric addition of trimethylsilylcyanide to aldehydes, ketones, aldimines, and ketimines, with good yields and excellent enantioselectivities. Asymmetric organocatalytic chlorination of β-ketoesters with N-chlorosuccinimide has also been achieved through hydrogen bond activation. The molecular framework of these N,N'-dioxides, with their multiple O-donors, also serves as a new tetradentate ligand that can coordinate a range of metal ions, including Cu(I), Cu(II), Ni(II), Mg(II), Fe(II), Co(II), In(III), Sc(III), La
Effect of reaction pressure on octane number and reformate and hydrogen yields in catalytic reforming
Moljord, K.; Hellenes, H.G.; Hoff, A.; Tanem, I.; Grande, K.; Holmen, A.
The effect of reaction pressure in catalytic reforming was studied in a pilot reactor with a commercial Pt-Re/Al{sub 2}O{sub 3} reforming catalyst and a hydrotreated naphtha from a North Sea crude. Reformate and hydrogen yields, research octane numbers (RON), and reformate composition at reactor pressures in the range of 12--25 bar were measured as a function of temperature in the range of 95--105 RON. Reformate and hydrogen yields increased as the pressure range. For the lower reaction pressures the hydrogen yields increased with increasing severity, but for the higher pressures the hydrogen yields started to decline above certain severities. RON was linearly dependent on the concentration of aromatics in the reformate, although the selectivity toward aromatics depends on both pressure and temperature. Less hydro dealkylation of C{sub 8} and heavier aromatics to benzene and toluene resulted in a shift toward xylenes and heavier aromatic components when pressure was lowered. Variations in the degree of paraffin isomerization did not influence RON significantly at those severities.
Methanol conversion to light olefins over SAPO-34. Sorption, diffusion, and catalytic reactions
Chen, D.; Rebo, H.P.; Moljord, K.; Holmen, A.
The catalytic conversion of methanol to lower olefins (MTO) is a way of converting natural gas and coal to chemicals via methanol. The effects of adsorption and diffusion of the reactants on methanol to olefins (MTO) and propene conversion over SAPO-34 have been studied in an oscillating microbalance reactor. The adsorption parameters of methanol and propene at reaction conditions (698 K) were determined by a pulse method, and the results were identical to the values obtained by extrapolation from low temperatures (323--398 K). Inverse uptake diffusion times were calculated form adsorption data at low temperatures, and these results were dependent on the temperature and the adsorbed amount. The inverse steady-state diffusion times calculated form the inverse uptake diffusion times were independent of the temperature and the adsorbed amount. The influence of diffusion on the reaction rates was estimated on the basis of the inverse steady-state diffusion times, using the Weisz-Prater criterion. The methanol conversion over SAPO-34 was influenced by diffusion of the reactant, while the propene conversion was not. A kinetic study revealed that both the rate constant and the site coverage of propene were much lower than that of methanol at 698 K. The deactivation behavior during the MTO reaction over SAPO-34 was studied by measuring both the adsorbed amount of methanol and the conversion at different coke contents. Catalyst deactivation was proposed to be due to a decreasing number of sites available for adsorption at high coke contents and a lower diffusivity, hence a lower effectiveness factor due to coke deposition.
Catalytic self-assembled monolayers on Au nanoparticles: the source of catalysis of a transphosphorylation reaction.
Zaupa, Giovanni; Mora, Claudia; Bonomi, Renato; Prins, Leonard J; Scrimin, Paolo
The catalytic activity of a series of Au monolayer protected colloids (Au MPCs) containing different ratios of the catalytic unit triazacyclononane⋅Zn(II) (TACN⋅Zn(II) ) and an inert triethyleneglycol (TEG) unit was measured. The catalytic self-assembled monolayers (SAMs) are highly efficient in the transphosphorylation of 2-hydroxy propyl 4-nitrophenyl phosphate (HPNPP), an RNA model substrate, exhibiting maximum values for the Michaelis-Menten parameters k(cat) and K(M) of 6.7×10(-3) s(-1) and 3.1×10(-4) M, respectively, normalized per catalytic unit. Despite the structural simplicity of the catalytic units, this renders these nanoparticles among the most active catalysts known for this substrate. Both k(cat) and K(M) parameters were determined as a function of the mole fraction of catalytic unit (x(1)) in the SAM. Within this nanoparticle (NP) series, k(cat) increases up till x(1) ≈0.4, after which it remains constant and K(M) decreases exponentially over the range studied. A theoretical analysis demonstrated that these trends are an intrinsic property of catalytic SAMs, in which catalysis originates from the cooperative effect between two neighboring catalytic units. The multivalency of the system causes an increase of the number of potential dimeric catalytic sites composed of two catalytic units as a function of the x(1) , which causes an apparent increase in binding affinity (decrease in K(M)). Simultaneously, the k(cat) value is determined by the number of substrate molecules bound at saturation. For values of x(1) >0.4, isolated catalytic units are no longer present and all catalytic units are involved in catalysis at saturation. Importantly, the observed trends are indicative of a random distribution of the thiols in the SAM. As indicated by the theoretical analysis, and confirmed by a control experiment, in case of clustering both k(cat) and K(M) values remain constant over the entire range of x(1) .
Catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles.
Zhang, Hong-Hao; Sun, Xiao-Xue; Liang, Jing; Wang, Yue-Ming; Zhao, Chang-Chun; Shi, Feng
The first catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles was established in the presence of chiral phosphoric acid, which tolerates a wide range of substrates with generally excellent diastereoselectivity and good enantioselectivity (up to >95 : 5 dr, 89 : 11 er). This approach will greatly enrich the chemistry of the catalytic asymmetric Povarov reaction, in particular ketone-involved transformations. Furthermore, this protocol represents the first diastereo- and enantio-selective construction of a spiro[indolin-3,2'-quinoline] framework bearing an indole moiety. This novel type of spiro-compound not only contains two chiral centers, including one quaternary stereogenic center, but also integrates two biologically important structures of spiro[indolin-3,2'-quinoline] and indole, which may find medicinal applications after bioassay.
Manned Evaluation of a Diver Heater for SDV Applications Using Hydrogen Catalytic Reactions
DIVER HEATER FOR SDV APPLICATIONS USING HYDROGEN CATALYTIC REACTIONS GAS CIRCUIT The basic heater design uses a gas ejector pump to recirculate the gas...entrance of the gas ejector pump. In this manner the hydrogen is mixed inside the pressure vessel with the recirculated gas and the fresh incoming air to...recirculatory flow then passes through a gas-to-water heat exchanger where the heat is removed and some of the water vapor condenses . The recirculatory flow then
Nonequilibrium Relaxation of Conformational Dynamics Facilitates Catalytic Reaction in an Elastic Network Model of T7 DNA Polymerase.
Zhao, Ziqing W; Xie, X Sunney; Ge, Hao
Nucleotide-induced conformational closing of the finger domain of DNA polymerase is crucial for its catalytic action during DNA replication. Such large-amplitude molecular motion is often not fully accessible to either direct experimental monitoring or molecular dynamics simulations. However, a coarse-grained model can offer an informative alternative, especially for probing the relationship between conformational dynamics and catalysis. Here we investigate the dynamics of T7 DNA polymerase catalysis using a Langevin-type elastic network model incorporating detailed structural information on the open conformation without the substrate bound. Such a single-parameter model remarkably captures the induced conformational dynamics of DNA polymerase upon dNTP binding, and reveals its close coupling to the advancement toward transition state along the coordinate of the target reaction, which contributes to significant lowering of the activation energy barrier. Furthermore, analysis of stochastic catalytic rates suggests that when the activation energy barrier has already been significantly lowered and nonequilibrium relaxation toward the closed form dominates the catalytic rate, one must appeal to a picture of two-dimensional free energy surface in order to account for the full spectrum of catalytic modes. Our semiquantitative study illustrates the general role of conformational dynamics in achieving transition-state stabilization, and suggests that such an elastic network model, albeit simplified, possesses the potential to furnish significant mechanistic insights into the functioning of a variety of enzymatic systems.
The Non-innocent Phenalenyl Unit: An Electronic Nest to Modulate the Catalytic Activity in Hydroamination Reaction
Mukherjee, Arup; Sen, Tamal K.; Ghorai, Pradip Kr; Mandal, Swadhin K.
The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, material chemistry to device physics acting as key electronic reservoir which has not only led to the best organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which in turn determines the outcome of the catalysis. PMID:24084653
Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation
Hu, Xiao-Qiang; Qi, Xiaotian; Chen, Jia-Rong; Zhao, Quan-Qing; Wei, Qiang; Lan, Yu; Xiao, Wen-Jing
Compared with the popularity of various C-centred radicals, the N-centred radicals remain largely unexplored in catalytic radical cascade reactions because of a lack of convenient methods for their generation. Known methods for their generation typically require the use of N-functionalized precursors or various toxic, potentially explosive or unstable radical initiators. Recently, visible-light photocatalysis has emerged as an attractive tool for the catalytic formation of N-centred radicals, but the pre-incorporation of a photolabile groups at the nitrogen atom largely limited the reaction scope. Here, we present a visible-light photocatalytic oxidative deprotonation electron transfer/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediation strategy for catalytic N-radical cascade reaction of unsaturated hydrazones. This mild protocol provides a broadly applicable synthesis of 1,6-dihydropyradazines with complete regioselectivity and good yields. The 1,6-dihydropyradazines can be easily transformed into diazinium salts that showed promising in vitro antifungal activities against fungal pathogens. DFT calculations are conducted to explain the mechanism. PMID:27048886
Theoretical study of catalytic efficiency of a Diels-Alderase catalytic antibody: an indirect effect produced during the maturation process.
Martí, Sergio; Andrés, Juan; Moliner, Vicent; Silla, Estanislao; Tuñón, Iñaki; Bertrán, Juan
The Diels-Alder reaction is one of the most important and versatile transformations available to organic chemists for the construction of complex natural products, therapeutics agents, and synthetic materials. Given the lack of efficient enzymes capable of catalyzing this kind of reaction, it is of interest to ask whether a biological catalyst could be designed from an antibody-combining site. In the present work, a theoretical study of the different behavior of a germline catalytic antibody (CA) and its matured form, 39 A-11, that catalyze a Diels-Alder reaction has been carried out. A free-energy perturbation technique based on a hybrid quantum-mechanics/molecular-mechanics scheme, together with internal energy minimizations, has allowed free-energy profiles to be obtained for both CAs. The profiles show a smaller barrier for the matured form, which is in agreement with the experimental observation. Free-energy profiles were obtained with this methodology, thereby avoiding the much more demanding two-dimensional calculations of the energy surfaces that are normally required to study this kind of reaction. Structural analysis and energy evaluations of substrate-protein interactions have been performed from averaged structures, which allows understanding of how the single mutations carried out during the maturation process can be responsible for the observed fourfold enhancement of the catalytic rate constant. The conclusion is that the mutation effect in this studied germline CA produces a complex indirect effect through coupled movements of the backbone of the protein and the substrate.
Study of catalytic upgrading of biomass tars using Indonesian iron ore
NASA Astrophysics Data System (ADS)
Wicakso, Doni Rahmat; Sutijan, Rochmadi, Budiman, Arief
Catalytic decomposition is a promising way for chemical upgrading process of low quality oil such as biomass tars. In this experiment, catalytic decomposition of biomass tars was performed over Indonesian low grade iron ore catalyst. This process is carried out in a fixed bedreactor which is equipped with preheater to convert the tars into vapor form. The reaction was studied at the temperature range of 500 - 700°C. The kinetic study of catalytic decomposition of biomass tars is represented using first order reaction. The results show that value of constant of chemical reaction is in range 0.2514 - 0.9642 cm3.gr-1.min-1 with value of the frequency factor (A) and the activation energy (E) are 48.98 min-1 and 5724.94 cal.mol-1, respectively.
A palladium-nanoparticle and silicon-nanowire-array hybrid: a platform for catalytic heterogeneous reactions.
Yamada, Yoichi M A; Yuyama, Yoshinari; Sato, Takuma; Fujikawa, Shigenori; Uozumi, Yasuhiro
We report the development of a silicon nanowire array-stabilized palladium nanoparticle catalyst, SiNA-Pd. Its use in the palladium-catalyzed Mizoroki-Heck reaction, the hydrogenation of an alkene, the hydrogenolysis of nitrobenzene, the hydrosilylation of an α,β-unsaturated ketone, and the C-H bond functionalization reactions of thiophenes and indoles achieved a quantitative production with high reusability. The catalytic activity reached several hundred-mol ppb of palladium, reaching a TON of 2 000 000.
Effect of reaction time on the characteristics of catalytically grown boron nitride nanotubes
Mohamed, Norani Muti E-mail: firstname.lastname@example.com E-mail: email@example.com; Ahmad, Pervaiz E-mail: email@example.com E-mail: email@example.com; Saheed, Mohamed Shuaib Mohamed E-mail: email@example.com E-mail: email@example.com; Burhanudin, Zainal Arif E-mail: firstname.lastname@example.com E-mail: email@example.com
The paper reports on the growth of boron nitride nanotube (BNNTs) on Si substrate by catalytic chemical vapor deposition technique and the effect of reaction time and temperature on the size and purity were investigated. Scanning electron microscopy image revealed the bamboo-like BNNTs of multiwalled type with interlayer spacing of 0.34 nm. EDX analysis described the presence of a small percentage of Mg in the sample, indicating the combination of base-tip growth model for the sample synthesized at 1200°C. The reaction time has an effect of extending the length of the BNNTs until the catalyst is oxidized or covered by growth precursor.
Synthesis of 3-Indolylglycine Derivatives via Dinuclear Zinc Catalytic Asymmetric Friedel-Crafts Alkylation Reaction.
Wang, Xin-Wei; Hua, Yuan-Zhao; Wang, Min-Can
A direct asymmetric Friedel-Crafts (F-C) alkylation reaction between a wide range of indoles and ethyl 2-(4-methoxyphenylimino)acetate catalyzed by Trost's dinuclear complex is reported. A series of 3-indolylglycine derivatives were synthesized in enantioselectivity of up to >99% enantiomeric excess (ee) using 10 mol% catalyst loading under mild conditions. This atom economic reaction could be run on a gram scale without impacting its enantioselectivity. The absolute stereochemistry of catalytic products was determined by correlation with a known configuration compound. A possible mechanism was proposed for the asymmetric induction.
Effect of reaction time on the characteristics of catalytically grown boron nitride nanotubes
NASA Astrophysics Data System (ADS)
Mohamed, Norani Muti; Ahmad, Pervaiz; Saheed, Mohamed Shuaib Mohamed; Burhanudin, Zainal Arif
The paper reports on the growth of boron nitride nanotube (BNNTs) on Si substrate by catalytic chemical vapor deposition technique and the effect of reaction time and temperature on the size and purity were investigated. Scanning electron microscopy image revealed the bamboo-like BNNTs of multiwalled type with interlayer spacing of 0.34 nm. EDX analysis described the presence of a small percentage of Mg in the sample, indicating the combination of base-tip growth model for the sample synthesized at 1200°C. The reaction time has an effect of extending the length of the BNNTs until the catalyst is oxidized or covered by growth precursor.
Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions
Somorjai, G.A.
The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In
"Metal-free" catalytic oxygen reduction reaction on heteroatom- doped graphene is caused by trace metal impurities.
Wang, Lu; Ambrosi, Adriano; Pumera, Martin
The oxygen reduction reaction (ORR) is of high industrial importance. There is a large body of literature showing that metal-based catalytic nanoparticles (e.g. Co, Mn, Fe or hybrid Mn/Co-based nanoparticles) supported on graphene act as efficient catalysts for the ORR. A significant research effort is also directed to the so-called "metal-free" oxygen reduction reaction on heteroatom-doped graphene surfaces. While such studies of the ORR on nonmetallic heteroatom-doped graphene are advertised as "metal-free" there is typically no sufficient effort to characterize the doped materials to verify that they are indeed free of any trace metal. Here we argue that the claimed "metal-free" electrocatalysis of the oxygen reduction reaction on heteroatom-doped graphene is caused by metallic impurities present within the graphene materials.
Catalytic asymmetric allylation reactions using BITIP catalysis and 2-substituted allylstannanes as surrogates for beta-keto ester dianions.
Keck, G E; Yu, T
[formula: see text] Catalytic asymmetric allylation (CAA) reactions using the indicated allylstannane and the BITIP catalysts previously described by us give high yields and enantioselectivities in additions to aldehydes. The products are convertible to beta-keto esters by oxidative cleavage of the olefin. These reactions thus provide a useful catalytic enantioselective method for chain extension with introduction of a versatile four-carbon unit.
A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions
NASA Astrophysics Data System (ADS)
Conte, Marco; Wilson, Karen; Chechik, Victor
A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X-band electron paramagnetic resonance spectroscopy.
Catalytic mechanism of transition-metal compounds on Mg hydrogen sorption reaction.
Barkhordarian, Gagik; Klassen, Thomas; Bormann, Rüdiger
The catalytic mechanisms of transition-metal compounds during the hydrogen sorption reaction of magnesium-based hydrides were investigated through relevant experiments. Catalytic activity was found to be influenced by four distinct physico-thermodynamic properties of the transition-metal compound: a high number of structural defects, a low stability of the compound, which however has to be high enough to avoid complete reduction of the transition metal under operating conditions, a high valence state of the transition-metal ion within the compound, and a high affinity of the transition-metal ion to hydrogen. On the basis of these results, further optimization of the selection of catalysts for improving sorption properties of magnesium-based hydrides is possible. In addition, utilization of transition-metal compounds as catalysts for other hydrogen storage materials is considered.
Catalytic reaction of 3-phenyl-2-propyn-1-ol with alcohols
Grigoryan, S.G.; Avetisyan, K.G.; Matnishyan, A.A.
The cyclic ketal 2,5-dimethyl-2,5-bis(3-phenyl-2-propynyloxy)-1,4-dioxane was obtained by the reaction of 3-phenyl-2-propyn-1=ol with propargyl alcohol in the presence of the HgO-BF/sub 3/ O(C/sub 2/H/sub 5/)/sub 2/ catalytic system. The transformation of 3-phenyl-2-propyn-1-ol and its ethers in methanol and ethanol by the action of the above-mentioned catalytic system leads to 1-phenyl-3-alkoxy-1-propanone, 1-phenyl-1,1,3-trialkoxypropane, and 1-phenyl-2-propen-1-one. The intermediate organomercury compound, which is the product from regioselective addition of mercuric oxide and the saturated alcohol at the triple bond, was isolated. Its protodemercuration led to the above-mentioned linear products. The formation of the cyclic ketal is presumably due to the preferred formation of mercury bis-hydroxypropargylide.
Biogenic synthesis of palladium nanoparticles using Pulicaria glutinosa extract and their catalytic activity towards the Suzuki coupling reaction.
Khan, Mujeeb; Khan, Merajuddin; Kuniyil, Mufsir; Adil, Syed Farooq; Al-Warthan, Abdulrahman; Alkhathlan, Hamad Z; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H
Green synthesis of nanomaterials finds the edge over chemical methods due to its environmental compatibility. Herein, we report a facile and eco-friendly method for the synthesis of palladium (Pd) nanoparticles (NPs) using an aqueous solution of Pulicaria glutinosa, a plant widely found in a large region of Saudi Arabia, as a bioreductant. The as-prepared Pd NPs were characterized using ultraviolet-visible (UV-vis) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform-infrared spectroscopy (FT-IR). The hydroxyl groups of the plant extract (PE) molecules were found mainly responsible for the reduction and growth of Pd NPs. FT-IR analysis confirmed the dual role of the PE, both as a bioreductant as well as a capping ligand, which stabilizes the surface of Pd NPs. The crystalline nature of the Pd NPs was identified using XRD analysis which confirmed the formation of a face-centered cubic structure (JCPDS: 87-0641, space group: Fm3m (225)). Furthermore, the as-synthesized Pd NPs demonstrated excellent catalytic activity towards the Suzuki coupling reaction under aqueous and aerobic conditions. Kinetic studies of the catalytic reaction monitored using GC confirmed that the reaction completes in less than 5 minutes.
Metal-Organic Frameworks derivatives for improving the catalytic activity of CO oxidation reaction.
Ji, Wenlan; Xu, Zhiling; Liu, Pengfei; Zhang, Suoying; Zhou, Weiqiang; Li, Hongfeng; Zhang, Tao; Li, Linjie; Lu, Xiaohua; Wu, Jiansheng; Zhang, Weina; Huo, Fengwei
Metal-Organic Frameworks (MOFs) based derivatives have attracted an increasing interest in various research fields. However, most of reported papers mainly focused on the pristine MOFs-based derivatives, and researches on the functional MOFs-based derivatives composites are rare. Here, a simple strategy was reported to design the functional MOFs based derivatives composites by the encapsulation of the metal nanoparticles (MNPs) in MOFs matrixes (MNPs@MOFs) and the high-temperature calcination of MNPs@MOFs composites. The as-prepared MNPs@metal oxide composites with the hierarchical pore structure exhibited excellent catalytic activity and high stability for CO oxidation reaction.
Convective stability in the presence of a catalytic chemical reaction. I.
NASA Technical Reports Server (NTRS)
Wankat, P. C.; Schowalter, W. R.
A linear analysis of hydrodynamic stability has been applied to a problem in which a fluid mixture is contained between two horizontal planes. One species diffuses to the lower plane where it is destroyed by a rapid exothermic or endothermic catalytic reaction. Results show that important coupling takes place between thermal and concentration fields. This coupling gives rise to unusual stabilizing or destabilizing effects, depending upon the value of Lewis number. Several examples are discussed. It is also shown how the results can be applied to other problems involving heat and mass transfer.
Impact of active phase chemical composition and dispersity on catalytic behavior in PROX reaction
NASA Astrophysics Data System (ADS)
Cherkezova-Zheleva, Z.; Paneva, D.; Todorova, S.; Kolev, H.; Shopska, M.; Yordanova, I.; Mitov, I.
Iron and iron-platinum catalysts supported on activated carbon have been successfully synthesized by wet impregnation method and low-temperature treatment in inert atmosphere. The content of the supported phases corresponds to 10 wt % Fe and 0.5 wt % Pt. Four catalytic samples were synthesized: Sample A—activated carbon impregnated with Fe nitrate; Sample B—activated carbon impregnated with Pt salt; Sample C—activated carbon impregnated consequently with Fe and Pt salts; Sample D—activated carbon impregnated simultaneously with Fe and Pt salts. The as-prepared materials were characterized by Mössbauer spectroscopy, X-ray diffraction, infrared and X-ray photoelectron spectroscopy. The spectra show that the activated carbon support and the preparation procedure give rise to the synthesis of isolated metal Pt ions and ultradispersed Fe and Pt oxide species. Probably the presence of different functional groups of activated carbon gives rise to registered very high dispersion of loaded species on support. The catalytic tests were carried out in PROX reaction. A lower activity of bimetallic Pt-Fe samples was explained with the increase in surface oxygen species as a result of predomination of iron oxide on the support leading to the increase in selectivity to the H2 oxidation. Partial agglomeration of supported iron oxide phase was registered after catalytic tests.
Asphaltene cracking in catalytic hydrotreating of heavy oils. 2. study of changes in asphaltene structure during catalytic hydroprocessing
Sachio, A.; Chisato, T.; Shinichi, N.; Yoshimi, S.
Characteristics in catalytic conversion of asphaltenes in petroleum heavy residues were studied in the hydrotreating process. A Boscan crude, an Athabasca bitumen, and a Khafji vacuum residue were tested as typical feedstocks. Various analyses were made to obtain the properties of asphaltenes before and after the reaction, e.g., changes of heteroatoms such as sulfur and metals, and decreases of molecular weight. The characteristic changes of asphaltene molecules were also investigated by electron spin resonance (ESR) and X-ray analyses. The association and coordination of vanadyl in asphaltenes were studied by the temperature dependence on the ESR spectra, and the sizes of the stacked crystallites and the aggregated asphaltene micelles were measured with X-ray diffraction and small-angle scattering. In the asphaltene cracking mechanism, it was clarified that the main reactions were the destruction of asphaltene micelles caused by vanadium removal and the depolymerization of asphaltene molecules by removal of heteroatoms such as sulfur.
Joint catalytic activation of CO/sub 2/ and NH/sub 3/ in reaction with butadiene under the action of palladium complexes
Dzhemilev, U.M.; Kunakova, R.V.; Sidorova, V.V.
In a continuation of the study of catalytic reactions in which small molecules participate they have examined the reaction of butadiene simultaneously with CO/sub 2/ and NH/sub 3/ in the presence of homogeneous Pd-containing catalyst complexes with the object of developing a single-step method for the synthesis of unsaturated higher formamides. The possibility of joint catalytic activation of small molecules (CO/sub 2/ and NH/sub 3/) has been demonstrated in their reaction with butadiene with the participation of palladium complexes, the products being mono- and bis-(2,7-octadienyl)formamides. It has been found that 2-pyrrolidone can take part in a telomerization reaction with butadiene in solutions containing palladium complexes, ammonia and carbon dioxide with the formation of N-2,7-octadienylpyrrolidone.
A mutagenesis study of a catalytic antibody
Jackson, D.Y.; Prudent, J.R.; Baldwin, E.P.; Schultz, P.G. )
The authors have generated seven site-specific mutations in the genes encoding the variable region of the heavy chain domain (V{sub H}) of the phosphocholine-binding antibody S107.S107 is a member of a family of well-characterized highly homologous antibodies that bind phosphorylcholine mono- and diesters. Two of these antibodies, MOPC-167 and T15, have previously been shown to catalyze the hydrolysis of 4-nitrophenyl N-trimethylammonioethyl carbonate. Two conserved heavy-chain residues, Tyr-33 and Arg-52, were postulated to be involved in binding and hydrolysis of 4-nitrophenylcholine carbonate esters. To more precisely define the catalytic roles of these residues, three Arg-52 mutants (R52K, R52Q, R52C) and four Tyr-33 mutants (Y33H, Y33F, Y33E, Y33D) of antibody S107 were generated. The genes encoding the V{sub H} binding domain of S107 were inserted into plasmid pUC-fl, and in vitro mutagenesis was performed. These results not only demonstrate the importance of electrostatic interactions in catalysis by antibody S107 but also show that catalytic side chains can be introduced into antibodies to enhance their catalytic efficiency.
Synergy among manganese, nitrogen and carbon to improve the catalytic activity for oxygen reduction reaction
NASA Astrophysics Data System (ADS)
Kang, Jian; Wang, Hui; Ji, Shan; Key, Julian; Wang, Rongfang
A highly active electrocatalyst for oxygen reduction reaction, manganese modified glycine derivative-carbon (Mn-CNx), is synthesized by a two-step carbonizing process. X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy are used to characterize structure and morphology of the catalysts. Electrochemical tests show that Mn-CNx has higher catalytic activity for oxygen reduction reaction than CNx derived glycine and Mn modified Vulcan carbon. Moreover, the half-wave potential of Mn-CNx is only 12 mV lower than that of commercial Pt/C. Mn-CNx also has excellent durability to methanol crossover in alkaline solution, and thus provides a promising low cost, non-precious metal cathode catalyst for fuel cells.
Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions.
Aguirre-Díaz, Lina María; Gándara, Felipe; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles
The aim of this research is to establish how metal-organic frameworks (MOFs) composed of more than one metal in equivalent crystallographic sites (solid solution MOFs) exhibit catalytic activity, which is tunable by virtue of the metal ions ratio. New MOFs with general formula [InxGa1-x(O2C2H4)0.5(hfipbb)] were prepared by the combination of Ga and In. They are isostructural with their monometal counterparts, synthesized with Al, Ga, and In. Differences in their behavior as heterogeneous catalysts in the three-component, one pot Strecker reaction illustrate the potential of solid solution MOFs to provide the ability to address the various stages involved in the reaction mechanism.
Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions.
Li, Gao; Abroshan, Hadi; Chen, Yuxiang; Jin, Rongchao; Kim, Hyung J
The catalytic activity of Au25(SR)18 nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in the presence of a base, e.g., ammonia or pyridine, and transition-metal ions M(z+), such as Cu(+), Cu(2+), Ni(2+) and Co(2+), as a Lewis acid is studied. The addition of a Lewis acid is found to significantly promote the catalytic activity of Au25(SR)18/CeO2 in the hydrogenation of benzaldehyde and a number of its derivatives. Matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry in conjunction with UV-vis spectroscopy confirm the generation of new species, Au25-n(SR)18-n (n = 1-4), in the presence of a Lewis acid. The pathways for the speciation of Au24(SR)17 from its parent Au25(SR)18 nanocluster as well as its structure are investigated via the density functional theory (DFT) method. The adsorption of M(z+) onto a thiolate ligand "-SR-" of Au25(SR)18, followed by a stepwise detachment of "-SR-" and a gold atom bonded to "-SR-" (thus an "Au-SR" unit) is found to be the most likely mechanism for the Au24(SR)17 generation. This in turn exposes the Au13-core of Au24(SR)17 to reactants, providing an active site for the catalytic hydrogenation. DFT calculations indicate that M(z+) is also capable of adsorbing onto the Au13-core surface, producing a possible active metal site of a different kind to catalyze the aldehyde hydrogenation reaction. This study suggests, for the first time, that species with an open metal site like adducts [nanoparticle-M]((z-1)+) or fragments Au25-n(SR)18-n function as the catalysts rather than the intact Au25(SR)18.
Intramolecular catalytic Friedel-Crafts reactions with allenyl cations for the synthesis of quinolines and their analogues.
Ishikawa, Teruhiko; Manabe, Shinobu; Aikawa, Toshiaki; Kudo, Takayuki; Saito, Seiki
[reaction: see text] This paper describes a novel method to synthesize a quinoline backbone by incorporating allenyl cations into a catalytic intramolecular Friedel-Crafts reaction. The initial products were isomerized and aromatized upon treatment with acid and base, respectively, to give quinolines. The basic concept also proved to be promising for 1-benzazepine, 1-benzazocine, or isoquinoline synthesis.
Strong counteranion effects on the catalytic activity of cationic silicon Lewis acids in Mukaiyama aldol and Diels-Alder reactions.
Hara, Kenji; Akiyama, Ryuto; Sawamura, Masaya
[chemical reaction: see text]. A toluene-coordinated silyl borate, [Et3Si(toluene)]B(C6F5)4, demonstrated catalytic activities significantly higher than those of Me3SiOTf and Me3SiNTf2 in Mukaiyama aldol and Diels-Alder reactions.
Site-specific growth of Au-Pd alloy horns on Au nanorods: a platform for highly sensitive monitoring of catalytic reactions by surface enhancement Raman spectroscopy.
Huang, Jianfeng; Zhu, Yihan; Lin, Ming; Wang, Qingxiao; Zhao, Lan; Yang, Yang; Yao, Ke Xin; Han, Yu
Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity.
Group IV organometallic compounds based on dianionic "pincer" ligands: synthesis, characterization, and catalytic activity in intramolecular hydroamination reactions.
Luconi, Lapo; Rossin, Andrea; Motta, Alessandro; Tuci, Giulia; Giambastiani, Giuliano
Neutral Zr(IV) and Hf(IV) diamido complexes stabilized by unsymmetrical dianionic N,C,N' pincer ligands have been prepared through the simplest and convenient direct metal-induced Caryl-H bond activation. Simple ligand modification has contributed to highlight the non-innocent role played by the donor atom set in the control of the cyclometallation kinetics. The as-prepared bis-amido catalysts were found to be good candidates for the intramolecular hydroamination/cyclization of primary aminoalkenes. The ability of these compounds to promote such a catalytic transformation efficiently (by providing, in some cases, fast and complete substrate conversion at room temperature) constitutes a remarkable step forward toward catalytic systems that can operate at relatively low catalyst loading and under milder reaction conditions. Kinetic studies and substrate-scope investigations, in conjunction with preliminary DFT calculations on the real systems, were used to elucidate the effects of the substrate substitution on the catalyst performance and to support the most reliable mechanistic path operative in the hydroamination reaction.
Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.
Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin
The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input.
Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols.
Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K
The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.
A General Approach to Catalytic Alkene Anti-Markovnikov Hydrofunctionalization Reactions via Acridinium Photoredox Catalysis.
Margrey, Kaila A; Nicewicz, David A
the anti-Markovnikov addition of mineral acids to olefins using lutidinium halide salts as convenient reagents to deliver the mineral acids. Acids including HCl, HF, H3PO4, and MeSO3H all participate in the hydrofunctionalization reactions, even with alkenes that are highly prone to polymerization. A combination of transient and steady-state absorption spectroscopy tools were employed to observe alkene cation radicals and the resultant acridine radical, lending support for an electron transfer mechanism. The origin of the anti-Markovnikov selectivity in these reactions is likely the result of a reversible addition of the nucleophile to the alkene cation radical resulting in a greater population of the more stable radical. Loss of a proton followed by reaction of the radical intermediate with the hydrogen atom donor completes the transformations. Again, by means of transient absorption spectroscopy, oxidative turnover of the acridine radical was observed to complete the dual catalytic cycle mechanistic picture.
Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.
Almonacid, Daniel E; Yera, Emmanuel R; Mitchell, John B O; Babbitt, Patricia C
Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes) from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3) show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1) catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56%) suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to refine
Effects of Finite Reaction Rates on the Kinetic Phase Transitions in the Catalytic Oxidation of Carbon Monoxide
NASA Astrophysics Data System (ADS)
López-Carreño, L. D.
Oxidation of carbon monoxide is one of the most extensively studied heterogeneous catalysis reactions, being important among other applications in automobile-emission control. Catalytic oxidation of carbon monoxide on platinum (111) surface was simulated by the Monte Carlo technique following an extended version of the model proposed by Ziff, Gulari and Barshad (ZGB). In the simulation, a simple square two-dimensional lattice of active sites replaces the surface of the catalyst. Finite reaction rates for (i) diffusion of the reactive species on the surface, (ii) reaction of a CO molecule with an oxygen atom in a nearest neighbor site, and (iii) desorption of unreacted CO molecules, have been taken into account. The produced CO2 desorbs instantly. The average coverage of O, CO and the CO2 production rate for a steady state configuration, as a function of the normalized CO partial pressure (PCO), shows two kinetic phase transitions. In the ZGB model these transitions occur at PCO ~ 0.39 and PCO ~ 0.53. For 0.39 < PCO > 0.53 a reactive (CO2 production) steady state is found. Outside of the interval, the only steady state is a poisoned catalyst of pure CO or pure O. Our results show that finite reaction rates shift the values in which these phase transitions occur.
Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction
Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng
Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.
Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions
NASA Astrophysics Data System (ADS)
Parlett, Christopher M. A.; Isaacs, Mark A.; Beaumont, Simon K.; Bingham, Laura M.; Hondow, Nicole S.; Wilson, Karen; Lee, Adam F.
The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.
Solar photo-thermal catalytic reactions to produce high value chemicals
Prengle, Jr, H W; Wentworth, W E
This report presents a summary of the research work accomplished to date on the utilization of solar photo-thermal energy to convert low cost chemical feedstocks into high $-value chemical products. The rationale is that the solar IR-VIS-UV spectrum is unique, supplying endothermic reaction energy as well as VIS-UV for photochemical activation. Chemical market analysis and product price distribution focused attention on speciality chemicals with prices >$1.00/lb, and a synthesis sequence of n-paraffins to aromatics to partial oxidized products. The experimental work has demonstrated that enhanced reaction effects result from VIS-UV irradiation of catalytically active V2O5/SiO2. Experiments of the past year have been on dehydrogenation and dehydrocyclization of n-paraffins to olefins and aromatics with preference for the latter. Recent results using n-hexane produced 95% conversion with 56% benzene; it is speculated that aromatic yield should reach {approximately}70% by further optimization. Pilot- and commercial-scale reactor configurations have been examined; the odds-on-favorite being a shallow fluid-bed of catalyst with incident radiation from the top. Sequencing for maximum cost effectiveness would be day-time endothermic followed by night-time exothermic reactions to produce the products.
All electron quantum chemical calculation of the entire enzyme system confirms a collective catalytic device in the chorismate mutase reaction.
Ishida, Toyokazu; Fedorov, Dmitri G; Kitaura, Kazuo
To elucidate the catalytic power of enzymes, we analyzed the reaction profile of Claisen rearrangement of Bacillus subtilis chorismate mutase (BsCM) by all electron quantum chemical calculations using the fragment molecular orbital (FMO) method. To the best of our knowledge, this is the first report of ab initio-based quantum chemical calculations of the entire enzyme system, where we provide a detailed analysis of the catalytic factors that accomplish transition-state stabilization (TSS). FMO calculations deliver an ab initio-level estimate of the intermolecular interaction between the substrate and the amino acid residues of the enzyme. To clarify the catalytic role of Arg90, we calculated the reaction profile of the wild-type BsCM as well as Lys90 and Cit90 mutant BsCMs. Structural refinement and the reaction path determination were performed at the ab initio QM/MM level, and FMO calculations were applied to the QM/MM refined structures. Comparison between three types of reactions established two collective catalytic factors in the BsCM reaction: (1) the hydrogen bonds connecting the Glu78-Arg90-substrate cooperatively control the stability of TS relative to the ES complex and (2) the positive charge on Arg90 polarizes the substrate in the TS region to gain more electrostatic stabilization.
Neutron diffraction studies for realtime leaching of catalytic Ni
Iles, Gail N. Reinhart, Guillaume; Devred, François; Henry, Paul F. Hansen, Thomas C.
The leaching of Al from intermetallic samples of Nickel Aluminium alloys to form Raney-type nickel catalysts is widely used in the hydrogenation industry, however, little is known of the leaching process itself. In this study, the leaching of Al was measured in realtime, in situ, using the high-flux powder neutron diffractometer, D20, at the Institut Laue-Langevin. Despite the liberation of hydrogen and effervescent nature of the reaction the transformation of the dry powder phases into Raney-type Ni was determined. Samples produced by gas-atomisation were found to leach faster than those produced using the cast and crushed technique. Regardless of processing route of the precursor powder, the formation of spongy-Ni occurs almost immediately, while Ni{sub 2}Al{sub 3} and NiAl{sub 3} continue to transform over longer periods of time. Small-angle scattering and broadening of the diffraction peaks is an evidence for the formation of the smaller Ni particles. Understanding the kinetics of the leaching process will allow industry to refine production of catalysts for optimum manufacturing time while knowledge of leaching dynamics of powders produced by different manufacturing techniques will allow further tailoring of catalytic materials.
Simultaneous determination of trace iron and aluminum by catalytic spectrophotometry based on a novel oxidation reaction of xylene cyanol FF.
Cai, Longfei; Xu, Chunxiu
A new, simple, sensitive and selective method for the simultaneous determination of trace iron and aluminum by catalytic spectrophotometry was presented, based on the catalytic effects of iron and aluminum on the discoloring reaction of xylene cyanol FF proceeded by hydrogen peroxide and potassium periodate in weak nitric acid medium. No catalytic effect was obtained in the presence of hydrogen peroxide or potassium periodate only. With the conditional rate constants determined in reaction systems catalyzed by Al or Fe only, the concentrations of Fe and Al in the samples can be calculated. The method was applied to the simultaneous determination of trace Fe and Al in tap water, lake water, river water and tea leaves without separation and preconcentration.
Use of the confined spaces of apo-ferritin and virus capsids as nanoreactors for catalytic reactions.
Maity, Basudev; Fujita, Kenta; Ueno, Takafumi
Self-assembled protein cages providing nanosized internal spaces which are capable of encapsulating metal ions/complexes, enzymes/proteins have great potential for use as catalytic nanoreactors in efforts to mimic confined cellular environments for synthetic applications. Despite many uses in biomineralization, drug delivery, bio-imaging and so on, applications in catalysis are relatively rare. Because of their restricted size, protein cages are excellent candidates for use as vessels to exert control over reaction kinetics and product selectivity. Virus capsids with larger internal spaces can encapsulate multiple enzymes and can mimic natural enzymatic reactions. The apo-ferritin cage is known to accommodate various metal ions/complexes and suitable for organic transformation reactions in an aqueous medium. This review highlights the importance, prospects and recent significant research on catalytic reactions using the apo-ferritin cage and virus capsids.
Kinetics of the catalytic reaction of 2,2-di-(chloromethyl)-1,3-propanediol with thionyl chloride
Bolotov, A.A.; V'yunov, K.A.
The aim of this work was to determine the partial rate constants for the catalytic formation of 4,4-di(chloromethyl)trimethylene sulfite and to establish the controlling stage of the complex process. The choice of DMFA as catalyst during investigation of the quantitative relationships governing the substitution of the hydroxyl group by the chlorine atom was based on the fact that the reaction with triethylamine and pyridine takes place in a more complicated manner; the initially formed triethylamine and pyridine hydrochlorides accelerate substitution, i.e., autocatalysts by the reaction products is observed. The slowest stage of the complex catalytic process in the reaction of 2,2-di(chloromethyl)-1,3-propanediol with thionyl chloride in the presence of dimethylformamide is the reaction of the alcohol-catalyst donor-acceptor complex with the thionyl chloride.
Applicability of fiber-optic-based Raman probes for on-line reaction monitoring of high-pressure catalytic hydrogenation reactions.
Hamminga, Gerben M; Mul, Guido; Moulijn, Jacob A
This study evaluates the applicability of fiber-optic-based Raman probes for on-line reaction monitoring of high-pressure catalytic hydrogenation reactions in batch autoclaves. First, based on trends in the strong intensity of the 945 cm(-1) C-O-C vibration of 1,3-dioxolane, the effect of various experimental parameters on sensitivity was evaluated and can be summarized as follows: (1) above 500 rpm a linear increase in stirring speed induces a linear decrease in Raman intensity; (2) a linear increase in hydrogen pressure also leads to a linear decrease of the Raman signal; (3) linear temperature elevation exponentially decreases the Raman intensity; and (4) increasing the catalyst particle concentration results in a steep nonlinear decrease of the Raman signal. Light scattering by gas bubbles, or combined scattering and absorption by (black) catalyst particles, reducing the amount of light collected by the optical fiber probe, explain the observed experimental trends. Second, the sensitivity of Raman spectroscopy was directly compared with attenuated total reflection-Fourier transform infrared (ATR-FT-IR) spectroscopy in the analysis of three different hydrogenation reactions over a Cu-ZnO catalyst. From the applied target molecules, diethyl maleate hydrogenation could be very well analyzed by Raman spectroscopy due to the high Raman scattering efficiency of the C=C bond, while for analysis of the hydrogenation of gamma-butyrolactone or 1-butanal, ATR-FT-IR is the technique of choice.
Catalytically active polymers obtained by molecular imprinting and their application in chemical reaction engineering.
Brüggemann, O
Molecular imprinting is a way of creating polymers bearing artificial receptors. It allows the fabrication of highly selective plastics by polymerizing monomers in the presence of a template. This technique primarily had been developed for the generation of biomimetic materials to be used in chromatographic separation, in extraction approaches and in sensors and assays. Beyond these applications, in the past few years molecular imprinting has become a tool for producing new kinds of catalysts. For catalytic applications, the template must be chosen, so that it is structurally comparable with the transition state (a transition state analogue, TSA) of a reaction, or with the product or substrate. The advantage of using these polymeric catalysts is obvious: the backbone withstands more aggressive conditions than a bio material could ever survive. Results are presented showing the applicability of a molecularly imprinted catalyst in different kinds of chemical reactors. It is demonstrated that the catalysts can be utilized not only in batch but also in continuously driven reactors and that their performance can be improved by means of chemical reaction engineering.
Highly enantioselective and anti-diastereoselective catalytic intermolecular glyoxylate-ene reactions: effect of the geometrical isomers of alkenes.
Zhang, Xiang; Wang, Min; Ding, Ran; Xu, Yun-He; Loh, Teck-Peng
An efficient method for the synthesis of homoallylic alcohols with high enantioselectivities and anti-diastereoselectivities via an In(III)-catalyzed intermolecular glyoxylate-ene reaction has been developed. The geometrical isomers of alkenes were shown to have different reactivities. Only the isomers of the alkenes having a proton β-cis to the substituent reacted in this catalytic system.
A Mesoporous Indium Metal-Organic Framework: Remarkable Advances in Catalytic Activity for Strecker Reaction of Ketones.
Reinares-Fisac, Daniel; Aguirre-Díaz, Lina María; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles; Gándara, Felipe
With the aim of developing new highly porous, heterogeneous Lewis acid catalysts for multicomponent reactions, a new mesoporous metal-organic framework, InPF-110 ([In3O(btb)2(HCOO)(L)], (H3btb = 1,3,5-tris(4-carboxyphenyl)benzene acid, L = methanol, water, or ethanol), has been prepared with indium as the metal center. It exhibits a Langmuir surface area of 1470 m(2) g(-1), and its structure consists of hexagonal pores with a 2.8 nm aperture, which allows the diffusion of multiple substrates. This material presents a large density of active metal sites resulting in outstanding catalytic activity in the formation of substituted α-aminonitriles through the one-pot Strecker reaction of ketones. In this respect, InPF-110 stands out compared to other catalysts for this reaction due to the small catalyst loadings required, and without the need for heat or solvents. Furthermore, X-ray single crystal diffraction studies clearly show the framework-substrate interaction through coordination to the accessible indium sites.
Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.
Baran, Talat; Inanan, Tülden; Menteş, Ayfer
The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature.
Aluminosilicates as controlled molecular environments for selective photochemical and catalytic reactions
Carrado, K.A.
This dissertation concerns research that involves photochemical, catalytic and spectroscopic studies of clays, pillared clays and zeolites. Incorporation of uranyl ions into hectorite, montmorillonite, bentonite and vermiculite clays was monitored by XRD and luminescence methods. Excitation and emission characteristics were studied in order to understand the behavior of uranyl ions in clays after various thermal treatments. Luminescence lifetime measurements elucidated the number of uranyl sites. Uranyl-exchanged clays were found to absorb light at lower energies (445-455nm) than analogous uranyl-exchanged zeolites (425nm). Each uranyl-exchanged clay was tested as a catalyst for the photoassisted oxidation of isopropyl alcohol. Energy transfer (ET) between uranyl and Eu(III) ions in different zeolite framework systems was examined. The efficiency of ET (eta/sub t/) was found to be affected by the type of framework present. Pillared bentonites were examined in the hydrocracking of decane. A catalytically and spectroscopically active dopant ion, Cr(III), was introduced into the clays in both pillared and unpillared forms depending upon synthetic conditions. EPR and DRS were employed to monitor the environment of Cr(III) for determination of its location - whether in the micropore structure or associated with alumina pillars. Catalytic behavior based upon this variability of location was examined. Incorporation of Cr(III) ions into an alumina pillar was found to increase the stability and activity with respect to an alumina PILC catalyst. The results of these studies suggest that selective, efficient catalysts can be designed around inorganic ions in aluminosilicate supports.
The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions
NASA Astrophysics Data System (ADS)
Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang
Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs.Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the
Little, D.M.
Don Little's Catalytic Reforming deals exclusively with reforming. With the increasing need for unleaded gasoline, the importance of this volume has escalated since it combines various related aspects of reforming technology into a single publication. For those with no practical knowledge of catalytic reforming, the chemical reactions, flow schemes and how the cat reformer fits into the overall refinery process will be of interest. Contents include: Catalytic reforming in refinery processing: How catalytic reformers work - chemical reactions; Process design; The catalyst, process variables and unit operation; Commercial processes; BTX operation; Feed preparation; naphtha hydrotreating and catalytic reforming; Index.
Effect of competition between catalytic particles C on the rate of the reversible diffusion-controlled reaction A+C⇌B+C
NASA Astrophysics Data System (ADS)
Felderhof, B. U.; Jones, R. B.
The effect of competition between catalytic particles C on the rate of the reversible diffusion-controlled reaction A+C⇌B+C is studied in a self-consistent approximation. The C-particles are assumed static with random configuration. The A- and B-particles diffuse in a fluid or solid background medium. Frequency-dependent effective rate coefficients are calculated as a function of the volume fraction of C-particles.
Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions
Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao
Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199
Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions.
Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei
The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction.
Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions
NASA Astrophysics Data System (ADS)
Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao
Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling.
Exposing the hidden complexity of stoichiometric and catalytic metathesis reactions by elucidation of Mg-Zn hybrids
Hevia, Eva; Chua, Jonathan Z.; García-Álvarez, Pablo; Kennedy, Alan R.; McCall, Matthew D.
Studying seemingly simple metathesis reactions between ZnCl2 and tBuMgCl has, surprisingly, revealed a much more complex chemistry involving mixed magnesium-zinc compounds that could be regarded as Mg-Zn hybrids. Thus, the reaction of equimolar amounts of ZnCl2 and tBuMgCl reveals the formation of the unprecedented mixed Mg-Zn complex [(THF)4Mg(μ-Cl)2Zn(tBu)(Cl)] (1), as a result of the co-complexation of the two anticipated exchange products of the metathesis. This magnesium zincate adopts a contacted ion-pair structure, closely related to Knochel's pioneering "Turbo" Grignard reagents. Furthermore, a second coproduct identified in this reaction is the solvent-separated mixed magnesium-zinc chloride complex [{Mg(THF)6}2+{Zn2Cl6}2-] (3) that critically diminishes the amount of ZnCl2 available for the intended metathesis reaction to take place. In another surprising result, when the reaction is carried out by using an excess of 3 M equivalents of the Grignard reagent (closer to the catalytic conditions employed by synthetic chemists), solvent-separated magnesium trialkyl zincate [{Mg2Cl3(THF)6}+{Zn(tBu)3}-] (4) is obtained that can be viewed as a model for the active species involved in the increasingly important organic transformations of Grignard reagents catalysed by ZnCl2. Furthermore, preliminary reactivity studies reveal that complex 4 can be used as an effective new reagent for direct Zn-I exchange reactions that allow the preparation and structural identification of the magnesium tris(aryl) zincate [{Mg2Cl3(THF)6}+{Zn(p-Tol)3}-] (5) that represents the first example of complete 3-fold activation of a zincate in a Zn-I exchange reaction which, in turn, can efficiently be used as a precursor for Negishi cross-coupling reactions. PMID:20212145
Catalytic performance of carbon nanotubes in H2O2 decomposition: experimental and quantum chemical study.
Voitko, Katerina; Tóth, Ajna; Demianenko, Evgenij; Dobos, Gábor; Berke, Barbara; Bakalinska, Olga; Grebenyuk, Anatolij; Tombácz, Etelka; Kuts, Volodymyr; Tarasenko, Yurij; Kartel, Mykola; László, Krisztina
The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability.
Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.
Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M
The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the
Catalytic B-H Bond Insertion Reactions Using Alkynes as Carbene Precursors.
Yang, Ji-Min; Li, Zi-Qi; Li, Mao-Lin; He, Qiao; Zhu, Shou-Fei; Zhou, Qi-Lin
Herein, we report transition-metal-catalyzed B-H bond insertion reactions between borane adducts and alkynes to afford organoboron compounds in excellent yields under mild reaction conditions. This successful use of alkynes as carbene precursors in these reactions constitutes a new route to organoboron compounds. The starting materials are safe and readily available, and the reaction exhibits 100% atom-economy. Moreover, an asymmetric version catalyzed by chiral dirhodium complexes produced chiral boranes with excellent enantioselectivity (up to 96% ee). This is the first report of highly enantioselective heteroatom-hydrogen bond insertion reactions of metal carbenes generated in situ from alkynes. The chiral products of the reaction could be easily transformed to widely used borates and diaryl methanol compounds without loss of optical purity, which demonstrates its potential utility in organic synthesis. A kinetics study indicated that the Cu-catalyzed B-H bond insertion reaction is first order with respect to the catalyst and the alkyne and zero order with respect to the borane adduct, and no kinetic isotopic effect was observed in the reaction of the adduct. These results, along with density functional theory calculations, suggest that the formation of the Cu carbene is the rate-limiting step and that the B-H bond insertion is a fast, concerted process.
The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. Research is proposed to study the reactivity of adsorbates for the direct NO decomposition and to investigate the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. An innovative infrared reactor system will be used to observe and determine the dynamic behavior and the reactivity of adsorbates during NO decomposition, oxygen spillover, and silanation. A series of experiments including X-ray diffraction, temperature programmed desorption, temperature programmed reaction, X-ray photoelectron spectroscopy will be used to characterized the catalysts. The information obtained from this study will provide a scientific basis for developing an effective catalyst for the NO decomposition under practical flue gas conditions.
Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, October 1--December 31, 1992
Heinemann, H.; Somorjai, G.A.; Perry, D.L.
Work on catalytic steam gasification with chars and coals will be extended from atmospheric to elevated pressures using the newly built pressure unit. The novel finding that coking of petroleum in the presence of small amounts of caustic greatly improves the gasification rates and characteristics of the coke will be extended to chars; in the oxidative coupling of methane over ternary catalysts, emphasis will be placed on low temperature coupling and on the oxidative production of syngas from methane at low temperature. Experimental work will continue on the synthesis of the mixed catalyst, and they will be characterized by a number of techniques, including elemental analyses, x-ray diffraction, and surface area determination.
First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface
NASA Astrophysics Data System (ADS)
Xue, Wenhua
Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL
Reactions of diborane with ammonia and ammonia borane: catalytic effects for multiple pathways for hydrogen release.
Nguyen, Vinh Son; Matus, Myrna H; Nguyen, Minh Tho; Dixon, David A
High-level electronic structure calculations have been used to construct portions of the potential energy surfaces related to the reaction of diborane with ammonia and ammonia borane (B2H6 + NH3 and B2H6 + BH3NH3)to probe the molecular mechanism of H2 release. Geometries of stationary points were optimized at the MP2/aug-cc-pVTZ level. Total energies were computed at the coupled-cluster CCSD(T) theory level with the correlation-consistent basis sets. The results show a wide range of reaction pathways for H2 elimination. The initial interaction of B2H6 + NH3 leads to a weak preassociation complex, from which a B-H-B bridge bond is broken giving rise to a more stable H3BHBH2NH3 adduct. This intermediate, which is also formed from BH3NH3 + BH3, is connected with at least six transition states for H2 release with energies 18-93 kal/mol above the separated reactants. The lowest-lying transition state is a six-member cycle, in which BH3exerts a bifunctional catalytic effect accelerating H2 generation within a B-H-H-N framework. Diborane also induces a catalytic effect for H2 elimination from BH3NH3 via a three-step pathway with cyclic transition states. Following conformational changes, the rate-determining transition state for H2 release is approximately 27 kcal/mol above the B2H6 + BH3NH3 reactants, as compared with an energy barrier of approximately 37 kcal/mol for H2 release from BH3NH3. The behavior of two separated BH3 molecules is more complex and involves multiple reaction pathways. Channels from diborane or borane initially converge to a complex comprising the H3BHBH2NH3adduct plus BH3. The interaction of free BH3 with the BH3 moiety of BH3NH3 via a six-member transition state with diborane type of bonding leads to a lower-energy transition state. The corresponding energy barrier is approximately 8 kcal/mol, relative to the reference point H3BHBH2NH3 adduct + BH3. These transition states are 27-36 kcal/mol above BH3NH3 + B2H6, but 1-9 kcal/mol below the
Perturbation theory in the catalytic rate constant of the Henri-Michaelis-Menten enzymatic reaction.
Bakalis, Evangelos; Kosmas, Marios; Papamichael, Emmanouel M
The Henry-Michaelis-Menten (HMM) mechanism of enzymatic reaction is studied by means of perturbation theory in the reaction rate constant k (2) of product formation. We present analytical solutions that provide the concentrations of the enzyme (E), the substrate (S), as well as those of the enzyme-substrate complex (C), and the product (P) as functions of time. For k (2) small compared to k (-1), we properly describe the entire enzymatic activity from the beginning of the reaction up to longer times without imposing extra conditions on the initial concentrations E ( o ) and S ( o ), which can be comparable or much different.
Catalytic three-component domino reaction for the preparation of trisubstituted oxazoles.
Wachenfeldt, Henrik v; Röse, Philipp; Paulsen, Filip; Loganathan, Nagarajan; Strand, Daniel
Multicomponent reactions are attractive for assembling functionalized heterocyclic compounds. To this end, an efficient gold-catalyzed three-component domino reaction to form oxazoles directly from imines, alkynes, and acid chlorides is presented. The reaction proceeds in a single synthetic step by using a gold(III)-N,N'-ethylenebis(salicylimine) (salen) catalyst to give trisubstituted oxazoles in up to 96 % yield. The substrate scope, a mechanistic study exploring the role of the gold catalyst, and the synthetic applications of the oxazole products are discussed.
Catalytic reaction energetics by single crystal adsorption calorimetry: hydrocarbons on Pt(111).
Lytken, Ole; Lew, Wanda; Campbell, Charles T
Single crystal adsorption calorimetry provides essential information about the energetics of surface reactions on well-defined surfaces where the adsorbed reaction products can be clearly identified. In this tutorial review, we cover the essentials of that technique, with emphasis on our lab's recent advances in sensitivity and temperature range, and demonstrate what can be achieved through a review of selected example studies concerning adsorption and dehydrogenation of hydrocarbons on Pt(111). A fairly complete reaction enthalpy diagram is presented for the dehydrogenation of cyclohexane to benzene on Pt(111).
Pt monolayer coating on complex network substrate with high catalytic activity for the hydrogen evolution reaction
Li, Man; Ma, Qiang; Zi, Wei; Liu, Xiaojing; Zhu, Xuejie; Liu, Shengzhong (Frank)
A deposition process has been developed to fabricate a complete-monolayer Pt coating on a large-surface-area three-dimensional (3D) Ni foam substrate using a buffer layer (Ag or Au) strategy. The quartz crystal microbalance, current density analysis, cyclic voltammetry integration, and X-ray photoelectron spectroscopy results show that the monolayer deposition process accomplishes full coverage on the substrate and the deposition can be controlled to a single atomic layer thickness. To our knowledge, this is the first report on a complete-monolayer Pt coating on a 3D bulk substrate with complex fine structures; all prior literature reported on submonolayer or incomplete-monolayer coating. A thin underlayer of Ag or Au is found to be necessary to cover a very reactive Ni substrate to ensure complete-monolayer Pt coverage; otherwise, only an incomplete monolayer is formed. Moreover, the Pt monolayer is found to work as well as a thick Pt film for catalytic reactions. This development may pave a way to fabricating a high-activity Pt catalyst with minimal Pt usage. PMID:26601247
Quantitative methylene blue decolourisation assays as rapid screening tools for assessing the efficiency of catalytic reactions.
Kruid, Jan; Fogel, Ronen; Limson, Janice Leigh
Identifying the most efficient oxidation process to achieve maximum removal of a target pollutant compound forms the subject of much research. There exists a need to develop rapid screening tools to support research in this area. In this work we report on the development of a quantitative assay as a means for identifying catalysts capable of decolourising methylene blue through the generation of oxidising species from hydrogen peroxide. Here, a previously described methylene blue test strip method was repurposed as a quantitative, aqueous-based spectrophotometric assay. From amongst a selection of metal salts and metallophthalocyanine complexes, monitoring of the decolourisation of the cationic dye methylene blue (via Fenton-like and non-Fenton oxidation reactions) by the assay identified the following to be suitable oxidation catalysts: CuSO4 (a Fenton-like catalyst), iron(II)phthalocyanine (a non-Fenton oxidation catalyst), as well as manganese(II) phthalocyanine. The applicability of the method was examined for the removal of bisphenol A (BPA), as measured by HPLC, during parallel oxidation experiments. The order of catalytic activity was identified as FePc > MnPc > CuSO4 for both BPA and MB. The quantitative MB decolourisation assay may offer a rapid method for screening a wide range of potential catalysts for oxidation processes.
Substrate Distortion and the Catalytic Reaction Mechanism of 5-Carboxyvanillate Decarboxylase
5-Carboxyvanillate decarboxylase (LigW) catalyzes the conversion of 5-carboxyvanillate to vanillate in the biochemical pathway for the degradation of lignin. This enzyme was shown to require Mn2+ for catalytic activity and the kinetic constants for the decarboxylation of 5-carboxyvanillate by the enzymes from Sphingomonas paucimobilis SYK-6 (kcat = 2.2 s–1 and kcat/Km = 4.0 × 104 M–1 s–1) and Novosphingobium aromaticivorans (kcat = 27 s–1 and kcat/Km = 1.1 × 105 M–1 s–1) were determined. The three-dimensional structures of both enzymes were determined in the presence and absence of ligands bound in the active site. The structure of LigW from N. aromaticivorans, bound with the substrate analogue, 5-nitrovanillate (Kd = 5.0 nM), was determined to a resolution of 1.07 Å. The structure of this complex shows a remarkable enzyme-induced distortion of the nitro-substituent out of the plane of the phenyl ring by approximately 23°. A chemical reaction mechanism for the decarboxylation of 5-carboxyvanillate by LigW was proposed on the basis of the high resolution X-ray structures determined in the presence ligands bound in the active site, mutation of active site residues, and the magnitude of the product isotope effect determined in a mixture of H2O and D2O. In the proposed reaction mechanism the enzyme facilitates the transfer of a proton to C5 of the substrate prior to the decarboxylation step. PMID:26714575
Kinetics and mechanism of the catalytic reaction between alcohols and dimethyl carbonate
NASA Astrophysics Data System (ADS)
Koledina, K. F.; Koledin, S. N.; Shchadneva, N. A.; Gubaidullin, I. M.
The mechanism of the reaction between alcohols and dimethyl carbonate, catalyzed by dicobalt octacarbonyl Co2(CO)8, is studied by means of mathematical modeling. Kinetic models for possible schemes of chemical transformations are constructed at different initial concentrations of the catalyst. Based on a comparative analysis of activation energies of possible stages of chemical transformations, possible reaction pathways are determined and an appropriate mechanism is selected.
A proton-shuttle reaction mechanism for histone deacetylase 8 and the catalytic role of metal ions.
Wu, Ruibo; Wang, Shenglong; Zhou, Nengjie; Cao, Zexing; Zhang, Yingkai
Zinc-dependent histone deacetylase 8 (HDAC8) catalyzes the removal of acetyl moieties from histone tails, and is critically involved in regulating chromatin structure and gene expression. The detailed knowledge of its catalytic process is of high importance since it has been established as a most promising target for the development of new antitumor drugs. By employing Born-Oppenheimer ab initio QM/MM molecular dynamics simulations and umbrella sampling, a state-of-the-art approach to simulate enzyme reactions, we have provided further evidence against the originally proposed general acid-base catalytic pair mechanism for Zinc-dependent histone deacetylases. Instead, our results indicated that HDAC8 employs a proton-shuttle catalytic mechanism, in which a neutral His143 first serves as the general base to accept a proton from the zinc-bound water molecule in the initial rate-determining nucleophilic attack step, and then shuttles it to the amide nitrogen atom to facilitate the cleavage of the amide bond. During the deacetylation process, the Zn(2+) ion changes its coordination mode and plays multiple catalytic roles. For the K(+) ion, which is located about 7 A from the catalytic Zn(2+) ion and conserved in class I and II HDACs, our simulations indicated that its removal would lead to the different transition state structure and a higher free energy reaction barrier for the rate-determining step. It is found that the existence of this conserved K(+) ion would enhance the substrate binding, increase the basicity of His143, strengthen the catalytic role of zinc ion, and improve the transition state stabilization by the enzyme environment.
Catalytic antibody light chain capable of cleaving a chemokine receptor CCR-5 peptide with a high reaction rate constant.
Mitsuda, Yukie; Hifumi, Emi; Tsuruhata, Kumi; Fujinami, Hiroko; Yamamoto, Naoki; Uda, Taizo
A monoclonal antibody (MAb), ECL2B-2, was obtained by immunizing a peptide possessing a part of a sequence of a chemokine receptor, CCR-5, which is present as a membrane protein on the macrophage surface, and which plays an important role in human immunodeficiency virus (HIV) infection. From the DNA and the deduced amino acid sequences of the light and heavy chains of ECL2B-2 MAb, molecular modeling was conducted to calculate the steric conformation of the antibody. Modeling suggested that the structure of ECL2B-2 could possess one or two catalytic triad(s), composed of Asp(1), Ser(27a) (or Ser(27e)), and His(93) (or His(27d)), in the light chain of ECL2B-2. The three amino acid residues, Asp(1), Ser(27a), and His(93), are identical to those of catalytic antibody light chains such as VIPase and i41SL1-2. The light chain of ECL2B-2 MAb degraded the antigenic peptide CCR-5 within about 100 h. Surprisingly, the light chain had a very high catalytic reaction rate constant (k(cat)) of 2.23 min(-1), which is greater by factors of tens to hundreds than those of natural catalytic antibodies obtained previously. The heavy chain of ECL2B-2 MAb, which has no catalytic triad because of a lack of His residue, did not degrade the CCR-5 peptide.
Kinetic method for the determination of traces of thyroxine by its catalytic effect on the Mn(III) metaphosphate-As(III) reaction.
Pastor, Ferenc T; Milovanović, Gordana A; Todorović, Marija
A new, highly sensitive and simple kinetic method for the determination of thyroxine was proposed. The method was based on the catalytic effect of thyroxine on the oxidation of As(III) by Mn(III) metaphosphate. The kinetics of the reaction was studied in the presence of orthophosphoric acid. The reaction rate was followed spectrophotometrically at 516 nm. It was established that orthophosphoric acid increased the reaction rate and that the extent of the non-catalytic reaction was extremely small. A kinetic equation was postulated and the apparent rate constant was calculated. The dependence of the reaction rate on temperature was investigated and the energy of activation and other kinetic parameters were determined. Thyroxine was determined under the optimal experimental conditions in the range 7.0 x 10(-9) to 3.0 x 10(-8) mol L(-1) with a relative standard deviation up to 6.7% and a detection limit of 2.7 x 10(-9) molL(-1). In the presence of 0.08 mol L(-1) chloride, the detection limit decreased to 6.6 x 10(-10) mol L(-1). The proposed method was applied for the determination of thyroxine in tablets. The accuracy of the method was evaluated by comparison with the HPLC method.
Catalytic hetero-ene reactions of 5-methyleneoxazolines: highly enantioselective synthesis of 2,5-disubstituted oxazole derivatives.
Luo, Weiwei; Zhao, Jiannan; Yin, Chengkai; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming
An efficient catalytic asymmetric hetero-ene reaction of 5-methyleneoxazolines with 1,2-dicarbonyl compounds (including α-ketoesters and glyoxal derivatives) was realized using Ni(II)-N,N'-dioxide complexes as the catalysts. It provides a rapid, high yielding (up to 99%) route for the preparation of 2,5-disubstituted oxazole derivatives in a highly enantioenriched form (up to >99% ee) under mild conditions.
Ru(II)/Organo Relay Catalytic Three-Component Reaction of 3-Diazooxindoles, Amines, and Nitroalkene: Formal Synthesis of (-)-Psychotrimine.
Lian, Xiao-Lei; Meng, Jing; Han, Zhi-Yong
A highly enantioselective carbenoid-associated N-H functionalization/Michael addition cascade reaction is developed by virtue of Ru(II)/chiral organo bifunctional catalyst relay catalysis. In this way, a variety of optically pure 3-amino-3-alkyloxindoles can be easily achieved. Moreover, on the basis of this metal/organo relay catalytic three-component protocol, a key intermediate for the formal synthesis of (-)-psychotrimine could be obtained in six steps with 25% overall yield.
Reduced graphene oxide: firm support for catalytically active palladium nanoparticles and game changer in selective hydrogenation reactions.
Cano, Manuela; Benito, Ana M; Urriolabeitia, Esteban P; Arenal, Raul; Maser, Wolfgang K
Simultaneous decomposition and reduction of a Pd(2+) complex in the presence of graphene oxide (GO) lead to the formation of Pd(0)-nanoparticles (Pd-NPs) with average sizes of 4 nm firmly anchored on reduced graphene oxide (RGO) sheets. The Pd-NP/RGO hybrids exhibited remarkable catalytic activity and selectivity in mild hydrogenation reactions where the acidic properties of RGO play an active role and may act as an important game-changer.
Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions
Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin
Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.
Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction
Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun
Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897
Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction
NASA Astrophysics Data System (ADS)
Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun
Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction.
Comment on ``Surface restructuring, kinetic oscillations, and chaos in heterogeneous catalytic reactions''
NASA Astrophysics Data System (ADS)
Kuzovkov, V. N.; Kortlüke, O.; von Niessen, W.
In a recent article Zhdanov studied the oscillating NO+H2 reaction on the Pt(100) single-crystal surface [V. P. Zhdanov, Phys. Rev. E 59, 6292 (1999)]. We have scrutinized his model and found fundamental errors in the chemical modeling, in the modeling of the surface reconstruction and in the simulation procedure itself.
Development of chiral thiourea catalysts and its application to asymmetric catalytic reactions.
Takemoto, Yoshiji
We have developed several multifunctional thiourea catalysts bearing a tertiary amine or an 1,2-amino alcohol in expectation of their synchronous activation of a nucleophile and an electrophile through both acid-base and hydrogen-bonding interactions. From these studies, it was revealed that the weak acidity of thioureas compared with metallic Lewis acids could be overcome by this modification. The bifunctional aminothiourea could be used efficiently for a wide range of diastereoselective and enantioselective nucleophilic reactions such as Michael addition of 1,3-dicarbonyl compounds to nitroolefines, aza-Henry reaction of nitroalkanes to N-Boc imines, and hydrazination of cyclic beta-keto esters. We also discovered that multifunctional thiourea catalyst, bearing an 1,2-amino alcohol moiety, significantly accelerated the Petasis-type reaction of alkenylboronic acids to N-phenoxycarbonyl quinolinium salts, prepared from quinolines and phenyl chloroformate, to afford 1,2-addition products with high enantioselectivity (up to 97% ee). Furthermore, to expand the synthetic applicability of the thiourea-catalyzed asymmetric reactions, tandem organocatalyzed reactions were explored to establish the concise one-pot synthesis of chiral densely functionalized three-, five-, and six-membered compounds.
Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.
Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu
The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).
Pressure Regulations on the Surface Properties of CeO2 Nanorods and Their Catalytic Activity for CO Oxidation and Nitrile Hydrolysis Reactions.
Li, Jing; Zhang, Zhiyun; Gao, Wei; Zhang, Sai; Ma, Yuanyuan; Qu, Yongquan
Surface properties of nanoscale CeO2 catalysts in terms of the surface Ce(3+) fraction and concentration of oxygen vacancy can affect their catalytic performance significantly. Continual adjustment on surface properties of CeO2 with the morphological preservation has not been realized by synthetic methods. The revisited studies show that surface properties of CeO2 nanorods can be effectively regulated by synthetic pressures while the rodlike morphology is well-preserved. Such phenomena are ascribed to the contact possibility between Ce(3+) species and dissolved O2, which is balanced by the rapidly increased and gradually saturated dissolution/recrystallization rate of Ce(OH)3 and linearly increased concentration of dissolved O2 with the increase of total air pressure or partial pressure of O2. Surface-property-dependent catalytic activity of CeO2 nanorods synthesized under various pressures was also demonstrated in two benchmark reactions-catalytic oxidation of CO and hydrolysis of nitrile. Such a finding of the pressure regulation on the reducible metal oxides provides an effective approach to rationally design novel catalysts for specific reactions, where ceria are supports, promoters, or actives.
A π-electronic covalent organic framework catalyst: π-walls as catalytic beds for Diels-Alder reactions under ambient conditions.
Wu, Yang; Xu, Hong; Chen, Xiong; Gao, Jia; Jiang, Donglin
We report a strategy for developing π-electronic covalent organic frameworks as heterogeneous catalysts that enable the use of columnar π-walls as catalytic beds to facilitate organic transformations in their one-dimensional open channels. The π-frameworks exhibit outstanding catalytic activity, promote Diels-Alder reactions under ambient conditions and are robust for cycle use.
Catalytic thermal cracking of post-consumer waste plastics to fuels. 2. Pilot study
Technology Transfer Automated Retrieval System (TEKTRAN)
Alternative gasoline and diesel fuels were prepared via catalytic and non-catalytic pyrolysis and distillation of waste polyethylene and polypropylene plastics. Reaction conditions were optimized using a bench-scale (2 L) batch reactor and then applied to pilot-scale production of crude plastic oil....
Solid State, Surface and Catalytic Studies of Oxides
Kung, H. H.
This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO{sub x}. Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO{sub x}, it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO{sub 2}/Al{sub 2}O{sub 3}. Ag/Al{sub 2}O{sub 3}, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.
Studies of coupled chemical and catalytic coal conversion methods
Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.
The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal's structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.
Studies of coupled chemical and catalytic coal conversion methods
Stock, L.M.; Chatterjee, K.; Cheng, C.; Ettinger, M.; Flores, F.; Jiralerspong, S.; Miyake, M.; Muntean, J.
The objective of this research was to convert coal into a soluble substance under mild conditions. The strategy involved two steps, first to breakdown the macromolecular network of coal, and second to add hydrogen catalytically. We investigated different basic reagents that could, in priciple, break down coal`s structure and alkylation strategies that might enhance its solubility. We examined O- and C-alkylation, the importance of the strength of the base, the character of the added alkyl groups and other reaction parameters. This work provided new information concerning the way in which hydrogen bonding, polarization interactions between aromatic structures and covalent bonding could be disrupted and solubility enhanced. The objective of our research was to explore new organochromium chemistry that might be feasible for the hydrogenation of coal under mild conditions.
Reaction pathway investigation on the selective catalytic reduction of NO with NH3 over Cu/SSZ-13 at low temperatures.
Su, Wenkang; Chang, Huazhen; Peng, Yue; Zhang, Chaozhi; Li, Junhua
The mechanism of the selective catalytic reduction of NO with NH3 was studied using Cu/SSZ-13. The adspecies of NO and NH3 as well as the active intermediates were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed surface reaction. The results revealed that three reactions were possible between adsorbed NH3 and NOx. NO2(-) could be generated by direct formation or NO3(-) reduction via NO. In a standard selective catalytic reduction (SCR) reaction, NO3(-) was hard to form, because NO2(-) was consumed by ammonia before it could be further oxidized to nitrates. Additionally, adsorbed NH3 on the Lewis acid site was more active than NH4(+). Thus, SCR mainly followed the reaction between Lewis acid site-adsorbed NH3 and directly formed NO2(-). Higher Cu loading could favor the formation of active Cu-NH3, Cu-NO2(-), and Cu-NO3(-), improving the SCR activity at low temperature.
Theoretical Studies of Reaction Surfaces
31 Aug 97 4. TITLE AND SUBTITLE 5 . FUNDING NUMBERS AASERT93 THEORETICAL STUDIES OF REACTION SURFACES F49620-93-1-0556 3484/XS 6. AUTHOR(S) 61103D DR...DUNCAN AVE ROOM B115 BOLLING AFB DC 20332- 8050 DR MICHAEL R. BERMAN 11. SUPPLEMENTARY NOTES 12a. DISTRIBUTION i AVAILABILITY STATEMENT Approved f or pill...reaction14 , and solvation of electrolytes1 5 . The EFP method described in the previous section has one drawback: the repulsive 3 potential relies on
Quantum-Mechanical Study on the Catalytic Mechanism of Alkaline Phosphatases.
Borosky, Gabriela L
Alkaline phosphatases (APs) catalyze the hydrolysis and transphosphorylation of phosphate monoesters. The catalytic mechanism was examined by quantum-mechanical calculations using an active-site model based on the X-ray crystal structure of the human placental AP. Free energies of activation and of reaction for the catalytic steps were evaluated for a series of aryl and alkyl phosphate esters, and the computational results were compared with experimental values available in the literature. Mechanistic observations previously reported in experimental works were rationalized by the present theoretical study, particularly regarding the difference in the rate-determining step between aryl and alkyl phosphates. The formation rate of the covalent phosphoserine intermediate followed a linear free energy relationship (LFER) with the pKa of the leaving group. This LFER, which could be experimentally determined only for less reactive alkyl phosphates, was verified by the present calculations to apply for the entire set of aryl and alkyl phosphate substrates.
Catalytic pyrolysis of tobacco rob: kinetic study and fuel gas produced.
Yang, Yi; Li, Tan; Jin, Shiping; Lin, Yixin; Yang, Haiping
The pyrolysis kinetics of tobacco rob (TR) was investigated using thermogravimetric analysis (TGA) under inert atmosphere, adding chemicals (dolomite and NiO) as catalysts by catalytic-mixing method. The TGA results showed that mass loss and mass loss rates were affected by catalysts. The conversion rates increased while the activation energy decreased. Moreover, the thermal decomposition behaviors of TR were studied in the fixed-bed reactor using dolomite and NiO/γ-Al2O3 as catalysts by catalyst-bed method. A series of experiments had been performed to explore the effects of catalysts, and reaction temperature on the composition and yield of fuel gas. The experiments demonstrated that the catalysts had a high activity of cracking tar and hydrocarbons, as well as yielding a high fuel gas production. For both methods, dolomite and NiO revealed better catalytic performance as a view of enhancing conversion rates and increasing product gas yield.
Superior catalytic performances of platinum nanoparticles loaded nitrogen-doped graphene toward methanol oxidation and hydrogen evolution reaction.
Liu, Dong; Li, Libo; You, Tianyan
The catalysts with excellent catalytic properties and low-cost are still highly desirable in many fields, such as fuel cells. In respect of this challenge, we have synthesized high-quality platinum nanoparticles loaded nitrogen-doped graphene (Pt/NG) by using formic acid as reduction agent and commercial-available nitrogen-doped graphene (N-graphene) as supporting materials. The morphology and component characterization demonstrate that high-loading Pt nanoparticles with a mean diameter of 2.5nm were uniformly dispersed on nitrogen-doped graphene. The resulting Pt/NG exhibit higher catalytic activity toward methanol oxidation and hydrogen evolution reaction compared with commercial Pt/C or self-synthesized platinum nanoparticles-loaded graphene. The superior catalytic performance of Pt/NG are discussed, and ascribed to the well-dispersed Pt nanoparticles and abundant edge plane sites on N-graphene. The resultant Pt/NG with high catalytic properties and cost-effective may emerge as a promising high-performance catalyst for fuel cells.
Bifunctional Molecular Photoswitches Based on Overcrowded Alkenes for Dynamic Control of Catalytic Activity in Michael Addition Reactions.
Pizzolato, Stefano F; Collins, Beatrice S L; van Leeuwen, Thomas; Feringa, Ben L
The emerging field of artificial photoswitchable catalysis has recently shown striking examples of functional light-responsive systems allowing for dynamic control of activity and selectivity in organocatalysis and metal-catalysed transformations. While our group has already disclosed systems featuring first generation molecular motors as the switchable central core, a design based on second generation molecular motors is lacking. Here, the syntheses of two bifunctionalised molecular switches based on a photoresponsive tetrasubstituted alkene core are reported. They feature a thiourea substituent as hydrogen-donor moiety in the upper half and a basic dimethylamine group in the lower half. This combination of functional groups offers the possibility for application of these molecules in photoswitchable catalytic processes. The light-responsive central cores were synthesized by a Barton-Kellogg coupling of the prefunctionalized upper and lower halves. Derivatization using Buchwald-Hartwig amination and subsequent introduction of the thiourea substituent afforded the target compounds. Control of catalytic activity in the Michael addition reaction between (E)-3-bromo-β-nitrostyrene and 2,4-pentanedione is achieved upon irradiation of stable-(E) and stable-(Z) isomers of the bifunctional catalyst 1. Both isomers display a decrease in catalytic activity upon irradiation to the metastable state, providing systems with the potential to be applied as ON/OFF catalytic photoswitches.
Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions.
Dybeck, Eric Christopher; Plaisance, Craig Patrick; Neurock, Matthew
A novel algorithm has been developed to achieve temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate timescales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC have been designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the timescales of the slow kinetically relevant non-equilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation and the reaction rate constants are rescaled accordingly. The algorithm has been utilized here to model the Fischer-Tropsch synthesis reaction over ruthenium nanoparticles. This reaction network has multiple timescale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to give reaction rates and selectivities indistinguishable from those calculated by an equivalent mean-field kinetic model. The computational savings of the algorithm can span many orders of magnitude in realistic systems and the computational cost is not limited by the magnitude of the timescale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.
Theoretical QM/MM studies of enzymatic pericyclic reactions.
Martí, S; Andrés, J; Moliner, V; Silla, E; Tuñón, I; Bertrán, J
The chorismate to prephenate enzyme catalyzed reaction has been used in this review as the conduit to show different theoretical approaches that have been used over the years in our laboratory to explain its molecular mechanism. This pericyclic reaction has the advantage that other protein scaffolds such as catalytic antibodies or some promiscuous enzymes present certain chorismate mutase activity. The obtained results on all these protein environments, by comparison with the uncatalyzed reaction in solution, have been used to propose, as a general conclusion, that the origin of enzyme catalysis is in the relative electrostatic stabilization of the transition state with respect to the Michaelis complex. This feature implies that reactants of catalyzed reaction were closer to the transition state than those of the non-catalyzed reaction. From this hypothesis, and considering the features of the wild type chorismate mutases as the optimal catalyst for the reaction, some mutations on both kinds of alternative proteins have been proposed which would presumably enhance the rate constant of the chemical step.The studies presented in this paper demonstrate that the improvements and developments of the methods and techniques of theoretical and computational chemistry are now mature enough to model physic-chemical properties of biological systems with good accuracy. The combination of a potent computational protocol with molecular engineering techniques can be a promising methodology to develop novel enzymes with new or more efficient catalytic functions.
Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.
Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie
The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5%) in α-MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2.
Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering
NASA Astrophysics Data System (ADS)
Rajagopalan, S.; Asthalter, T.; Rabe, V.; Laschat, S.
Nuclear inelastic scattering (NIS) of synchrotron radiation, also known as nuclear resonant vibrational spectroscopy (NRVS), has been shown to provide valuable insights into metal-centered vibrations at Mössbauer-active nuclei. We present a study of the iron-centered vibrational density of states (VDOS) during the first step of the Gif-type oxidation of cyclohexene with a novel trinuclear Fe3(μ 3-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe3(μ 3-O) in pyridine solution, Fe3(μ 3-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe3(μ 3-O)/Zn/acetic acid/pyridine/cyclohexene (reaction mixture) for reaction times of 1 min, 5 min, and 30 min. The projected VDOS of the Fe atoms was calculated on the basis of pseudopotential density functional calculations. Two possible reaction intermediates were identified as [Fe(III)(C5H5N)2(O2CCH3)2]+ and Fe(II)(C5H5N)4(O2CCH3)2, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.
Structure of RNase Sa2 complexes with mononucleotides--new aspects of catalytic reaction and substrate recognition.
Bauerová-Hlinková, Vladena; Dvorský, Radovan; Perecko, Dusan; Povazanec, Frantisek; Sevcík, Jozef
Although the mechanism of RNA cleavage by RNases has been studied for many years, there remain aspects that have not yet been fully clarified. We have solved the crystal structures of RNase Sa2 in the apo form and in complexes with mononucleotides. These structures provide more details about the mechanism of RNA cleavage by RNase Sa2. In addition to Glu56 and His86, which are the principal catalytic residues, an important role in the first reaction step of RNA cleavage also seems to be played by Arg67 and Arg71, which are located in the phosphate-binding site and form hydrogen bonds with the oxygens of the phosphate group of the mononucleotides. Their positive charge very likely causes polarization of the bonds between the oxygens and the phosphorus atom, leading to electron deficiency on the phosphorus atom and facilitating nucleophilic attack by O2' of the ribose on the phosphorus atom, leading to cyclophosphate formation. The negatively charged Glu56 is in position to attract the proton from O2' of the ribose. Extended molecular docking of mononucleotides, dinucleotides and trinucleotides into the active site of the enzyme allowed us to better understand the guanosine specificity of RNase Sa2 and to predict possible binding subsites for the downstream base and ribose of the second and third nucleotides.
Kinetics of the phosphotransferase reaction of the catalytic subunit of the tick salivary gland cAMP-dependent protein kinase
Mane, S.D.; Essenberg, R.C.; Sauer, J.R.
The catalytic subunit of the cAMP dependent protein kinase was purified 100-fold from tick salivary glands. The enzyme mechanism of the phosphotransferase reaction catalyzed by this subunit was investigated. Highly purified enzyme did not show ATP-ase activity in the absence of protein substrates. Initial velocities were measured using histone H-1 or a synthetic heptapeptide, Kemptide, as P/sub i/ acceptors and (..gamma..-/sup 32/P) ATP as a phosphodonor. Patterns were consistent with a sequential, but not a ping pong mechanism. At high concentration (>2Km), histone showed substrate inhibition which was noncompetitive versus ATP. Product inhibition by Mg.ADP was competitive versus ATP and noncompetitive with respect to H-1. Phosphohistone on the other hand was noncompetitive with respect to H-1, but gave parabolic competitive inhibition against ATP. Dead-end inhibition by AMP-PNP, an analogue of ATP, was competitive and noncompetitive against ATP and H-1, respectively. The inhibitory of cAMP dependent protein kinase was noncompetitive with ATP and competitive with histone. These studies strongly suggest that the tick salivary gland protein kinase has a sequential mechanism with primarily ordered addition of ATP followed by protein substrate and ordered release of phosphoprotein and ADP, but some random character.
Catalytic partial oxidation of iso-octane over rhodium catalysts: An experimental, modeling, and simulation study
Hartmann, M.; Minh, H.D.; Maier, L.; Deutschmann, O.
Catalytic partial oxidation of iso-octane over a rhodium/alumina coated honeycomb monolith is experimentally and numerically studied at short-contact times for varying fuel-to-oxygen ratios. A new experimental set-up with well-defined inlet and boundary conditions is presented. The conversion on the catalyst and in the gas-phase is modeled by detailed reaction mechanisms including 857 gas-phase and 17 adsorbed species. Elementary-step based heterogeneous and homogeneous reaction mechanisms are implemented into two-dimensional flow field description of a single monolith channel. Experiment and simulation provide new insights into the complex reaction network leading to varying product distribution as function of fuel-to-oxygen ratio. At fuel rich conditions, the formation of by-products that can serve as coke precursors is observed and interpreted. (author)
High catalytic activity of palladium(II)-exchanged mesoporous sodalite and NaA zeolite for bulky aryl coupling reactions: reusability under aerobic conditions.
Choi, Minkee; Lee, Dong-Hwan; Na, Kyungsu; Yu, Byung-Woo; Ryoo, Ryong
Exchange for the better: Mesoporous sodalite and NaA zeolite exchanged with Pd(2+) exhibit remarkably high activity and reusability in C-C coupling reactions under aerobic atmosphere. It is proposed that the catalytic reactions are mediated by a molecular Pd(0) species generated in situ within the pores (see picture), which is oxidized back to Pd(2+) by O(2), preventing the formation of catalytically inactive Pd(0) agglomerates.
Visible to near-infrared plasmon-enhanced catalytic activity of Pd hexagonal nanoplates for the Suzuki coupling reaction
NASA Astrophysics Data System (ADS)
Trinh, T. Thuy; Sato, Ryota; Sakamoto, Masanori; Fujiyoshi, Yoshifumi; Haruta, Mitsutaka; Kurata, Hiroki; Teranishi, Toshiharu
Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111} and six {100} planes. The Pd hexagonal nanoplates with well-defined and tunable longitudinal localized surface plasmon resonance (LSPR) have enabled the direct harvesting of visible to near-infrared light for catalytic cross coupling reactions. Upon plasmon excitation, the catalytic Suzuki coupling reactions of iodobenzene and phenylboronic acid accelerate by a plasmonic photocatalytic effect of plasmon induced hot electrons. The turnover frequency (TOF) of the Pd hexagonal nanoplates in a reaction illuminated with a λ = 300-1000 nm Xenon lamp at 176 mW cm-2 was 2.5 and 2.7 times higher than that of non-plasmonic {111}-enclosed Pd nanooctahedra and {100}-enclosed Pd nanocubes, respectively, and 1.7 times higher than the TOF obtained when the reaction was thermally heated to the same temperature.Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111
Interfacial Reaction Studies Using ONIOM
NASA Technical Reports Server (NTRS)
Cardelino, Beatriz H.
In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.
Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification.
Ji, Bolin; Tang, Peixin; Yan, Kelu; Sun, Gang
1,2,3,4-Butanetetracarboxylic acid (BTCA) reacts with cellulose in two steps with catalysis of alkaline salts such as sodium hypophosphite: anhydride formation and esterification of anhydride with cellulose. The alkali metal ions were found effective in catalyzing formation of BTCA anhydride in a previous report. In this work, catalytic functions of the alkaline salts in the esterification reaction between BTCA anhydride and cellulose were investigated. Results revealed that acid anions play an important role in the esterification reaction by assisting removal of protons on intermediates and completion of the esterification between cellulose and BTCA. Besides, alkaline salts with lower pKa1 values of the corresponding acids are more effective ones for the reaction since addition of these salts could lead to lower pH values and higher acid anion concentrations in finishing baths. The mechanism explains the results of FTIR and wrinkle recovery angles of the fabrics cured under different temperatures and times.
Ultraviolet-Visible (UV-Vis) Microspectroscopic System Designed for the In Situ Characterization of the Dehydrogenation Reaction Over Platinum Supported Catalytic Microchannel Reactor.
Suarnaba, Emee Grace Tabares; Lee, Yi Fuan; Yamada, Hiroshi; Tagawa, Tomohiko
An ultraviolet visible (UV-Vis) microspectroscopic system was designed for the in situ characterization of the activity of the silica supported platinum (Pt) catalyst toward the dehydrogenation of 1-methyl-1,4-cyclohexadiene carried out in a custom-designed catalytic microreactor cell. The in situ catalytic microreactor cell (ICMC) with inlet/outlet ports was prepared using quartz cover as the optical window to facilitate UV-Vis observation. A fabricated thermometric stage was adapted to the UV-Vis microspectrophotometer to control the reaction temperature inside the ICMC. The spectra were collected by focusing the UV-Vis beam on a 30 × 30 µm area at the center of ICMC. At 393 K, the sequential measurement of the spectra recorded during the reaction exhibited a broad absorption peak with maximum absorbance at 260 nm that is characteristic for gaseous toluene. This result indicates that the silica supported Pt catalyst is active towards the dehydrogenation of 1-methyl-1,4-cyclohexadiene at the given experimental conditions. The onset of coke formation was also detected based on the appearance of absorption bands at 300 nm. The UV-Vis microspectroscopic system developed can be used further in studying the mechanism of the dehydrogenation reaction.
Conversion of KCl into KBH4 by Mechano-Chemical Reaction and its Catalytic Decomposition
NASA Astrophysics Data System (ADS)
Bilen, Murat; Gürü, Metin; Çakanyildirim, Çetin
Production of KBH4, in the presence of KCl, B2O3 and MgH2 by means of a mechanical reaction and a dehydrogenation kinetic, constitute the main parts of this study. Operating time and reactant ratio are considered as two parameters for the mechanical reaction to obtain the maximum yield. The production process was carried out in a ball milling reactor, and the product residue was purified with ethylene diamine (EDA) and subsequently characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and x-ray Diffraction (XRD) analyses. Optimum time for mechano-chemical treatment and reactant ratio (MgH2/KCl) were obtained as 1000 min and 1.0, respectively. Synthesized and commercial KBH4 were compared by hydrolysis tests in the presence of Co1-xNix/Al2O3 heterogeneous catalyst. Hydrogen generation rates, activation energy and order of the KBH4 decomposition reaction were obtained as 1578 {mL}_{{{{H}}2 }} min^{ - 1} {g}_{{catalyst}}^{ - 1} , 39.2 kJ mol-1 and zero order, respectively.
Catalytic Enantioselective [2,3]-Rearrangements of Allylic Ammonium Ylides: A Mechanistic and Computational Study
A mechanistic study of the isothiourea-catalyzed enantioselective [2,3]-rearrangement of allylic ammonium ylides is described. Reaction kinetic analyses using 19F NMR and density functional theory computations have elucidated a reaction profile and allowed identification of the catalyst resting state and turnover-rate limiting step. A catalytically relevant catalyst–substrate adduct has been observed, and its constitution elucidated unambiguously by 13C and 15N isotopic labeling. Isotopic entrainment has shown the observed catalyst–substrate adduct to be a genuine intermediate on the productive cycle toward catalysis. The influence of HOBt as an additive upon the reaction, catalyst resting state, and turnover-rate limiting step has been examined. Crossover experiments have probed the reversibility of each of the proposed steps of the catalytic cycle. Computations were also used to elucidate the origins of stereocontrol, with a 1,5-S···O interaction and the catalyst stereodirecting group providing transition structure rigidification and enantioselectivity, while preference for cation−π interactions over C–H···π is responsible for diastereoselectivity. PMID:28230365
Catalytic Enantioselective [2,3]-Rearrangements of Allylic Ammonium Ylides: A Mechanistic and Computational Study.
West, Thomas H; Walden, Daniel M; Taylor, James E; Brueckner, Alexander C; Johnston, Ryne C; Cheong, Paul Ha-Yeon; Lloyd-Jones, Guy C; Smith, Andrew D
A mechanistic study of the isothiourea-catalyzed enantioselective [2,3]-rearrangement of allylic ammonium ylides is described. Reaction kinetic analyses using (19)F NMR and density functional theory computations have elucidated a reaction profile and allowed identification of the catalyst resting state and turnover-rate limiting step. A catalytically relevant catalyst-substrate adduct has been observed, and its constitution elucidated unambiguously by (13)C and (15)N isotopic labeling. Isotopic entrainment has shown the observed catalyst-substrate adduct to be a genuine intermediate on the productive cycle toward catalysis. The influence of HOBt as an additive upon the reaction, catalyst resting state, and turnover-rate limiting step has been examined. Crossover experiments have probed the reversibility of each of the proposed steps of the catalytic cycle. Computations were also used to elucidate the origins of stereocontrol, with a 1,5-S···O interaction and the catalyst stereodirecting group providing transition structure rigidification and enantioselectivity, while preference for cation-π interactions over C-H···π is responsible for diastereoselectivity.
Catalytic Asymmetric Synthesis of 3-Hydroxy-3-trifluoromethyl Benzofuranones via Tandem Friedel-Crafts/Lactonization Reaction.
Ren, Hai; Wang, Pan; Wang, Lijia; Tang, Yong
A highly enantioselective and regioselective chiral Lewis acid catalyzed tandem Friedel-Crafts/lactonization reaction is reported, providing direct access to plenty of 3-hydroxy-3-trifluoromethyl benzofuran-2-ones in up to 94% yields with up to >99% ee. Mechanistic study reveals that the interactions between the phenolic hydroxyl group and trifluoropyruvate are the most likely contributing factor to the high enantio- and regioselectivity. Optically pure (-)-BHFF can be obtained in gram-scale with 0.05 mol % catalyst, demonstrating the potentially utility of this method in medicinal chemistry.
Catalytic reaction profile for NADH-dependent reduction of aromatic aldehydes by xylose reductase from Candida tenuis.
Mayr, Peter; Nidetzky, Bernd
Kinetic substituent effects have been used to examine the catalytic reaction profile of xylose reductase from the yeast Candida tenuis, a representative aldo/keto reductase of primary carbohydrate metabolism. Michaelis-Menten parameters (k(cat) and K(m)) for NADH-dependent enzymic aldehyde reductions have been determined using a homologous series of benzaldehyde derivatives in which substituents in meta and para positions were employed to systematically perturb the properties of the reactive carbonyl group. Kinetic isotope effects (KIEs) on k(cat) and k(cat)/K(m) for enzymic reactions with meta-substituted benzaldehydes have been obtained by using NADH (2)H-labelled in the pro-R C4-H position, and equilibrium constants for the conversion of these aldehydes into the corresponding alcohols (K(eq)) have been measured in the presence of NAD(H) and enzyme. Aldehyde dissociation constants (K(d)) and the hydride transfer rate constant (k(7)) have been calculated from steady-state rate and KIE data. Quantitative structure-activity relationship analysis was used to factor the observed substituent dependence of k(cat)/K(m) into a major electronic effect and a productive positional effect of the para substituent. k(cat)/K(m) (after correction for substituent position) and K(eq) obeyed log-linear correlations over the substituent parameter, Hammett sigma, giving identical slope values (rho) of +1.4 to +1.7, whereas the same Hammett plot for logK(d) yielded rho=-1.5. This leads to the conclusion that electron-withdrawing substituents facilitate the reaction and increase binding to about the same extent. KIE values for k(cat) (1.8) and k(cat)/K(m) (2.7), and likewise k(7), showed no substituent dependence. Therefore, irrespective of the observed changes in reactivity over the substrate series studied no shift in the character of the rate-limiting transition state of hydride transfer occurred. The signs and magnitudes of rho values suggest this transition state to be product
Development of catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium complexes.
Tsubogo, Tetsu; Saito, Susumu; Seki, Kazutaka; Yamashita, Yasuhiro; Kobayashi, Shu
Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from calcium isopropoxide and chiral bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford 1,4-addition products, glutamic acid derivatives, in high yields with high enantioselectivities. During the investigation of the 1,4-addition reactions, we unexpectedly found that a [3 + 2] cycloaddition occurred in the reactions with crotonate derivatives, affording substituted pyrrolidine derivatives in high yields with high enantioselectivities. On the basis of this finding, we investigated asymmetric [3 + 2] cycloadditions, and it was revealed that several kinds of optically active substituted pyrrolidine derivatives containing contiguous stereogenic tertiary and quaternary carbon centers were obtained with high diastereo- and enantioselectivities. In addition, optically active pyrrolidine cores of hepatitis C virus RNA-dependent polymerase inhibitors and potential effective antiviral agents have been synthesized using this [3 + 2] cycloaddition reaction. NMR spectroscopic analysis and observation of nonamplification of enantioselectivity in nonlinear effect experiments suggested that a monomeric calcium species with an anionic ligand was formed as an active catalyst. A stepwise mechanism of the [3 + 2] cycloaddition, consisting of 1,4-addition and successive intramolecular Mannich-type reaction was suggested. Furthermore, modification of the Schiff base structure resulted in a modification of the reaction course from a [3 + 2] cycloaddition to a 1,4-addition, affording 3-substituted glutamic acid derivatives with high diasterero- and enantioselectivities.
General base catalysis in the urate oxidase reaction: evidence for a novel Thr-Lys catalytic diad.
Imhoff, Rebecca D; Power, Nicholas P; Borrok, M Jack; Tipton, Peter A
Urate oxidase catalyzes the oxidation of urate without the involvement of any cofactors. The gene encoding urate oxidase from Bacillus subtilis has been cloned and expressed, and the enzyme was purified and characterized. Formation of the urate dianion is believed to be a key step in the oxidative reaction. Rapid-mixing chemical quench studies provide evidence that the dianion is indeed an intermediate; at 15 degrees C the dianion forms within the mixing time of the rapid-quench instrument, and it disappears with a rate constant of 8 s(-)(1). Steady-state kinetic studies indicate that an ionizable group on the enzyme with a pK of 6.4 must be unprotonated for catalysis, and it is presumed that the role of this group is to abstract a proton from the substrate. Surprisingly, examination of the active site provided by the previously reported crystal structure does not reveal any obvious candidates to act as the general base. However, Thr 69 is hydrogen-bonded to the ligand at the active site, and Lys 9, which does not contact the ligand, is hydrogen-bonded to Thr 69. The T69A mutant enzyme has a V(max) that is 3% of wild type, and the K9M mutant enzyme has a V(max) that is 0.4% of wild type. The ionization at pH 6.4 that is observed with wild-type enzyme is absent in both of these mutants. It is proposed that these residues form a catalytic diad in which K9 deprotonates T69 to allow it to abstract the proton from the N9 position of the substrate to generate the dianion.
Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992
Ekerdt, J.G.
This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.
Carbene radicals in cobalt(II)-porphyrin-catalysed carbene carbonylation reactions; a catalytic approach to ketenes.
Paul, Nanda D; Chirila, Andrei; Lu, Hongjian; Zhang, X Peter; de Bruin, Bas
One-pot radicals: Cobalt(III)-carbene radicals, generated by metallo-radical activation of diazo compounds and N-tosylhydrazone sodium salts with cobalt(II) complexes of porphyrins, readily undergo radical addition to carbon monoxide, allowing the catalytic production of ketenes. These ketenes subsequently react with various amines, alcohols and imines in one-pot tandem transformations to produce differently substituted amides, esters and β-lactams in good isolated yields.
Studies on the catalytic mechanism of pig purple acid phosphatase.
Wynne, C J; Hamilton, S E; Dionysius, D A; Beck, J L; de Jersey, J
Several independent experiments failed to reveal any evidence in support of the involvement of a phosphoryl-enzyme intermediate in the catalytic mechanism of pig allantoic fluid purple acid phosphatase: (i) attempts to label enzyme with phosphate derived from [32P]p-nitrophenyl phosphate were unsuccessful; (ii) values of kcat for a series of phosphate derivative varied over a wide range, with the enzyme showing a marked preference for activated ester and anhydride substrates over those with a stable leaving group; (iii) burst titrations revealed a "burst" of p-nitrophenol from p-nitrophenyl phosphate only when the enzyme was added after the substrate, suggesting that this result was an artifact of the order of addition of reagents; (iv) transphosphorylation from p-nitrophenyl phosphate to acceptor alcohols could not be detected, even under conditions where a transphosphorylation to hydrolysis ratio as low as 0.015 could have been measured; (v) enzyme-catalyzed exchange of 180 between phosphate and water was demonstrated, although at a rate much slower than that observed for other phosphatases where the involvement of a phosphoryl-enzyme intermediate in the mechanism has been clearly established. The present results are compared with those obtained in similar studies on other phosphatases, particularly the highly homologous beef spleen purple acid phosphatase, and their implications for the catalytic mechanism of the purple acid phosphatases are discussed.
Catalytic Direct-type 1,4-Addition Reactions of Alkylazaarenes.
Suzuki, Hirotsugu; Igarashi, Ryo; Yamashita, Yasuhiro; Kobayashi, Shū
1,4-addition reactions of alkylazaarenes catalyzed by strong Brønsted bases have been developed for the first time. The desired reactions with α,β-unsaturated amides proceeded under mild reaction conditions to give the 1,4-adducts in high yields. Both ortho- and para-substituted azaarenes afforded the desired adducts in high yields. Regioselective reactions of di- or trimethylpyridine were found to be possible depending on the acidity of the α-hydrogen atoms. Furthermore, a candidate of allosteric protein kinase modulators was synthesized in two steps. An asymmetric variant of this reaction was also found to be feasible.
Caruana, C.M.
Chemical engineers here and abroad are finding that the marriage of catalysts and membranes holds promise for faster and more specific reactions, although commercialization of this technology is several years away. Catalytic membrane reactors (CMRs) combine a heterogeneous catalyst and a permselective membrane. Reactions performed by CMRs provide higher yields--sometimes as much as 50% higher--because of better reaction selectivity--as opposed to separation selectivity. CMRs also can work at very high temperatures, using ceramic materials that would not be possible with organic membranes. Although the use of CMRs is not widespread presently, the development of new membranes--particularly porous ceramic and zeolite membranes--will increase the potential to improve yields of many catalytic processes. The paper discusses ongoing studies, metal and advanced materials for membranes, the need for continued research, hydrogen recovery from coal-derived gases, catalytic oxidation of sulfides, CMRs for water purification, and oxidative coupling of methane.
Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions
Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Čejka, Jiří
Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate. PMID:24790940
Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions.
Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Cejka, Jiří
Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate.
High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system
NASA Technical Reports Server (NTRS)
Jachimowski, C. J.
An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.
Study of positive and negative plasma catalytic oxidation of ethylene.
Van Wesenbeeck, K; Hauchecorne, B; Lenaerts, S
The effect of introducing a photocatalytically active coating inside a plasma unit is investigated. This technique combines the advantages of high product selectivity from catalysis and the fast start-up from plasma technology. In this study, a preselected TiO2 coating is applied on the collector electrode of a DC corona discharge unit as non-thermal plasma reactor, in order to study the oxidation of ethylene. For both positive and negative polarities an enhanced mineralization is observed while the formation of by-products drastically decreases. The plasma catalytic unit gave the best results when using negative polarity at a voltage of 15 kV. This shows the potential of plasma catalysis as indoor air purification technology.
Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction.
Vallet, Ana; Ovejero, Gabriel; Rodríguez, Araceli; Peres, José A; García, Juan
Active nickel catalysts (7 wt%) supported over Mg-Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min(-1) and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min(-1), respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T(r)=0.098 g(Ni) min mL(-1). After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T(r)=0.098 g(Ni) min mL(-1), attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity.
Chemicals from Lignin by Catalytic Fast Pyrolysis, from Product Control to Reaction Mechanism.
Ma, Zhiqiang; Custodis, Victoria; Hemberger, Patrick; Bährle, Christian; Vogel, Frédéric; Jeschk, Gunnar; van Bokhoven, Jeroen A
Conversion of lignin into renewable and value-added chemicals by thermal processes, especially pyrolysis, receives great attention. The products may serve as feedstock for chemicals and fuels and contribute to the development of a sustainable society. However, the application of lignin conversion is limited by the low selectivity from lignin to the desired products. The opportunities for catalysis to selectively convert lignin into useful chemicals by catalytic fast pyrolysis and our efforts to elucidate the mechanism of lignin pyrolysis are discussed. Possible research directions will be identified.
Reply to ``Comment on `Surface restructuring, kinetic oscillations, and chaos in heterogeneous catalytic reactions' ''
NASA Astrophysics Data System (ADS)
Zhdanov, V. P.
In my numeration, the criticism of my simulations of kinetic oscillations in NO reduction by H2 on Pt(100) [V. P. Zhdanov, Phys. Rev. E 59, 6292 (1999)] by Kuzovkov, Kortlüke, and von Niessen [preceding paper, Phys. Rev. 63, 023101 (2001)] contains 19 comments. I show that four comments are irrelevant. The other 15 comments are wrong, because they either contradict the basic principles of the theory of phase transitions, Monte Carlo simulations, and catalytic chemistry or ignore numerous experimental data on adsorbate-induced restructuring of the Pt(100) surface.
Catalytic, Enantioselective Sulfenofunctionalisation of Alkenes: Mechanistic, Crystallographic, and Computational Studies
Denmark, Scott E.; Hartmann, Eduard; Kornfilt, David J. P.; Wang, Hao
The stereocontrolled introduction of vicinal heteroatomic substituents into organic molecules is one of the most powerful ways of adding value and function. Whereas many methods exist for the introduction of oxygen- and nitrogen-containing substituents, the number stereocontrolled methods for the introduction of sulfur-containing substituents pales by comparison. Previous reports from these laboratories have described the sulfenofunctionalization of alkenes that construct vicinal carbon-sulfur and carbon-oxygen, carbon-nitrogen as well as carbon-carbon bonds with high levels of diastereospecificity and enantioselectivity. This process is enabled by the concept of Lewis base activation of Lewis acids that provides activation of Group 16 electrophiles. To provide a foundation for expansion of substrate scope and improved selectivities, we have undertaken a comprehensive study of the catalytically active species. Insights gleaned from kinetic, crystallographic and computational methods have led to the introduction of a new family of sulfenylating agents that provide significantly enhanced selectivities. PMID:25411883
Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(III) corrole 1-Fe.
Avidan-Shlomovich, Shlomit; Gross, Zeev
The amphipolar iron(III) corrole 1-Fe is one of the most efficient catalysts for the decomposition of peroxynitrite, the toxin involved in numerous diseases. This research focused on the mechanism of that reaction at physiological pH, where peroxynitrite is in equilibrium with its much more reactive conjugated acid, by focusing on the elementary steps involved in the catalytic cycle. Kinetic investigations uncovered the formation of a reaction intermediate in a process that is complete within a few milliseconds (k1 ∼ 3 × 10(7) M(-1) s(-1) at 5 °C, about 7 orders of magnitude larger than the first order rate constant for the non-catalyzed process). Multiple evidence points towards iron-catalyzed homolytic O-O bond cleavage to form nitrogen dioxide and hydroxo- or oxo-iron(iv) corrole. The iron(iv) intermediate was found to decay via multiple pathways that proceed at similar rates (k2 about 10(6) M(-1) s(-1)): reaction with nitrogen dioxide to form nitrate, nitration of the corrole macrocyclic, and dimerization to binuclear iron(iv) corrole. Catalysis in the presence of substrates affects the decay of the iron intermediate by either oxidative nitration (phenolic substrates) or reduction (ascorbate). A large enough excess of ascorbate accelerates the catalytic decomposition of PN by 1-Fe by orders of magnitude, prevents other decay routes of the iron intermediate, and eliminates nitration products as well. This suggests that the beneficial effect of the iron corrole under the reducing conditions present in most biological media might be even larger than in the purely chemical system. The acquired mechanistic insight is of prime importance for the design of optimally acting catalysts for the fast and safe decomposition of reactive oxygen and nitrogen species.
Catalytic cracking of palm oil for the production of biofuels: optimization studies.
Tamunaidu, Pramila; Bhatia, Subhash
Oil palm is widely grown in Malaysia. Palm oil has attracted the attention of researchers to develop an 'environmentally friendly' and high quality fuel, free of nitrogen and sulfur. In the present study, the catalytic cracking of palm oil to biofuel was studied over REY catalyst in a transport riser reactor at atmospheric pressure. The effect of reaction temperature (400-500 degrees C), catalyst/palm oil ratio (5-10) and residence time (10-30s) was studied over the yield of bio-gasoline and gas as fuel. Design of experiments was used to study the effect of operating variables over conversion of palm oil and yield of hydrocarbon fuel. The response surface methodology was used to determine the optimum value of the operating variables for maximum yield of bio-gasoline fraction in the liquid product obtained.
Layered materials with coexisting acidic and basic sites for catalytic one-pot reaction sequences.
Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro
Acidic montmorillonite-immobilized primary amines (H-mont-NH(2)) were found to be excellent acid-base bifunctional catalysts for one-pot reaction sequences, which are the first materials with coexisting acid and base sites active for acid-base tamdem reactions. For example, tandem deacetalization-Knoevenagel condensation proceeded successfully with the H-mont-NH(2), affording the corresponding condensation product in a quantitative yield. The acidity of the H-mont-NH(2) was strongly influenced by the preparation solvent, and the base-catalyzed reactions were enhanced by interlayer acid sites.
Studies of coupled chemical and catalytic coal conversion methods
Stock, L.M.
C-Alkylation has been utilized in the solubilization of various coals. Low rank, high oxygen Illinois No. 6 coal was alkylated with different alkylating agents under different conditions to determine the most suitable reaction conditions. A new method of alkylating coal with n-butyl lithium and potassium tertiary butoxide in refluxing heptane has been studied. The influence of the solvent for alkylation on the pyridine solubility of the product was studied. The pyridine solubility of the products obtained with n-butyl iodide ranged from 39% for the reaction in heptane to 5l% for the reaction in tetrahydropyran. Tetrahydrofuran, in contrast, produced only 33% pyridine soluble product. The reactivity pattern for alkylation was determined by deuterium and carbon NMR spectroscopy of the products that were obtained with deuterium and carbon-13 labelled alkylating agents.
A Diode Laser Study of the Catalytic Oxidation Dynamics of Acetaldehyde on Polycrystalline Platinum
NASA Astrophysics Data System (ADS)
Edington, Sean Coleman
The catalytic oxidation of acetaldehyde on platinum was studied using a flow reactor equipped with a tunable diode laser absorption spectrometer and a quadrupole mass spectrometer. Reaction mixtures containing this molecule in varying proportion with oxygen and with argon as a carrier gas were flowed over a polycrystalline platinum mesh, which was resistively heated to different temperatures between 700 and 1000 K. The products of these reactions were monitored using mass spectrometry and the state-resolved spectra of CO 2 produced were collected using high-resolution tunable diode laser absorption spectroscopy. These data were analyzed to yield information about the dynamics of the reaction. Results indicate that production of CO and CO2 by this reaction proceeds via two distinct pathways. Acetaldehyde adsorbed on the surface decomposes to acetyl, which in turn decomposes CO and CHx. The adsorbed CO so prepared desorbs to yield the bulk of CO generated across all reaction conditions and also yields CO2 with a relatively deactivated asymmetric stretching mode under conditions of high temperature and low oxygen coverage. The acetyl-derived CHx dehydrogenates to yield surface carbon and H adatoms. Total oxidation of this surface carbon is the primary source of CO2 produced under all reaction conditions except those mentioned previously and is found to yield products with a preferentially excited asymmetric stretch. Combination of the CHx-derived H adatoms with surface oxygen drives the production of water by this reaction. During the course of the work described here, two notable improvements were made to our experimental apparatus. The first of these was the modification of the data acquisition process to significantly improve the signal-to-noise ratio achievable by our laser spectrometer with no increase in data collection time. The second was the development of data analysis software which significantly improved the efficiency and thoroughness of the process by
Advanced catalytic performance of Au-Pt double-walled nanotubes and their fabrication through galvanic replacement reaction.
Chen, Lu; Kuai, Long; Yu, Xue; Li, Wenzheng; Geng, Baoyou
Bimetallic tubular nanostructures have been the focus of intensive research as they have very interesting potential applications in various fields including catalysis and electronics. In this paper, we demonstrate a facile method for the fabrication of Au-Pt double-walled nanotubes (Au-Pt DWNTs). The DWNTs are fabricated through the galvanic displacement reaction between Ag nanowires and various metal ions, and the Au-Pt DWNT catalysts exhibit high active catalytic performances toward both methanol electro-oxidation and 4-nitrophenol (4-NP) reduction. First, they have a high electrochemically active surface area of 61.66 m(2) g(-1), which is close to the value of commercial Pt/C catalysts (64.76 m(2) g(-1)), and the peak current density of Au-Pt DWNTs in methanol oxidation is recorded as 138.25 mA mg(-1), whereas those of Pt nanotubes, Au/Pt nanotubes (simple mixture), and commercial Pt/C are 24.12, 40.95, and 120.65 mA mg(-1), respectively. The Au-Pt DWNTs show a markedly enhanced electrocatalytic activity for methanol oxidation compared with the other three catalysts. They also show an excellent catalytic performance in comparison with common Au nanotubes for 4-nitrophenol (4-NP) reduction. The attractive performance exhibited by these prepared Au-Pt DWNTs can be attributed to their unique structures, which make them promising candidates as high-performance catalysts.
Catalytic solid substrate room temperature phosphorimetry for the determination of trace rhamnose based on its condensation reaction with calcein
NASA Astrophysics Data System (ADS)
Liu, Jia-Ming; Lin, Li-Ping; Wang, Hong-Xin; Lin, Shao-Qin; Zhang, Li-Hong; Cai, Wen-Lian; Lin, Xuan; Pan, You-Zhu; Wang, Xin-Xing; Li, Zhi-Ming; Jiao, Li; Cui, Ma-Lin
Calcein (R) could not only emit strong and stable room temperature phosphorescence (RTP) on filter paper using I - as perturber, but also could be oxidized by H 2O 2 to form a non-phosphorescence compound (R'), resulting in the quenching of RTP signal of R. Moreover, the ortho-hydrogen of phenolic hydroxyl in R took condensation reaction with rhamnose (Rha) to produce non-phosphorescence compound (R-Rha) causing the RTP signal of R to further quench, and R-Rha was oxidized by H 2O 2 to form R' and Rha, bringing about the sharp RTP signal quenching of R. Thus, a new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace Rha based on its strong catalytic effect on H 2O 2 oxidizing R has been established, with the detection limit (LD) of 7.8 zg spot -1 (corresponding concentration: 2.0 × 10 -17 g ml -1, sample volume: 0.40 μl spot -1). This method has been applied to determine trace Rha in cigarettes and jujubes, with the results coinciding well with those determined by a high performance liquid chromatography (HPLC). The component of R-Rha also was analyzed by means of HPLC, mass spectrometer and nuclear magnetic resonance (NMR) measurements. The mechanism of catalytic SSRTP for the determination of trace Rha was discussed.
Computational study of a model system of enzyme-mediated [4+2] cycloaddition reaction.
Gordeev, Evgeniy G; Ananikov, Valentine P
A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.
Spectroscopic investigation of the reaction mechanism of CopB-B, the catalytic fragment from an archaeal thermophilic ATP-driven heavy metal transporter.
Völlmecke, Christian; Kötting, Carsten; Gerwert, Klaus; Lübben, Mathias
The mechanism of ATP hydrolysis of a shortened variant of the heavy metal-translocating P-type ATPase CopB of Sulfolobus solfataricus was studied. The catalytic fragment, named CopB-B, comprises the nucleotide binding and phosphorylation domains. We demonstrated stoichiometric high-affinity binding of one nucleotide to the protein (K(diss) 1-20 microm). Mg is not necessary for nucleotide association but is essential for the phosphatase activity. Binding and hydrolysis of ATP released photolytically from the caged precursor nitrophenylethyl-ATP was measured at 30 degrees C by infrared spectroscopy, demonstrating that phosphate groups are not involved in nucleotide binding. The hydrolytic kinetics was biphasic, and provides evidence for at least one reaction intermediate. Modelling of the forward reaction gave rise to three kinetic states connected by two intrinsic rate constants. The lower kinetic constant (k(1) = 4.7 x 10(-3) s(-1) at 30 degrees C) represents the first and rate-limiting reaction, probably reflecting the transition between the open and closed conformations of the domain pair. The subsequent step has a faster rate (k(2) = 17 x 10(-3) s(-1) at 30 degrees C), leading to product formation. Although the latter appears to be a single step, it probably comprises several reactions with presently unresolved intermediates. Based on these data, we suggest a model of the hydrolytic mechanism.
Experimental Study of Serpentinization Reactions
NASA Technical Reports Server (NTRS)
Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.
Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.
Catalytic Effects of Oxide Surfaces on Diels-Alder Cycloaddition between Furan and Methyl Acrylate: A DFT Study
NASA Astrophysics Data System (ADS)
Salavati-Fard, Taha; Jenness, Glen; Caratzoulas, Stavros; Doren, Douglas
Using density functional theory with periodic boundary conditions, we study the catalytic effects of oxide surfaces such as ZrO_2 and HfO_2 on Diels-Alder reaction between furan and methyl acrylate. The cycloadduct can be dehydrated later to produce methyl benzoic which is an important step toward benzoic acid production. The gas-phase and on-surface reaction mechanisms are studied in detail. The surface hydration effects on the reaction mechanism and energy profile are studied as well. Our calculations show that the oxide surfaces catalyze the reaction significantly through the interaction of metal sites with methyl acrylate. The calculations are interpreted by making use of electronic density of states and band structure of the catalyst.
Insight into the Catalytic Mechanism of Bimetallic Platinum–Copper Core–Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions
Ma, Lu; Luo, Xiangyi; Kropf, A. Jeremy; Wen, Jianguo; Wang, Xiaoping; Lee, Sungsik; Myers, Deborah J.; Miller, Dean; Wu, Tianpin; Lu, Jun; Amine, Khalil
The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt–Cu core–shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li–O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt–Cu core–shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.
Reaction of Cu(I) with dialkyl peroxides: Cu(II)-alkoxides, alkoxy radicals, and catalytic C-H etherification.
Gephart, Raymond T; McMullin, Claire L; Sapiezynski, Nicholas G; Jang, Eun Sil; Aguila, Mae Joanne B; Cundari, Thomas R; Warren, Timothy H
Kinetic analysis of the reaction of the copper(I) β-diketiminate [Cl(2)NN]Cu ([Cu(I)]) with (t)BuOO(t)Bu to give [Cu(II)]-O(t)Bu (1) reveals first-order behavior in each component implicating the formation of free (t)BuO(•) radicals. Added pyridine mildly inhibits this reaction indicating competition between (t)BuOO(t)Bu and py for coordination at [Cu(I)] prior to peroxide activation. Reaction of [Cu(I)] with dicumyl peroxide leads to [Cu(II)]-OCMe(2)Ph (3) and acetophenone suggesting the intermediacy of the PhMe(2)CO(•) radical. Computational methods provide insight into the activation of (t)BuOO(t)Bu at [Cu(I)]. The novel peroxide adduct [Cu(I)]((t)BuOO(t)Bu) (4) and the square planar [Cu(III)](O(t)Bu)(2) (5) were identified, each unstable toward loss of the (t)BuO(•) radical. Facile generation of the (t)BuO(•) radical is harnessed in the catalytic C-H etherification of cyclohexane with (t)BuOO(t)Bu at rt employing [Cu(I)] (5 mol %) to give the ether Cy-O(t)Bu in 60% yield.
Kinetic catalytic determination of trace Cu(II) in water samples with the thioglycolic/thiolactic acid-chromate reaction.
Rustoiu-Csavdari, A; Mihai, D; Bâldea, I
The use of two novel similar indicator reactions as applied to the kinetic determination of Cu(II) in water is investigated. The methods rely on the catalytic effect of the analyte on the oxidation of thioglycolic (TGA) and thiolactic (TLA) acids by chromate in acidic media. The extent of the reactions was followed spectrophotometrically at 345 nm. Pseudo-first-order rate coefficients, k(obsd), were determined as a function of catalyst concentration. Interference of Fe(III) and Pb(II) was suppressed by complexation with pyrophosphate. For the reaction of TGA, a linear regression for k(obsd) versus [Cu(II)] was obtained for the entire concentration range considered. Although the plot corresponding to TLA oxidation exhibits a sharp change of slope at approximately 1.8x10(-5) M Cu(II), it can still be described effectively by two linear regressions with different slopes. The reaction of TGA is more sensitive than that of TLA at low Cu(II) concentration. The opposite is true for higher catalyst contents. The detection limits were 65 microg L(-1) for TGA and of 80 microg L(-1) for TLA oxidation, respectively. The relative standard deviations, of 0.4% for TGA and 1.1% for TLA oxidation, respectively, were obtained for five replicate runs at 1000 microg L(-1). Samples of river and wastewater from the mining region of Baia-Mare, Northern Romania were analyzed using the more sensitive reaction of thioglycolic acid. Results were compared to those obtained by the officially standardized methods. Good agreement was obtained, even for an untreated sample. Measurements did not require prior separation of interfering species.
Multifunctional role of His159in the catalytic reaction of serine palmitoyltransferase.
Shiraiwa, Yuka; Ikushiro, Hiroko; Hayashi, Hideyuki
Serine palmitoyltransferase (SPT) belongs to the fold type I family of the pyridoxal 5'-phosphate (PLP)-dependent enzyme and forms 3-ketodihydrosphingosine (KDS) from l-serine and palmitoyl-CoA. Like other alpha-oxamine synthase subfamily enzymes, SPT is different from most of the fold type I enzymes in that its re face of the PLP-Lys aldimine is occupied by a His residue (His(159)) instead of an aromatic amino acid residue. His(159) was changed into alanine or aromatic amino acid residues to examine its role during catalysis. All mutant SPTs formed the PLP-l-serine aldimine with dissociation constants several 10-fold higher than that of the wild type SPT and catalyzed the abortive transamination of l-serine. These results indicate that His(159) is not only the anchoring site for l-serine but regulates the alpha-deprotonation of l-serine by fixing the conformation of the PLP-l-serine aldimine to prevent unwanted side reactions. Only H159A SPT retained activity and showed a prominent 505-nm absorption band of the quinonoid species during catalysis. Global analysis of the time-resolved spectra suggested the presence of the two quinonoid intermediates, the first formed from the PLP-l-serine aldimine and the second from the PLP-KDS aldimine. Accumulation of these quinonoid intermediates indicated that His(159) promotes both the Claisen-type condensation as an acid catalyst and the protonation at Calpha of the second quinonoid to form the PLP-KDS aldimine. These results, combined with the previous model building study (Ikushiro, H., Fujii, S., Shiraiwa, Y., and Hayashi, H. (2008) J. Biol. Chem. 283, 7542-7553), lead us to propose a novel mechanism, in which His(159) plays multiple roles by exploiting the stereochemistry of Dunathan's conjecture.
Multifunctional Role of His159in the Catalytic Reaction of Serine Palmitoyltransferase*
Shiraiwa, Yuka; Ikushiro, Hiroko; Hayashi, Hideyuki
Serine palmitoyltransferase (SPT) belongs to the fold type I family of the pyridoxal 5′-phosphate (PLP)-dependent enzyme and forms 3-ketodihydrosphingosine (KDS) from l-serine and palmitoyl-CoA. Like other α-oxamine synthase subfamily enzymes, SPT is different from most of the fold type I enzymes in that its re face of the PLP-Lys aldimine is occupied by a His residue (His159) instead of an aromatic amino acid residue. His159 was changed into alanine or aromatic amino acid residues to examine its role during catalysis. All mutant SPTs formed the PLP-l-serine aldimine with dissociation constants several 10-fold higher than that of the wild type SPT and catalyzed the abortive transamination of l-serine. These results indicate that His159 is not only the anchoring site for l-serine but regulates the α-deprotonation of l-serine by fixing the conformation of the PLP-l-serine aldimine to prevent unwanted side reactions. Only H159A SPT retained activity and showed a prominent 505-nm absorption band of the quinonoid species during catalysis. Global analysis of the time-resolved spectra suggested the presence of the two quinonoid intermediates, the first formed from the PLP-l-serine aldimine and the second from the PLP-KDS aldimine. Accumulation of these quinonoid intermediates indicated that His159 promotes both the Claisen-type condensation as an acid catalyst and the protonation at Cα of the second quinonoid to form the PLP-KDS aldimine. These results, combined with the previous model building study (Ikushiro, H., Fujii, S., Shiraiwa, Y., and Hayashi, H. (2008) J. Biol. Chem. 283, 7542–7553), lead us to propose a novel mechanism, in which His159 plays multiple roles by exploiting the stereochemistry of Dunathan's conjecture. PMID:19346561
Catalytic asymmetric aldol addition reactions of 3-fluoro-indolinone derived enolates.
Zhang, Lijun; Zhang, Wenzhong; Mei, Haibo; Han, Jianlin; Soloshonok, Vadim A; Pan, Yi
Reported herein is a Cu(i)/bisoxazoline ligand-catalyzed aldol reaction of unprotected tertiary enolates generated in situ from 3-(1,1-dihydroxy-2,2,2-trifluoroethyl)-substituted derivatives of 3-fluoro-2-oxindoles. A range of α-fluoro-β-aryl/hetaryl/alkyl-β-hydroxy-indolin-2-ones containing C-F quaternary stereogenic centers of high pharmaceutical importance were furnished in good yields and satisfactory diastereo- and enantioselectivities. The reactions were conducted under operationally convenient conditions and displayed wide substrate/functional group generality including unprotected N-H on the tertiary enolates, and aromatic, hetero-aromatic and aliphatic aldehydes.
Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.
Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya
Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long
Spatially resolved characterization of catalyst-coated membranes by distance-controlled scanning mass spectrometry utilizing catalytic methanol oxidation as gas-solid probe reaction.
Li, Nan; Assmann, Jens; Schuhmann, Wolfgang; Muhler, Martin
The spatially resolved catalytic activity of a catalyst-coated membrane (CCM), which is the essential part of PEM fuel cells, was visualized rapidly without any damage by a distance-controlled scanning mass spectrometer with an improved resolution of 250 microm. Methanol oxidation was identified as a suitable gas-solid probe reaction for the characterization of local catalytic activity. In addition, defects were manually generated in the CCM to simulate inhomogeneous coating and pinholes. The measurements successfully demonstrated that catalytically active and less active regions can be clearly distinguished. Simultaneously, the local topography was recorded, providing additional information on the location of the scratches and pinholes. The catalytic results were highly reproducible due to the constant-distance feedback loop rendering scanning mass spectrometry a promising tool for the quantitative quality control of CCMs.
Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics
Battaglia, Francine; Agblevor, Foster; Klein, Michael; Sheikhi, Reza
A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.
Catalytic Asymmetric Synthesis of Chiral 2-Vinylindole Scaffolds by Friedel-Crafts Reaction.
Arai, Takayoshi; Tsuchida, Akiko; Miyazaki, Tomoya; Awata, Atsuko
A chiral bis(imidazolidine)pyridine (PyBidine)-Ni(OTf)2 complex smoothly catalyzed an asymmetric Friedel-Crafts reaction of 2-vinylindoles with nitroalkenes to give chiral indoles in a highly enantioselective manner while maintaining the 2-vinyl functionality. The chiral 2-vinylindoles offer unique chiral scaffolds for diverse transformations.
Metal nanoparticle/ionic liquid/cellulose: new catalytically active membrane materials for hydrogenation reactions.
Gelesky, Marcos A; Scheeren, Carla W; Foppa, Lucas; Pavan, Flavio A; Dias, Silvio L P; Dupont, Jairton
Transition metal-containing membrane films of 10, 20, and 40 μm thickness were obtained by the combination of irregularly shaped nanoparticles with monomodal size distributions of 4.8 ± 1.1 nm (Rh(0)) and 3.0 ± 0.4 nm (Pt(0)) dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI·(NTf)(2)) with a syrup of cellulose acetate (CA) in acetone. The Rh(0) and Pt(0) metal concentration increased proportionally with increases in film thickness up to 20 μm, and then the material became metal saturated. The presence of small and stable Rh(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The augmentation of the IL content resulted in an increase of elasticity and decrease in tenacity and toughness, whereas the stress at break was not influenced. The introduction of IL probably causes an increase in the separation between the cellulose macromolecules that results in a higher flexibility, lower viscosity, and better formability of the cellulose material. The nanoparticle/IL/CA combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The nanoparticle/IL/cellulose acetate film membranes display higher catalytic activity (up to 7353 h(-1) for the 20 μm film of CA/IL/Pt(0)) and stability than the nanoparticles dispersed only in the IL.
Kinetic studies of elementary chemical reactions
Durant, J.L. Jr.
This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.
Catalytic wet oxidation of aqueous methylamine: comparative study on the catalytic performance of platinum-ruthenium, platinum, and ruthenium catalysts supported on titania.
Song, Aiying; Lu, Gongxuan
Promotion of the dispersion of Ru species supported on TiO2 was achieved by introduction of Pt component and the role of Pt in enhancing the catalytic performances of Pt-Ru was investigated with catalytic wet air oxidation of methylamine used as a probing reaction. It was found that Pt-Ru/TiO2 displayed a much better catalytic performance compared with Pt/TiO2 and Ru/TiO2 catalysts due to having the highest dispersion of active species. Both high total organic carbon conversion and nitrogen selectivity (∼100%) over Pt-Ru/TiO2 catalyst were achieved at low temperature (200 °C). X-ray photoelectron spectroscopy characterization indicated that there were strong interactions between metal particles and the support, which may increase the catalytic performance of catalysts.
Catalytic reduction of NO by CO over rhodium catalysts. 2. Effect of oxygen on the nature, population, and reactivity of surface species formed under reaction conditions
Kondarides, D.I.; Chafik, T.; Verykios, X.E.
The effect of oxygen on the nature, population, and reactivity of surface species formed during reduction of NO by CO over Rh/TiO{sub 2} catalysts has been examined employing FTIR and transient MS techniques. It has been found that the activity of Rh is hindered by accumulation of surface oxygen originating from NO decomposition and gas-phase oxygen in the feed. Adsorbed CO and reduced TiO{sub 2{minus}x} species in the vicinity of Rh particles act as oxygen atom scavengers and, under fuel-rich conditions, remove atomic oxygen from the surface and restore the catalytic properties. Results of the present study provide additional evidence that production of N{sub 2} is related to dissociation of adsorbed Rh-NO{sup {minus}} while production of N{sub 2}O is related to the presence of Rh(NO){sub 2}. The presence of reduced RH{sup 0} sites is necessary for the formation of both reduction products. In the absence of oxygen in the feed, surface isocyanate species are also observed under reaction conditions. Their formation requires the presence of adjacent Rh{sup 0}-CO and reduced Rh{sup 0} sites. Although these species are favored under conditions in which NO conversion to reduction products is observed, there is no evidence that they are catalytically active species.
[Studies on photo-electron-chemical catalytic degradation of the malachite green].
Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming
A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds.
Fe-complex of a tetraamido macrocyclic ligand: Spectroscopic characterization and catalytic oxidation studies
NASA Astrophysics Data System (ADS)
Sullivan, Shane Z.; Ghosh, Anindya; Biris, Alexandru S.; Pulla, Sharon; Brezden, Anna M.; Collom, Samulel L.; Woods, Ross M.; Munshi, Pradip; Schnackenberg, Laura; Pierce, Brad S.; Kannarpady, Ganesh K.
This work presents the spectroscopic characterization and reaction studies of a Fe III-complex (2) of a tetraamido macrocyclic ligand (1, 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[a,g]cyclotridecene-6,7,14,16-tetraone). 2 was characterized primarily by means of EPR. In agreement with the magnetic moment ( μeff = 3.87 BM), EPR spectroscopy of 2 shows signals consistent with S = 3/2 intermediate-spin ferric-iron. Besides EPR, mass spectrometry, UV/vis spectroscopy and cyclic voltammetry were used to further characterize 2. 2 is soluble in water and activates hydrogen peroxide under ambient conditions. 2 catalytically bleaches dyes, pulp and paper effluents and oxidizes several amines to their corresponding N-oxides with high turnover number and good yields.
Molecular orbital studies of enzyme activity: catalytic mechanism of serine proteinases.
Scheiner, S; Lipscomb, W N
The catalytic activity of the serine proteinases is studied using molecular orbital methods on a model of the enzyme-substrate complex. A mechanism is employed in which Ser-195, upon donating a proton to the His-57-Asp-102 dyad, attacks the substrate to form the tetrahedral intermediate. As His-57 then donates a proton to the leaving group, the intermediate decomposes to the acyl enzyme. An analogous process takes place during deacylation, as a water molecule takes the place of Ser-195 as the nucleophile. The motility of the histidine is found to be an important factor in both steps. An attempt is made to include the effects of those atoms not explicitly included in the calculations and to compare the reaction rate of the proposed mechanism with that of the uncatalyzed hydrolysis. This mechanism is found to be in good agreement with structural and kinetic data. PMID:1061145
One-pot hydrothermal synthesis of magnetically recoverable palladium/reduced graphene oxide nanocomposites and its catalytic applications in cross-coupling reactions.
Fu, Wenzhi; Zhang, Zhuqing; Zhuang, Peiyuan; Shen, Jianfeng; Ye, Mingxin
A facile, green, economical approach was designed to deposit palladium nanoparticles on magnetic reduced graphene oxide nanosheets (Pd-Fe3O4/rGO) via a one-pot hydrothermal synthesis method. The prepared Pd-Fe3O4/rGO nanocomposites were thoroughly characterized by Transmission electron microscopy, Scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. Importantly, the highly efficient catalytic property of the as-obtained Pd-Fe3O4/rGO catalyst was demonstrated for the Suzuki-Miyaura coupling reaction and Mizoroki-Heck coupling reaction. Significantly, the Suzuki-Miyaura coupling reactions could be efficiently performed in an environmentally friendly aqueous solution with no need for further additives. Besides, the nanocomposites could be conveniently separated from reaction system with an external permanent magnet for recycling and the inherent catalytic activity of the nanocomposites did not exacerbate after six repeated applications.
Studies on green and efficient catalytic oxidation of a triazole compound
NASA Astrophysics Data System (ADS)
Luo, J.; Liu, Y. C.; Huang, K. H.; Chai, T.; Wang, J. H.; Yu, Y. W.; Yuan, J. M.; Chang, S. J.; Guo, J. H.; Zhang, J.
1-Methyl-3,5-dinitro-1,2,4-triazole is an insensitive energetic compound that can be prepared by oxidizing the nitrate salt of 1-methylguanazole. The influence of the reaction time, reaction temperature, reactant ratio, feeding method and catalytic oxidation method on the yield were discussed. The results show that the optimum reaction conditions are as follows: mass ratio of sodium tungstate to nitrate salt to 1-methylguanazole, 4:4.4; time, 5.5h; and temperature, 65-75°C. The yield of this oxidation reaction reached 51.36%.
Asymmetric Catalytic aza-Morita-Baylis-Hillman Reaction for the Synthesis of 3-Substituted-3-Aminooxindoles with Chiral Quaternary Carbon Centers
Hu, Fang-Le; Wei, Yin; Shi, Min; Pindi, Suresh; Li, Guigen
Asymmetric catalytic aza-Morita-Baylis-Hillman (aza-MBH) reaction of isatin-derived ketimines with MVK has been established by using chiral amino and phosphino catalysts. The reaction resulted in biomedically important 3-substituted 3-amino-2-oxindoles in good yields (>80% for most cases) and excellent enantioselectivity (90–99%ee). Twenty-eight cases assembled with chiral quaternary stereogenic centers have been examined under convenient systems. PMID:23407608
Structural Basis on the Catalytic Reaction Mechanism of Novel 1,2-Alpha L-Fucosidase (AFCA) From Bifidobacterium Bifidum
Nagae, M.; Tsuchiya, A.; Katayama, T.; Yamamoto, K.; Wakatsuki, S.; Kato, R.
1,2-alpha-L-fucosidase (AfcA), which hydrolyzes the glycosidic linkage of Fucalpha1-2Gal via an inverting mechanism, was recently isolated from Bifidobacterium bifidum and classified as the first member of the novel glycoside hydrolase family 95. To better understand the molecular mechanism of this enzyme, we determined the x-ray crystal structures of the AfcA catalytic (Fuc) domain in unliganded and complexed forms with deoxyfuconojirimycin (inhibitor), 2'-fucosyllactose (substrate), and L-fucose and lactose (products) at 1.12-2.10 A resolution. The AfcA Fuc domain is composed of four regions, an N-terminal beta region, a helical linker, an (alpha/alpha)6 helical barrel domain, and a C-terminal beta region, and this arrangement is similar to bacterial phosphorylases. In the complex structures, the ligands were buried in the central cavity of the helical barrel domain. Structural analyses in combination with mutational experiments revealed that the highly conserved Glu566 probably acts as a general acid catalyst. However, no carboxylic acid residue is found at the appropriate position for a general base catalyst. Instead, a water molecule stabilized by Asn423 in the substrate-bound complex is suitably located to perform a nucleophilic attack on the C1 atom of L-fucose moiety in 2'-fucosyllactose, and its location is nearly identical near the O1 atom of beta-L-fucose in the products-bound complex. Based on these data, we propose and discuss a novel catalytic reaction mechanism of AfcA.
Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.
Denmark, Scott E; Heemstra, John R
The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.
Fuel-rich, catalytic reaction experimental results. [fuel development for high-speed civil transport aircraft
NASA Technical Reports Server (NTRS)
Rollbuhler, Jim
Future aeropropulsion gas turbine combustion requirements call for operating at very high inlet temperatures, pressures, and large temperature rises. At the same time, the combustion process is to have minimum pollution effects on the environment. Aircraft gas turbine engines utilize liquid hydrocarbon fuels which are difficult to uniformly atomize and mix with combustion air. An approach for minimizing fuel related problems is to transform the liquid fuel into gaseous form prior to the completion of the combustion process. Experimentally obtained results are presented for vaporizing and partially oxidizing a liquid hydrocarbon fuel into burnable gaseous components. The presented experimental data show that 1200 to 1300 K reaction product gas, rich in hydrogen, carbon monoxide, and light-end hydrocarbons, is formed when flowing 0.3 to 0.6 fuel to air mixes through a catalyst reactor. The reaction temperatures are kept low enough that nitrogen oxides and carbon particles (soot) do not form. Results are reported for tests using different catalyst types and configurations, mass flowrates, input temperatures, and fuel to air ratios.
Electron transfer properties and catalytic competence of cytochrome b5 in the fusion protein Hmwb5-EGFP in reactions catalyzed by cytochrome P450 3A4.
Yantsevich, A V; Gilep, A A; Usanov, S A
In the present paper we describe studies on molecular mechanisms of protein-protein interactions between cytochrome P450 3A4 (CYP3A4) and cytochrome b(5), the latter being incorporated into the artificial recombinant protein Hmwb(5)-EGFP containing full-length cytochrome b(5) (functional module) and a mutant form of the green fluorescent protein EGFP (signal module) fused into a single polypeptide chain. It is shown that cytochrome b(5) within the fusion protein Hmwb(5)-EGFP can be reduced by NADPH-cytochrome P450 reductase in the presence of NADPH, the rate of reduction being dependent on solution ionic strength, indicating that the signal module does not prevent the interaction of the flavo- and hemeproteins. Interaction of cytochrome P450 3A4 and Hmwb(5)-EGFP was estimated based on spin equilibrium shift of cytochrome P450 3A4 to high-spin state in the presence of Hmwb(5)-EGFP, as well as based on steady-state fluorescence anisotropy of the EGFP component of the fusion protein in the presence of CYP3A4. The engineering of chimeric protein Hmwb(5)-EGFP gives an independent method to determine dissociation constant for the complex of cytochrome P450 and cytochrome b(5) that is less sensitive to environmental factors compared to spectrophotometric titration used before. Reconstitution of catalytic activity of cytochrome P450 3A4 in the reaction of testosterone 6beta-hydroxylation in the presence of Hmwb(5)-EGFP indicates that cytochrome b(5) in the fusion protein is able to stimulate the hydroxylation reaction. Using other fusion proteins containing either cytochrome b(5) or its hydrophilic domain to reconstitute catalytic activity of cytochrome P450 3A4 showed that the hydrophobic domain of cytochrome b(5) participates not only in hemeprotein interaction, but also in electron transfer from cytochrome b(5) to cytochrome P450.
Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research
NASA Astrophysics Data System (ADS)
Horn, R.; Ihmann, K.; Ihmann, J.; Jentoft, F. C.; Geske, M.; Taha, A.; Pelzer, K.; Schlögl, R.
A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000°C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100μm sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecular beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10ms. A detection time resolution of up to 20ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N2 and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N2 to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250°C on a Pt catalyst are presented. The detection of CH3• radicals is successfully demonstrated.
Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research
Horn, R.; Ihmann, K.; Ihmann, J.; Jentoft, F.C.; Geske, M.; Taha, A.; Pelzer, K.; Schloegl, R.
A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000 deg. C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100 {mu}m sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecular beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10 ms. A detection time resolution of up to 20 ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N{sub 2} and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N{sub 2} to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250 deg. C on a Pt catalyst are presented. The detection of CH{sub 3}{center_dot} radicals is successfully demonstrated.
Compartmentalization and Cell Division through Molecular Discreteness and Crowding in a Catalytic Reaction Network
Kamimura, Atsushi; Kaneko, Kunihiko
Explanation of the emergence of primitive cellular structures from a set of chemical reactions is necessary to unveil the origin of life and to experimentally synthesize protocells. By simulating a cellular automaton model with a two-species hypercycle, we demonstrate the reproduction of a localized cluster; that is, a protocell with a growth-division process emerges when the replication and degradation speeds of one species are respectively slower than those of the other species, because of overcrowding of molecules as a natural outcome of the replication. The protocell exhibits synchrony between its division process and replication of the minority molecule. We discuss the effects of the crowding molecule on the formation of primitive structures. The generality of this result is demonstrated through the extension of our model to a hypercycle with three molecular species, where a localized layered structure of molecules continues to divide, triggered by the replication of a minority molecule at the center. PMID:25370530
Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium
Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye
Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.
Unstable Reaction Intermediates and Hysteresis during the Catalytic Cycle of 5-Aminolevulinate Synthase
Stojanovski, Bosko M.; Hunter, Gregory A.; Jahn, Martina; Jahn, Dieter; Ferreira, Gloria C.
5-Aminolevulinate (ALA), an essential metabolite in all heme-synthesizing organisms, results from the pyridoxal 5′-phosphate (PLP)-dependent enzymatic condensation of glycine with succinyl-CoA in non-plant eukaryotes and α-proteobacteria. The predicted chemical mechanism of this ALA synthase (ALAS)-catalyzed reaction includes a short-lived glycine quinonoid intermediate and an unstable 2-amino-3-ketoadipate intermediate. Using liquid chromatography coupled with tandem mass spectrometry to analyze the products from the reaction of murine erythroid ALAS (mALAS2) with O-methylglycine and succinyl-CoA, we directly identified the chemical nature of the inherently unstable 2-amino-3-ketoadipate intermediate, which predicates the glycine quinonoid species as its precursor. With stopped-flow absorption spectroscopy, we detected and confirmed the formation of the quinonoid intermediate upon reacting glycine with ALAS. Significantly, in the absence of the succinyl-CoA substrate, the external aldimine predominates over the glycine quinonoid intermediate. When instead of glycine, l-serine was reacted with ALAS, a lag phase was observed in the progress curve for the l-serine external aldimine formation, indicating a hysteretic behavior in ALAS. Hysteresis was not detected in the T148A-catalyzed l-serine external aldimine formation. These results with T148A, a mALAS2 variant, which, in contrast to wild-type mALAS2, is active with l-serine, suggest that active site Thr-148 modulates ALAS strict amino acid substrate specificity. The rate of ALA release is also controlled by a hysteretic kinetic mechanism (observed as a lag in the ALA external aldimine formation progress curve), consistent with conformational changes governing the dissociation of ALA from ALAS. PMID:24920668
Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction
Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.
A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.
From biodiversity to catalytic diversity: how to control the reaction mechanism by the nature of metallophytes.
Escande, Vincent; Olszewski, Tomasz K; Grison, Claude
Phytoextraction is widely used for the reclamation of degraded sites, particularly to remove trace metals from contaminated soils. Whereas this technique demonstrates several advantages, the biomass resulting from phytoextraction processes is highly enriched in metallic elements and constitutes therefore a problematic waste. We show here that this biomass can be used for the preparation of novel polymetallic extracts, with high potential as catalysts or reagents in organic synthesis. This new concept of ecocatalysis constitutes an innovative recycling of metallic elements whose current known reserves could be exhausted in the coming decades. The ecocatalysts Eco-Zn and Eco-Ni prepared respectively from Zn and Ni hyperaccumulating plants display two distinct chemical reactivities, starting from the same substrates. Eco-Zn led to the formation of esters of commercial interest for the fragrance industry, following a hydro-acyloxy-addition reaction pathway. In contrast, Eco-Ni afforded chlorinated products thank to the hydrochlorination of alkenes. Both ecocatalysts allowed the synthesis of valuable products in high yields through methodologies in line with the spirit of sustainable chemistry.
Study of flame quenching and near-wall combustion of lean burn fuel-air mixture in a catalytically activated spark-ignited lean burn engine
Nedunchezhian, N.; Dhandapani, S.
A study of the catalytic activation of charge near the combustion chamber wall and of the flame quenching phenomenon was carried out to identify whether flame quenches due to catalytic activation or due to thermal quenching. It was found that (1) the diffusion rate of fuel into the boundary sublayer limits the catalytic surface reaction rate during combustion; (2) the results of the present flame quench model indicate that the flame quenches due to the heat loss to walls, and the depletion of fuel due to the catalyst coated on the combustion chamber walls does not affect flame quenching; (3) the catalysts coated on the combustion chamber surface do not contribute increased hydrocarbon emissions, but actually reduce them; (4) each catalyst has a specific surface temperature, at which the Damkoehler number for surface reaction is unity.
Physical organic studies of organometallic reactions
Bergman, Robert G.
The mechanisms of reactions of organotransition metal complexes have only begun to be understood in detail during the last ten years. The complementary interaction of techniques and concepts developed earlier in studies of organic reaction mechanisms, with those commonly used in inorganic chetnistry, has played a crucial role in helping to elucidate organor.1etall.ic reaction mechanisms. A few systems in which this interaction has proved especially fruitful are discussed in this article.
A dual arylboronic acid--aminothiourea catalytic system for the asymmetric intramolecular hetero-Michael reaction of α,β-unsaturated carboxylic acids.
Azuma, Takumi; Murata, Akihiro; Kobayashi, Yusuke; Inokuma, Tsubasa; Takemoto, Yoshiji
A bifunctional aminoboronic acid has been used to facilitate for the first time the intramolecular aza- and oxa-Michael reactions of α,β-unsaturated carboxylic acids. The combination of an arylboronic acid with a chiral aminothiourea allowed for these reactions to proceed successfully in an enantioselective manner to afford the desired heterocycles in high yields and ee's (up to 96% ee). The overall utility of this dual catalytic system was demonstrated by a one-pot enantioselective synthesis of (+)-erythrococcamide B, which proceeded via sequential Michael and amidation reactions.
Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction
NASA Astrophysics Data System (ADS)
Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian; Shen, Yuhua
Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) -doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m2/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and addresses the disposal issue of waste biomass simultaneously for environment clean.
Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction
NASA Astrophysics Data System (ADS)
Gomes, Ruth; Dutta, Saikat; Bhaumik, Asim
A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.
Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction
Gomes, Ruth; Bhaumik, Asim; Dutta, Saikat
A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.
Synthesis, characterization, crystal structure determination and catalytic activity in epoxidation reaction of two new oxidovanadium(IV) Schiff base complexes
NASA Astrophysics Data System (ADS)
Tahmasebi, Vida; Grivani, Gholamhossein; Bruno, Giuseppe
The five coordinated vanadium(IV) Schiff base complexes of VOL1 (1) and VOL2 (2), HL1 = 2-{(E)-[2-bromoethyl)imino]methyl}-2- naphthol, HL2 = 2-{(E)-[2-chloroethyl)imino]methyl}-2- naphthol, have been synthesized and they were characterized by using single-crystal X-ray crystallography, elemental analysis (CHN) and FT-IR spectroscopy. Crystal structure determination of these complexes shows that the Schiff base ligands (L1 and L2) act as bidentate ligands with two phenolato oxygen atoms and two imine nitrogen atoms in the trans geometry. The coordination geometry around the vanadium(IV) is distorted square pyramidal in which vanadium(IV) is coordinated by two nitrogen and two oxygen atoms of two independent ligands in the basal plane and by one oxygen atom in the apical position. The catalytic activity of the Schiff base complexes of 1 and 2 in the epoxidation of alkenes were investigated using different reaction parameters such as solvent effect, oxidant, alkene/oxidant ratio and the catalyst amount. The results showed that in the presence of TBHP as oxidant in 1: 4 and 1:3 ratio of the cyclooctene/oxidant ratio, high epoxide yield was obtained for 1 (76%) and 2 (80%) with TON(= mole of substrate/mole of catalyst) of 27 and 28.5, respectively, in epoxidation of cyclooctene.
Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.
Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias
Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications.
Bifunctional Ag@SiO 2 /Au Nanoparticles for Probing Sequential Catalytic Reactions by Surface-Enhanced Raman Spectroscopy
Wu, Yiren; Su, Dong; Qin, Dong
Here, we report the synthesis of bifunctional Ag@SiO2/Au nanoparticles with an "islands in the sea" configuration by titrating HAuCl4 solution into an aqueous suspension of Ag@SiO2 core–shell nanocubes in the presence of NaOH, ascorbic acid, and poly(vinyl pyrrolidone) at pH 11.9. The NaOH plays an essential role in generating small pores in the SiO2 shell in situ, followed by the epitaxial deposition of Au from the Ag surface through the pores, leading to the formation of Au islands (6–12 nm in size) immersed in a SiO2 sea. Furthermore, by controlling the amount of HAuCl4 titrated into the reaction system, themore » Au islands can be made to pass through and protrude from the SiO2 shell, embracing catalytic activity toward the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. And while the Ag in the core provides a strong surface-enhanced Raman scattering activity, the SiO2 sea helps maintain the Au component as compact, isolated, and stabilized islands. The Ag@SiO2/Au nanoparticles can serve as a bifunctional probe to monitor the stepwise Au-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol by NaBH4 and Ag-catalyzed oxidation of 4-aminothiophenol to trans-4,4'-dimercaptoazobenzene by the O2 from air in the same reaction system.« less
Structural study of the X-ray-induced enzymatic reaction of octahaem cytochrome C nitrite reductase.
Trofimov, A A; Polyakov, K M; Lazarenko, V A; Popov, A N; Tikhonova, T V; Tikhonov, A V; Popov, V O
Octahaem cytochrome c nitrite reductase from the bacterium Thioalkalivibrio nitratireducens catalyzes the reduction of nitrite to ammonium and of sulfite to sulfide. The reducing properties of X-ray radiation and the high quality of the enzyme crystals allow study of the catalytic reaction of cytochrome c nitrite reductase directly in a crystal of the enzyme, with the reaction being induced by X-rays. Series of diffraction data sets with increasing absorbed dose were collected from crystals of the free form of the enzyme and its complexes with nitrite and sulfite. The corresponding structures revealed gradual changes associated with the reduction of the catalytic haems by X-rays. In the case of the nitrite complex the conversion of the nitrite ions bound in the active sites to NO species was observed, which is the beginning of the catalytic reaction. For the free form, an increase in the distance between the oxygen ligand bound to the catalytic haem and the iron ion of the haem took place. In the case of the sulfite complex no enzymatic reaction was detected, but there were changes in the arrangement of the active-site water molecules that were presumably associated with a change in the protonation state of the sulfite ions.
Study on preparation of NiOOH by a new catalytic electrolysis method
Sun Yanzhi; Pan Junqing Wan Pingyu; Liu Xiaoguang
The present paper reports a new catalytic electrolysis method to prepare NiOOH. KMnO{sub 4} is proposed as a catalyst to play the role of electron-transfer medium in the electrolysis preparation of NiOOH for the first time. Through the self-redox reaction of KMnO{sub 4}, the highly efficient electron-transfer process between the electrolyte and the electrode of the spherical Ni(OH){sub 2} is realized, thus resulting in a high electrolytic efficiency and short electrolysis time. The mechanism of catalytic electrolysis is preliminarily discussed. The experimental results show that the electrode prepared with the NiOOH powders by catalytic electrolysis offers a discharge capacity of 267 mAh g{sup -1} at a current density of 120 mA g{sup -1} and exhibits good cycling performance.
Synthesis of magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts and their catalytic performance for Knoevenagel reaction
Li, Qingyuan; Jiang, Sai; Ji, Shengfu Ammar, Muhammad; Zhang, Qingmin; Yan, Junlei
Novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 through in situ method. The structures of the catalysts were characterized by TEM, SEM, XRD, FT-IR, VSM, N{sub 2} adsorption/desorption and CO{sub 2}-TPD technology. The catalytic activity and recovery properties of the catalysts for the Knoevenagel reaction of p-chlorobenzaldehyde with malononitrile were evaluated. The results showed that the magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts had the larger surface areas, the suitable superparamagnetism, and good catalytic activity for Knoevenagel reaction. The conversion of p-chlorobenzaldehyde can reach ~98% and the selectivity of the production can reach ~99% over35.8%ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} (MZC-5) catalyst under the reaction condition of 25 °C and 4 h. The magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts also had good substrates adaptation. After reaction, the catalyst can be easily separated from the reaction mixture by an external magnet. The recovery catalyst can be reused five times and the conversion of p-chlorobenzaldehyde can be kept over 90%. - Graphical abstract: Novel magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 and the as-synthesized catalysts exhibited a good catalytic activity for the Knoevenagel reaction. - Highlights: • A series of novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized. • The catalysts had the larger surface areas and the suitable superparamagnetism. • The catalysts exhibited good catalytic activity for the Knoevenagel reaction. • After reaction the catalyst can be easily separated by an external magnet. • The recovery catalyst can be reused five times and can keep its catalytic activity.
In situ spectroscopic studies on vapor phase catalytic decomposition of dimethyl oxalate.
Hegde, Shweta; Tharpa, Kalsang; Akuri, Satyanarayana Reddy; K, Rakesh; Kumar, Ajay; Deshpande, Raj; Nair, Sreejit A
Dimethyl Oxalate (DMO) has recently gained prominence as a valuable intermediate for the production of compounds of commercial importance. The stability of DMO is poor and hence this can result in the decomposition of DMO under reaction conditions. The mechanism of DMO decomposition is however not reported and more so on catalytic surfaces. Insights into the mechanism of decomposition would help in designing catalysts for its effective molecular transformation. It is well known that DMO is sensitive to moisture, which can also be a factor contributing to its decomposition. The present work reports the results of decomposition of DMO on various catalytic materials. The materials studied consist of acidic (γ-Al2O3), basic (MgO), weakly acidic (ZnAl2O4) and neutral surfaces such as α-Al2O3 and mesoporous precipitated SiO2. Infrared spectroscopy is used to identify the nature of adsorption of the molecule on the various surfaces. The spectroscopy study is done at a temperature of 200 °C, which is the onset of gas phase decomposition of DMO. The results indicate that the stability of DMO is lower than the corresponding acid, i.e. oxalic acid. It is also one of the products of decomposition. Spectroscopic data suggest that DMO decomposition is related to surface acidity and the extent of decomposition depends on the number of surface hydroxyl groups. Decomposition was also observed on α-Al2O3, which was attributed to the residual surface hydroxyl groups. DMO decomposition to oxalic acid was not observed on the basic surface (MgO).
Impact of Lewis acids on Diels-Alder reaction reactivity: a conceptual density functional theory study.
Xia, Yue; Yin, Dulin; Rong, Chunying; Xu, Qiong; Yin, Donghong; Liu, Shubin
Density functional theory (DFT) and conceptual/chemical DFT studies are carried out in this work for the normal electron demand Diels-Alder reaction between isoprene and acrolein to compare chemical reactivity and regioselectivity of the reactants in the absence and presence of Lewis acid (LA) catalysts. A cyclic coplanar structure of acrolein-LA complex has been observed and the natural bond orbital analysis has been employed to interpret the interaction between acrolein and LAs. Reactivity indices from frontier molecular orbital energies are proved to be adequate and efficient to evaluate the catalytic property of LAs. Linear relationships have been discovered among the bond order, bond length, catalytic activation, and chemical reactivity for the systems concerned. The validity and applicability of maximum hardness principle, minimum polarizability principle, and minimum electrophilicity principle are examined and discussed in the prediction of the major regioselective isomer and the preferred reaction pathway for the reactions in the present study.
Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds
NASA Astrophysics Data System (ADS)
Koledina, K. F.; Gubaidullin, I. M.
The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.
Aaron, Timothy Mark; Shah, Minish Mahendra; Jibb, Richard John
A catalytic reactor is provided with one or more reaction zones each formed of set(s) of reaction tubes containing a catalyst to promote chemical reaction within a feed stream. The reaction tubes are of helical configuration and are arranged in a substantially coaxial relationship to form a coil-like structure. Heat exchangers and steam generators can be formed by similar tube arrangements. In such manner, the reaction zone(s) and hence, the reactor is compact and the pressure drop through components is minimized. The resultant compact form has improved heat transfer characteristics and is far easier to thermally insulate than prior art compact reactor designs. Various chemical reactions are contemplated within such coil-like structures such that as steam methane reforming followed by water-gas shift. The coil-like structures can be housed within annular chambers of a cylindrical housing that also provide flow paths for various heat exchange fluids to heat and cool components.
An experimental study for enhancing the catalytic effects of various copper forms on the oxidation of ferrous iron.
Babak, Manizhe Moradi Shahre; Goharrizi, Ataallah Soltani; Mirzaei, Mohammad; Roayaei, Emad
In this research the catalytic effect of copper compounds (ionic, oxide and oxide nanopowder) on the oxidation of ferrous iron by aeration was studied experimentally. When copper exists in solution, the oxidation rate of iron(II) will increase. The experimental results showed that the oxidation rate increases with an increasing copper concentration. From the experimental data it can be determined that the copper oxide nanopowder is the most effective for the oxidation reaction among the used copper forms. Aeration is the most economical oxidation method when water exhibits a high ferrous iron concentration.
Lagrangian Approach to Study Catalytic Fluidized Bed Reactors
NASA Astrophysics Data System (ADS)
Madi, Hossein; Hossein Madi Team; Marcelo Kaufman Rechulski Collaboration; Christian Ludwig Collaboration; Tilman Schildhauer Collaboration
Lagrangian approach of fluidized bed reactors is a method, which simulates the movement of catalyst particles (caused by the fluidization) by changing the gas composition around them. Application of such an investigation is in the analysis of the state of catalysts and surface reactions under quasi-operando conditions. The hydrodynamics of catalyst particles within a fluidized bed reactor was studied to improve a Lagrangian approach. A fluidized bed methanation employed in the production of Synthetic Natural Gas from wood was chosen as the case study. The Lagrangian perspective was modified and improved to include different particle circulation patterns, which were investigated through this study. Experiments were designed to evaluate the concepts of the model. The results indicate that the setup is able to perform the designed experiments and a good agreement between the simulation and the experimental results were observed. It has been shown that fluidized bed reactors, as opposed to fixed beds, can be used to avoid the deactivation of the methanation catalyst due to carbon deposits. Carbon deposition on the catalysts tested with the Lagrangian approach was investigated by temperature programmed oxidation (TPO) analysis of ex-situ catalyst samples. This investigation was done to identify the effects of particles velocity and their circulation patterns on the amount and type of deposited carbon on the catalyst surface. Ecole Polytechnique Federale de Lausanne(EPFL), Paul Scherrer Institute (PSI)
The interaction of catalytic metal ions and ionizing groups in equilibrium studies and in transient intermediates of metal-substituted alcohol dehydrogenases.
Maret, W; Gerber, M; Zeppezauer, M; Dunn, M F
The step of ternary complex interconversion in the reaction catalyzed by horse liver alcohol dehydrogenase has been resolved into five distinct molecular species with the aid of metal-substitution studies in combination with rapid-scanning spectrophotometry. A correlation with electronic absorption spectra at equilibrium provides structural insights into these intermediates. In contrast to NADH, NAD+ only leads to a conformational change of the protein when a negative charge has been created in the vicinity of the catalytic metal ion. This paper presents also a reevaluation of previous assignments of catalytically important groups in the light of some recent results.
Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification
Castro-Dominguez, Bernardo; Mardilovich, Ivan P.; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G.; Kazantzis, Nikolaos K.; Ma, Yi Hua
Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields. PMID:27657143
Isothermal activation of Mo2O5(2+)-ZSM-5 precursors during methane reactions: effects of reaction products on structural evolution and catalytic properties.
Lacheen, Howard S; Iglesia, Enrique
The dynamics of carburization of Mo-oxo precursors exchanged onto H-ZSM-5 strongly influence initial induction periods and steady-state rates during catalytic pyrolysis of CH4 to alkenes and arenes at 900-1000 K. The effects of co-reactants and of activating conditions were examined by on-line time-resolved mass spectrometric analysis of effluent streams using rigorous analyses to account for equilibrium effects on measured rates. Ethene co-reactants and the larger hydrocarbons to which it converts on acid sites in H-ZSM-5 led to much faster carburization of exchanged (Mo2O5)(5+) dimers and to shorter induction periods than with pure CH4 reactants, but steady-state pyrolysis rates were unchanged, indicating that CH4 and C2H4 form similar MoCx clusters during carburization of exchanged Mo-oxo precursors. H2 treatment at 973 K before CH4 reactions led to reduction of Mo(6+) species to Mo(4+), which carburize faster than (Mo2O5)(5+) precursors during initial contact with CH4. This H2 pretreatment or the use of CH4-H2 reactant mixtures did not influence steady-state pyrolysis rates, once contributions from reverse reactions were taken into account. With pure CH4 streams, (Mo2O5)(5+)-ZSM-5 converts to active MoCx clusters within zeolite channels via autocatalytic processes, in which higher hydrocarbons, initially formed during initial conversion of MoOx to MoCx structures, lead to faster carburization of downstream catalyst sections. Concurrently, H2O and CO2 formed during this incipient carburization of exchanged (Mo2O5)(5+) and unexchanged MoO3 present in trace amounts inhibit and even prevent carburization and lengthen activation periods. Activation protocols with C2H4 were also successful in the activation of more refractory high-valent metal-oxo species, such as WOx and VOx, exchanged onto H-ZSM-5. The formation of active carbide structures occurred in less than 300 s, instead of 4 ks and 16 ks for VOx and WOx samples, respectively, in pure CH4 reactants. These
Kinetic Studies of Reactions in Solution Using Fast Mass Spectrometry
to be a facile and ambient synthesis of cyclic azines (6). 2.e) Identifying catalyst arrest mechanisms in a Ruthenium -catalyzed hydroxylation...active catalyst molecules in a ruthenium catalyzed hydroxylation reaction 6 3. Monitoring Catalytic Processes on Electrode Surfaces in Real-Time
Catalytic distillation structure
Smith, Jr., Lawrence A.
Catalytic distillation structure for use in reaction distillation columns, a providing reaction sites and distillation structure and consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and being present with the catalyst component in an amount such that the catalytic distillation structure consist of at least 10 volume % open space.
Heck-type reactions of imine derivatives: a DFT study.
Li, Zhe; Fu, Yao; Zhang, Song-Lin; Guo, Qing-Xiang; Liu, Lei
The mechanism of a recently discovered intramolecular Heck-type coupling of oximes with aryl halides (Angew. Chem. Int. Ed. 2007, 46, 6325) was systematically studied by using density functional methods enhanced with a polarized continuum solvation model. The overall catalytic cycle of the reaction was found to consist of four steps: oxidative addition, migratory insertion, beta-H elimination, and catalyst regeneration, whereas an alternative base-promoted C-H activation pathway was determined to be less favorable. Migratory insertion was found to be the rate determining step in the catalytic cycle. The apparent activation barrier of migratory insertion of the (E)-oxime was +20.5 kcal mol(-1), whereas the barrier of (Z)-oxime was as high as +32.7 kcal mol(-1). However, (Z)-oxime could isomerize to form the more active (E)-oxime with the assistance of K(2)CO(3), so that both the (E)- and (Z)-oxime substrates could be transformed to the desired product. Our calculations also indicated that the Z product was predominant in the equilibrium of the isomerization of the imine double bond, which constituted the reason for the good Z-selectivity observed for the reaction. Furthermore, we examined the difference between the intermolecular Heck-type reactions of imines and of olefins. It was found that in the intermolecular Heck-type coupling of imines, the apparent activation barrier of migratory insertion was as high as +35 kcal mol(-1), which should be the main obstacle of the reaction. The analysis also revealed the main problem for the intermolecular Heck-type reactions of imines, which was that the breaking of a C=N pi bond was much more difficult than the breaking of a C=C pi bond. After systematic examination of a series of substituted imines, (Z)-N-amino imine and N-acetyl imine were found to have relatively low barriers of migratory insertion, so that they might be possible substrates for intermolecular Heck-type coupling.
Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions
NASA Astrophysics Data System (ADS)
Baran, Talat; Menteş, Ayfer
In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.
Kinetic Studies and Mechanism of Hydrogen Peroxide Catalytic Decomposition by Cu(II) Complexes with Polyelectrolytes Derived from L-Alanine and Glycylglycine
Skounas, Spyridon; Methenitis, Constantinos; Pneumatikakis, George; Morcellet, Michel
The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H2O2] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293–308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands. PMID:20721280
Kinetic Studies and Mechanism of Hydrogen Peroxide Catalytic Decomposition by Cu(II) Complexes with Polyelectrolytes Derived from L-Alanine and Glycylglycine.
Skounas, Spyridon; Methenitis, Constantinos; Pneumatikakis, George; Morcellet, Michel
The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H(2)O(2)] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293-308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands.
Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.
Nguyen, Luan; Tao, Franklin Feng
Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.
Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis
NASA Astrophysics Data System (ADS)
Nguyen, Luan; Tao, Franklin Feng
Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.
Synthesis of magnetically recyclable ZIF-8@SiO2@Fe3O4 catalysts and their catalytic performance for Knoevenagel reaction
NASA Astrophysics Data System (ADS)
Li, Qingyuan; Jiang, Sai; Ji, Shengfu; Ammar, Muhammad; Zhang, Qingmin; Yan, Junlei
Novel magnetic ZIF-8@SiO2@Fe3O4 catalysts were synthesized by encapsulating magnetic SiO2@Fe3O4 nanoparticles into ZIF-8 through in situ method. The structures of the catalysts were characterized by TEM, SEM, XRD, FT-IR, VSM, N2 adsorption/desorption and CO2-TPD technology. The catalytic activity and recovery properties of the catalysts for the Knoevenagel reaction of p-chlorobenzaldehyde with malononitrile were evaluated. The results showed that the magnetic ZIF-8@SiO2@Fe3O4 catalysts had the larger surface areas, the suitable superparamagnetism, and good catalytic activity for Knoevenagel reaction. The conversion of p-chlorobenzaldehyde can reach ~98% and the selectivity of the production can reach ~99% over35.8%ZIF-8@SiO2@Fe3O4 (MZC-5) catalyst under the reaction condition of 25 °C and 4 h. The magnetic ZIF-8@SiO2@Fe3O4 catalysts also had good substrates adaptation. After reaction, the catalyst can be easily separated from the reaction mixture by an external magnet. The recovery catalyst can be reused five times and the conversion of p-chlorobenzaldehyde can be kept over 90%.
Alpha resonant scattering for astrophysical reaction studies
Yamaguchi, H.; Kahl, D.; Nakao, T.; Wakabayashi, Y.; Kubano, S.; Hashimoto, T.; Hayakawa, S.; Kawabata, T.; Iwasa, N.; Teranishi, T.; Kwon, Y. K.; Binh, D. N.; Khiem, L. H.; Duy, N. G.
Several alpha-induced astrophysical reactions have been studied at CRIB (CNS Radioactive Ion Beam separator), which is a low-energy RI beam separator at Center for Nuclear Study (CNS) of the University of Tokyo. One of the methods to study them is the α resonant scattering using the thick-target method in inverse kinematics. Among the recent studies at CRIB, the measurement of {sup 7}Be+α resonant scattering is discussed. Based on the result of the experiment, we evaluated the contributions of high-lying resonances for the {sup 7}Be(α,γ) reaction, and proposed a new cluster band in {sup 11}C.
High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism
NASA Astrophysics Data System (ADS)
Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong
Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.
High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism
Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong
Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface. PMID:27619990
Computer simulations studies of the catalytic oxidation of carbon monoxide on platinum metals
NASA Astrophysics Data System (ADS)
Kaukonen, H.-P.; Nieminen, R. M.
The steady-state catalytic oxidation process of carbon monoxide on platinum metal surfaces is studied using two irreversible kinetic computer simulation models: (a) An extended version of the model introduced by Ziff, Gulari, and Barshad (ZGB) with the effects of CO desorption and diffusion as well as finite reaction probability taken into account. The different physical processes, diffusion and desorption are studied independently and their effect on the equilibrium window, i.e., the regime where steady CO2 formation occurs is determined. (b) An interaction model where adatom-adatom nearest-neighbor (nn) interactions are taken explicitly into account through Boltzmann terms J1, J2, and J3 which are the energies of the CO-CO, O-O, and CO-O interactions, respectively. The phase diagrams in the temperature-CO-partial pressure (T,pCO-) plane are determined for different values of the nn interactions. The behavior of the system is dependent on the sign of J1(=J2 in the simulations) as well as the sign of the difference J1-J3. There is thus a clear analogy with a two-component equilibrium lattice gas with nn interactions.
Theoretical studies of chemical reaction dynamics
Schatz, G.C.
This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.
Studies of coupled chemical and catalytic coal conversion methods
Stock, L.M.
The objective of our work is coal liquefaction under relatively mild conditions. Our attempts were to depolymerize the coal macromolecule to smaller fragments which could be more easily solubilized in conventional organic solvents. During the last few months we have been working on nonreductive C-alkylation procedures. The effectiveness of the newly introduced alkyl groups for the disruption of intemolecular hydrogen bonds and pi-pi interactions between the aromatic sheets in the coal mdcromolecule had been recognized. During the present quarter, a new approach for the depolymerization of the coal macromolecule was tried. This was aimed towards carbon-carbon bond cleavage in the presence of strong bases. Such bond cleavage reactions are well known with the alkali metals. Electron transfer reactions take place from the metals to the aromatic nuclei resulting in the formation of anion radicals (or dianions) which subsequently undergo carbon-carbon bond cleavage. In our work, instead of using the alkali metals, we have used bases to cleave the carbon-carbon bonds by base catalyzed hydrocarbon elimination reactions.Such anionic fragmentation reactions involving strong bases are not very well established. The only discrete evidence of carbon-carbon bond cleavage with bases were obtained from some earlier works of Grovenstein.
Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction
Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; ...
The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs).more » Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.« less
Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction
Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; Adzic, Radoslav R.
The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs). Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.
Response of a catalytic reaction to periodic variation of the CO pressure: increased CO2 production and dynamic phase transition.
Machado, Erik; Buendía, Gloria M; Rikvold, Per Arne; Ziff, Robert M
We present a kinetic Monte Carlo study of the dynamical response of a Ziff-Gulari-Barshad model for CO oxidation with CO desorption to periodic variation of the CO pressure. We use a square-wave periodic pressure variation with parameters that can be tuned to enhance the catalytic activity. We produce evidence that, below a critical value of the desorption rate, the driven system undergoes a dynamic phase transition between a CO2 productive phase and a nonproductive one at a critical value of the period and waveform of the pressure oscillation. At the dynamic phase transition the period-averaged CO2 production rate is significantly increased and can be used as a dynamic order parameter. We perform a finite-size scaling analysis that indicates the existence of power-law singularities for the order parameter and its fluctuations, yielding estimated critical exponent ratios beta/nu approximately 0.12 and gamma/nu approximately 1.77. These exponent ratios, together with theoretical symmetry arguments and numerical data for the fourth-order cumulant associated with the transition, give reasonable support for the hypothesis that the observed nonequilibrium dynamic phase transition is in the same universality class as the two-dimensional equilibrium Ising model.
Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings
Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; ...
Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has amore » sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.« less
Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings
Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; Belianinov, Alex
Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.
EPR Spectroscopy of catalytic systems based on nickel complexes of 1,4-diaza-1,3-butadiene (α-diimine) ligands in hydrogenation and polymerization reactions
NASA Astrophysics Data System (ADS)
Titova, Yu. Yu.; Belykh, L. B.; Schmidt, F. K.
EPR spectroscopy is used to study catalytic hydration and polymerization reaction systems based on α-diimine complexes of Ni(0) and Ni(II) with the general formula NiBr2(DAD-R) (R = -C3H7 or -CH3) or Ni(DAD-CH3)2 (DAD(-C3H7) = 1,4-bis(2,6-diiso-propylphenyl)-2,3-(dimethyl-1,4-diazabuta-1,3-diene, DAD(-CH3) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene)), in combination with Lewis acids (AlEt3, AlEt2Cl, AlEtCl2, B(F5C6)3, BF3.OEt2). Ni(I) complexes of the form (DAD-R)NiX2AlX'y(C2H5)3-y composition (an aluminum atom can be replaced by a boron atom) were identified, where R = -CH3 or -C3H7, X = Br, and X' = Cl or -C2H5 and α-diimine anion radicals are included in derivatives of aluminum or boron. Oxidation reactions of the Ni(DAD-CH3)2 complex with aluminum alkyl halides and boron derivatives with formation of paramagnetic nickel complexes are observed. It is found that there is no direct relationship between the polymerization activity of ethylene or hydration of the alkenes and the concentration of paramagnetic particles.
Kinetic study of irreversible inhibition of an enzyme consumed in the reaction it catalyses. Application to the inhibition of the puromycin reaction by spiramycin and hydroxylamine.
Dinos, G P; Coutsogeorgopoulos, C
A systematic procedure for the kinetic study of irreversible inhibition when the enzyme is consumed in the reaction which it catalyses, has been developed and analysed. Whereas in most reactions the enzymes are regenerated after each catalytic event and serve as reusable transacting effectors, in the consumed enzymes each catalytic center participates only once and there is no enzyme turnover. A systematic kinetic analysis of irreversible inhibition of these enzyme reactions is presented. Based on the algebraic criteria proposed in this work, it should be possible to evaluate either the mechanism of inhibition (complexing or non-complexing), or the type of inhibition (competitive, non-competitive, uncompetitive, mixed non-competitive). In addition, all kinetic constants involved in each case could be calculated. An experimental application of this analysis is also presented, concerning peptide bond formation in vitro. Using the puromycin reaction, which is a model reaction for the study of peptide bond formation in vitro and which follows the same kinetic law as the enzymes under study, we have found that: (i) the antibiotic spiramycin inhibits the puromycin reaction as a competitive irreversible inhibitor in a one step mechanism with an association rate constant equal to 1.3 x 10(4) M-1 s-1 and, (ii) hydroxylamine inhibits the same reaction as an irreversible non-competitive inhibitor also in a one step mechanism with a rate constant equal to 1.6 x 10(-3) M-1 s-1.
Environmentally-benign catalysts for the selective catalytic reduction of NO(x) from diesel engines: structure-activity relationship and reaction mechanism aspects.
Liu, Fudong; Yu, Yunbo; He, Hong
Selective catalytic reduction of NOx using NH3 or hydrocarbons (NH3-SCR or HC-SCR) in oxygen-rich exhaust from diesel engines remains a major challenge in environmental catalysis. The development of highly efficient, stable and environmentally-benign catalysts for SCR processes is very important for practical use. In this feature article, the structure-activity relationship of vanadium-free catalysts in the NH3-SCR reaction is discussed in detail, including Fe-, Ce-based oxide catalysts and Fe-, Cu-based zeolite catalysts, which is beneficial for catalyst redesign and activity improvement. Based on our research, a comprehensive mechanism contributing to the performance of Ag/Al2O3 in HC-SCR is provided, giving a clue to the design of a catalytic system with high efficiency.
a Nonthermal Model for Catalytic Surface Reaction of the Type A2+B2→2AB:
NASA Astrophysics Data System (ADS)
Khan, K. M.; Ahmad, W.; Iqbal, K.
The kinetics of irreversible dimer-dimer reaction of the type A2+B2→2AB has already been studied through Monte Carlo simulation via a model based on Langmuir-Hinshelwood (thermal) mechanism. The results of this study are well known. There is single transition point (yC) at yB=0.5 (where yB is partial pressure of B2 dimer in gas phase), which separates the two poisoned states from each other. Here, we have studied this reaction on the basis of a nonthermal model, which involves the precursor motion of B2 molecule. The most interesting feature of this model is that it yields a steady reactive window. The phase diagram is similar to the ZGB model. The reactive window is separated by continuous and discontinuous irreversible phase transitions. The width of the reactive window depends upon the mobility of the precursors. The dependence of production rate on partial pressure of B2 is shown by simple mathematical equations in our model. Some interesting results are observed when reaction between precursors and chemisorbed B atoms is considered.
Studies on exhaust emissions of catalytic coated spark ignition engine with adulterated gasoline.
Muralikrishna, M V S; Kishor, K; Venkata Ramana Reddy, Ch
Adulteration of automotive fuels, especially, gasoline with cheaper fuels is widespread throughout south Asia. Some adulterants decrease the performance and life of the engine and increase the emission of harmful pollutants causing environmental and health problems. The present investigation is carried out to study the exhaust emissions from a single cylinder spark ignition (SI) engine with kerosene blended gasoline with different versions of the engine, such as conventional engine and catalytic coated engine with different proportions of the kerosene ranging from 0% to 40% by volume in steps of 10% in the kerosene-gasoline blend. The catalytic coated engine used in the study has copper coating of thickness 400 microns on piston and inner surface of the cylinder head. The pollutants in the exhaust, carbon monoxide (CO) and unburnt hydrocarbons (UBHC) are measured with Netel Chromatograph CO and HC analyzer at peak load operation of the engine. The engine is provided with catalytic converter with sponge iron as a catalyst to control the pollutants from the exhaust of the engine. An air injection is also provided to the catalytic converter to further reduce the pollutants. The pollutants found to increase drastically with adulterated gasoline. Copper-coated engine with catalytic converter significantly reduced pollutants, when compared to conventional engine.
Catalytic distillation process
Smith, L.A. Jr.
A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.
Catalytic distillation process
Smith, Jr., Lawrence A.
A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.
Theoretical study of catalytic effects in micellar solutions.
Rescic, J; Vlachy, V; Bhuiyan, L B; Outhwaite, C W
The catalytic effect of charged micelles as manifested through the increased collision frequency between the counterions of an electrolyte in the presence of such micelles is explored by the Monte Carlo simulation technique and various theoretical approaches. The micelles and ions are pictured as charged hard spheres embedded in a dielectric continuum with the properties of water at 298 K with the charge on micelles varying from zero to z(m) = 50 negative elementary charges. Analytical theories such as (i) the symmetric Poisson-Boltzmann theory, (ii) the modified Poisson-Boltzmann theory, and (iii) the hypernetted-chain integral equation are applied and tested against the Monte Carlo data for micellar ions (m) with up to 50 negative charges in aqueous solution with monovalent counterions (c; z(c) = +1) and co-ions (co; z(co) = -1). The results for the counterion-counterion pair correlation function at contact, g(cc)(sigma(cc)), are calculated in a micellar concentration range from c(m) = 5 x 10(-)(6) to 0.1 mol/dm(3) with an added +1:-1 electrolyte concentration of 0.005 mol/dm(3) (for most cases), and for various model parameters. Our computations indicate that even a small concentration of a highly charged polyelectrolyte added to a +1:-1 electrolyte solution strongly increases the probability of finding two counterions in contact. This result is in agreement with experimental data. For low charge on the micelles (z(m) below -8), all the theories are in qualitative agreement with the new computer simulations. For highly charged micelles, the theories either fail to converge (the hypernetted-chain theory) or, alternatively, yield poor agreement with computer data (the symmetric Poisson-Boltzmann and modified Poisson-Boltzmann theories). The nonlinear Poisson-Boltzmann cell model results yield reasonably good agreement with computer simulations for this system.
Asymmetric Catalytic Enantio- and Diastereoselective Boron Conjugate Addition Reactions of α-Functionalized α,β-Unsaturated Carbonyl Substrates.
Xie, Jian-Bo; Lin, Siqi; Qiao, Shuo; Li, Guigen
An efficient catalytic system has been established for the asymmetric boron conjugate addition of B2pin2 onto α-functionalized (involving C, N, O, and Cl) α,β-unsaturated carbonyls under mild, neutral conditions involving Cu[(S)-(R)-ppfa]Cl, AgNTf2, and alcohols. The dual additives of AgNTf2 and alcohols were found to play crucial roles for achieving high catalytic activity and enantio- and diastereoselectivity (up to 98% ee and 70:1 dr).
Assembling formation of highly dispersed Pd nanoparticles supported 1D carbon fiber electrospun with excellent catalytic active and recyclable performance for Suzuki reaction
NASA Astrophysics Data System (ADS)
Yu, Dongdong; Bai, Jie; Wang, Junzhong; Liang, Haiou; Li, Chunping
In this work, the preparation of the palladium nanoparticles with carbon nanofibers (Pd NPs/CNFs) catalyst for the Suzuki reaction was described. In the process, palladium nanoparticles were formed in the reaction of palladium chloride and glucose. The Pd NPs/CNFs complex catalyst was prepared in subsequent calcination processes, a series of characterization revealed that the Pd NPs were well-dispersed on the surfaces of the carbon nanofibers or embedded in the carbon nanofibers. This catalyst showed high catalytic activity for the Suzuki reaction of aryl halide and aryl boronic acid in the ethanol/water (v/v = 4/3) solution, and the catalyst still had good stability after 10 cycles.
Theoretical study of catalytic mechanism for single-site water oxidation process
Lin, Xiangsong; Hu, Xiangqian; Concepcion, Javier J.; Chen, Zuofeng; Liu, Shubin; Meyer, Thomas J.; Yang, Weitao
Water oxidation is a linchpin in solar fuels formation, and catalysis by single-site ruthenium complexes has generated significant interest in this area. Combining several theoretical tools, we have studied the entire catalytic cycle of water oxidation for a single-site catalyst starting with [RuII(tpy)(bpm)(OH2)]2+ (i.e., [RuII-OH2]2+; tpy is 2,2′∶6′,2′′-terpyridine and bpm is 2,2′-bypyrimidine) as a representative example of a new class of single-site catalysts. The redox potentials and pKa calculations for the first two proton-coupled electron transfers (PCETs) from [RuII-OH2]2+ to [RuIV = O]2+ and the following electron-transfer process to [RuV = O]3+ suggest that these processes can proceed readily in acidic or weakly basic conditions. The subsequent water splitting process involves two water molecules, [RuV = O]3+ to generate [RuIII-OOH]2+, and H3O+ with a low activation barrier (∼10 kcal/mol). After the key O---O bond forming step in the single-site Ru catalysis, another PECT process oxidizes [RuIII-OOH]2+ to [RuIV-OO]2+ when the pH is lower than 3.7. Two possible forms of [RuIV-OO]2+, open and closed, can exist and interconvert with a low activation barrier (< 7 kcal/mol) due to strong spin-orbital coupling effects. In Pathway 1 at pH = 1.0, oxygen release is rate-limiting with an activation barrier ∼12 kcal/mol while the electron-transfer step from [RuIV-OO]2+ to [RuV - OO]3+ becomes rate-determining at pH = 0 (Pathway 2) with Ce(IV) as oxidant. The results of these theoretical studies with atomistic details have revealed subtle details of reaction mechanisms at several stages during the catalytic cycle. This understanding is helpful in the design of new catalysts for water oxidation. PMID:22615356
Laser Studies of Gas Phase Radical Reaction.
1nai Irvest-aator Or.G. Hancock gn; FILE CO, Contr3ctor : Oxford University . Physical Chemistry Laboratory. South Parks Road.AD-A 193 689 Oxfor o~d...HIF spectrum and study of reaction of this and the CCI radical with atoms vi) sea;rchtrr; f(r FC) 'ndlict of the 0 *CF, reaction. OXFORD UNIVERSITY -. - SOUTH...0 Awtilability Codes I Avail 'and/or Dis Spcal0 Spoo OXFORD UNIVERSITY Tt SOUTH PARKS ROAD OXFCRD OXFORD X3Z U.S. Army Contract DAJA45-85-C-0034
Molecular Beam Studies of Low Energy Reactions.
COMPLETING PORN . REPORT NUMBER 1 2. GOVT ACCESSION NO. S. RECIPIENT'S CATALOG NUMBER A D A Oaq J- 4. TITLE (And Subtitle) . TYPE OF REPORT & PERIOD COVERED...Gatlinburg, Tenn . in 1981. 2+ c) Studies were made of the charge transfer reaction Ar + Ar 4 2+ Ar + Ar at relative energies from 2 to 1000 eV. Reasons for
In situ infrared study of adsorbed species during catalytic oxidation and carbon dioxide adsorption
NASA Astrophysics Data System (ADS)
Khatri, Rajesh A.
Hydrogen is considered to be the fuel of the next century. Hydrogen can be produced by either water splitting using the solar or nuclear energy or by catalytic cracking and reforming of the fossil fuels. The water splitting process using solar energy and photovoltaics is a clean way to produce hydrogen, but it suffers from very low efficiency. A promising scheme to produce H 2 from natural gas involves following steps: (i) partial oxidation and reforming of natural gas to syngas, (ii) water-gas shift reaction to convert CO in the syngas to additional H2, (iii) separation of the H2 from CO2, and (iv) CO2 sequestration. The requirements for the above scheme are (i) a highly active coke resistant catalyst for generation of syngas by direct partial oxidation, (ii) a highly active sulfur tolerant catalyst for the water-gas shift reaction, and (iii) a low cost sorbent with high CO2 adsorption capacity for CO2 sequestration. This dissertation will address the mechanisms of partial oxidation, CO2 adsorption, and water-gas shift catalysis using in situ IR spectroscopy coupled with mass spectrometry (MS). The results from these studies will lead to a better understanding of the reaction mechanism and design of both the catalyst and sorbent for production of hydrogen with zero emissions. Partial oxidation of methane is studied over Rh/Al2O 3 catalyst to elucidate the reaction mechanism for synthesis gas formation. The product lead-lag relationship observed with in situ IR and MS results revealed that syngas is produced via a two-step reforming mechanism: the first step involving total oxidation of CH4 to CO2 and H 2O and the second step involving the reforming of unconverted methane with CO2 and H2O to form syngas. Furthermore, the Rh on the catalyst surface remains predominantly in the partially oxidized state (Rhdelta+ and Rh0). For the water-gas shift reaction, addition of Re to the Ni/CeO2 catalyst enhanced the water gas shift activity by a factor of three. The activity
Comparison of the catalytic activity for the Suzuki-Miyaura reaction of (η(5)-Cp)Pd(IPr)Cl with (η(3)-cinnamyl)Pd(IPr)(Cl) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl).
Melvin, Patrick R; Hazari, Nilay; Lant, Hannah M C; Peczak, Ian L; Shah, Hemali P
Complexes of the type (η(3)-allyl)Pd(L)(Cl) and (η(3)-indenyl)Pd(L)(Cl) are highly active precatalysts for the Suzuki-Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η(5)-Cp)Pd(L)(Cl) for Suzuki-Miyaura reactions. Here, we compare the catalytic activity of (η(5)-Cp)Pd(IPr)(Cl) (IPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene, Cp) with two commercially available catalysts (η(3)-cinnamyl)Pd(IPr)(Cl) (Cin) and (η(3)-1-t-Bu-indenyl)Pd(IPr)(Cl) ( (tBu) Ind). We show that Cp gives slightly better catalytic activity than Cin, but significantly inferior activity than (tBu) Ind. This order of activity is rationalized by comparing the rates at which the precatalysts are activated to the monoligated Pd(0) active species along with the tendency of the starting precatalysts to comproportionate with monoligated Pd(0) to form inactive Pd(I) dimers. As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (Cp (Dim) ) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently Cp (Dim) is a poor catalyst for the Suzuki-Miyaura reaction.
Steam reformer with catalytic combustor
NASA Technical Reports Server (NTRS)
Voecks, Gerald E. (Inventor)
A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.
Steam reformer with catalytic combustor
Voecks, Gerald E.
A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.
Analysis of the effect of temperature and reaction time on yields, compositions and oil quality in catalytic and non-catalytic lignin solvolysis in a formic acid/water media using experimental design.
Oregui Bengoechea, Mikel; Miletíc, Nemanja; Vogt, Mari H; Arias, Pedro L; Barth, Tanja
The catalytic solvolysis of Norway spruce (Picea abies L.) lignin in a formic acid/water media was explored at different temperatures and reaction times (283-397°C and 21-700min, respectively). Non-catalyzed experiments were compared with the effect of three different type of bifunctional catalysts (Pd/Al2O3, Rh/Al2O3 and Ru/Al2O3) and a solid Lewis acid (γ-Al2O3). We demonstrated that surface response methodology (RSM) and principal component analysis (PCA) were an adequate tool to: (i) evaluate the effect of the catalysts, temperature and reaction time in the oil yield, oil quality (H/C and O/C ratios, and Mw) and composition of the oil, (ii) establish the differences and/or similarities between the three bifunctional catalyst and (iii) to determine the role of the noble metal and the alumina support in the reaction system. In addition, the most active catalysts, Ru/Al2O3, and the optimum reaction conditions were determined (i.e. 340°C and 6h).
Enhanced Peroxide Resistance of In Vitro Mutagenized Fluorideresistant Klebsiella pneumoniae Ureases for Catalytic Buffering of Agent Decontamination Reactions
1 ENHANCED PEROXIDE RESISTANCE OF IN VITRO MUTAGENIZED FLUORIDE- RESISTANT Klebsiella pneumoniae UREASES FOR CATALYTIC BUFFERING OF...oxidative surety agent decontamination technologies. Ammonia production from urea by urease neutralizes the production of O- alkylphosphonic acids...resulting from the hydrolysis of Nerve agents such as Sarin and VX. Fluoride production from Sarin hydrolysis inhibits native urease at low mM
Porous Gold Nanoparticle-Decorated Nanoreactors Prepared from Smartly Designed Functional Polystyrene-block-Poly(d,l-Lactide) Diblock Copolymers: Toward Efficient Systems for Catalytic Cascade Reaction Processes.
Poupart, Romain; Benlahoues, Antoine; Le Droumaguet, Benjamin; Grande, Daniel
Original porous catalytic supports can be engineered via an effective and straightforward synthetic route to polystyrene-block-poly(d,l-lactide) diblock copolymer precursors displaying an acid-cleavable acetal junction between both blocks. To this purpose, we synthesized an acetal-containing heterodifunctional initiator, thus enabling to combine two different polymerization methods, i.e., first atom transfer radical polymerization (ATRP) of styrene, and then ring-opening polymerization (ROP) of d,l-lactide. Thanks to the labile nature of the acetal junction, oriented porous frameworks could be obtained upon trifluoroacetic acid-mediated cleavage of the latter, after orientation of the block copolymer nanodomains by solvent vapor annealing. The resulting porous materials bearing a reactive aldehyde function at the pore surface allowed for further chemical modification via reductive amination with amino-containing compounds, such as tetraethylenepentamine, thus leading to amine-functionalized porous polystyrene. In situ generated gold nanoparticles could then be immobilized within such functionalized porous nanoreactors, and these hybrid materials could find interesting applications in heterogeneous supported catalysis. In this regard, model catalytic reactions, including C-C homocoupling of benzeneboronic acid derivatives, hydride-mediated reduction of nitroaromatic compounds, and especially unprecedented "one-pot" cascade reactions consisting of the latter consecutive reactions from 3-nitrobenzeneboronic acid, were successfully monitored by different chromatographic and spectroscopic techniques.
Using potassium catalytic gasification to improve the performance of solid oxide direct carbon fuel cells: Experimental characterization and elementary reaction modeling
NASA Astrophysics Data System (ADS)
Yu, Xiankai; Shi, Yixiang; Wang, Hongjian; Cai, Ningsheng; Li, Chen; Ghoniem, Ahmed F.
The performance of a solid oxide electrolyte direct carbon fuel cell (SO-DCFC) is limited by the slow carbon gasification kinetics at the typical operating temperatures of cell: 650-850 °C. To overcome such limitation, potassium salt is used as a catalyst to speed up the dry carbon gasification reactions, increasing the power density by five-fold at 700-850 °C. The cell performance is shown to be sensitive to the bed temperature, emphasizing the role of gasification rates and that of CO production. Given the finite bed size, the cell performance is time-dependent as the amount of CO available changes. A reduced elementary reaction mechanism for potassium-catalyzed carbon gasification was proposed using kinetic data obtained from the experimental measurements. A comprehensive model including the catalytic gasification reactions and CO electrochemistry is used to examine the impact of the catalytic carbon gasification process on the device performance. The power density is maximum around 50% of the OCV, where carbon utilization is also near maximum. Results show that bed height and porosity impact the power density; a thicker bed maintains the power almost constant for longer times while lower porosity delivers higher power density in the early stages.
Auto-combustion synthesis, Mössbauer study and catalytic properties of copper-manganese ferrites
NASA Astrophysics Data System (ADS)
Velinov, N.; Petrova, T.; Tsoncheva, T.; Genova, I.; Koleva, K.; Kovacheva, D.; Mitov, I.
Spinel ferrites with nominal composition Cu 0.5Mn 0.5Fe 2 O 4 and different distribution of the ions are obtained by auto-combustion method. Mössbauer spectroscopy, X-ray Diffraction, Thermogravimetry-Differential Scanning Calorimetry, Scanning Electron Microscopy and catalytic test in the reaction of methanol decomposition is used for characterization of synthesized materials. The spectral results evidence that the phase composition, microstructure of the synthesized materials and the cation distribution depend on the preparation conditions. Varying the pH of the initial solution microstructure, ferrite crystallite size, cation oxidation state and distribution of ions in the in the spinel structure could be controlled. The catalytic behaviour of ferrites in the reaction of methanol decomposition also depends on the pH of the initial solution. Reduction transformations of mixed ferrites accompanied with the formation of Hägg carbide χ-Fe 5 C 2 were observed by the influence of the reaction medium.
Preparation of acid-base bifunctional mesoporous KIT-6 (KIT: Korea Advanced Institute of Science and Technology) and its catalytic performance in Knoevenagel reaction
Xu, Ling; Wang, Chunhua; Guan, Jingqi
Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH{sub 2} containing different aluminum content have been synthesized through post synthetic grafting method. The materials were characterized by X-ray diffraction (XRD), scanning electron micrographs (SEM), transmission electron micrographs (TEM), Fourier-transform infrared spectroscopy (FTIR), IR spectra of pyridine adsorption, NH{sub 3}-TPD and TG analysis. The characterization results indicated that the pore structure of KIT-6 was well kept after the addition of aluminum and grafting of aminopropyl groups. The acid amount of Al-KIT-6 increased with enhancing aluminum content. Catalytic results showed that weak acid and weak base favor the Knoevenagel reaction, while catalysts with strong acid and weak base exhibited worse catalytic behavior. - Graphical abstract: The postulated steps of mechanism for the acid-base catalyzed process are as follows: (1) the aldehyde gets activated by the surface acidic sites which allow the amine undergoes nucleophilic to attack the carbonyl carbon of benzaldehyde. (2) Water is released in the formation of imine intermediate. (3) The ethyl cyanoacetate reacts with the intermediate. (4) The benzylidene ethyl cyanoacetate is formed and the amine is regenerated. - Highlights: • KIT-6 and Al-KIT-6-NH{sub 2} with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH{sub 2} within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH{sub 2} shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction.
Study on the thermal deactivation of motorcycle catalytic converters by laboratory aging tests.
Chen, Yi-Chi; Chen, Lu-Yen; Yu, Yi-Hsien; Jeng, Fu-Tien
Catalytic converters are used to curb exhaust pollution from motorcycles in Taiwan. A number of factors, including the length of time the converter is used for and driving conditions, affect the catalysts' properties during periods of use. The goal of this study is to resolve the thermal deactivation mechanism of motorcycle catalytic converters. Fresh catalysts were treated under different aging conditions by laboratory-scale aging tests to simulate the operation conditions of motorcycle catalytic converters. The aged catalysts were characterized by analytical techniques in order to provide information for investigating deactivation phenomena. The time-dependent data of specific surface areas were subsequently used to construct kinetics of sintering at the specific temperature. According to the analytical results of the catalysts' properties, the increase in aging temperature causes an increase in pore size of the catalysts and a decrease in the specific surface area. The aged catalysts all exhibited lower performances than the fresh ones. The reduction in catalytic activity is consistent with the reduction in the loss of specific surface area. The finding of catalytic properties' dependence on temperature is consistent with the thermally activated theory. In contrast, the effect of the aging time on the specific surface area was only significant during the initial few hours. The high correlation between specific surface areas measured by the Brunauer-Emmett-Teller (BET) method and predicted by the constructed model verifies that the prediction models can predict the sintering rate reasonably under the aging conditions discussed in this study. As compared to automobile catalytic converters, the differences of structures and aging conditions are made less obvious by the deactivation phenomena of motorcycles.
Laser Studies of Gas Phase Radical Reactions.
Acremonium chrysogenum , was prepared according to the published procedure [6]. This fungal enzyme had a specific activity of 0.023 IUmg1, and was estimated to...Dist-lbitionj Avdielbiity Codes jAvail atidjor Dist 6a A-I . p -1- Laser Studies of Gas Phase Radical Reactions G. Hancock Physical Chemistry...some additional experiments concerning the formation of carbene radicals in liquid phase enzyme cleavage studies are described. Keywords Laser
Superior catalytic activity derived from a two-dimensional Ti3C2 precursor towards the hydrogen storage reaction of magnesium hydride.
Liu, Yongfeng; Du, Hufei; Zhang, Xin; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge
The superior catalytic effects derived from a 2D Ti3C2 (MXene), synthesized by the exfoliation of Ti3AlC2 powders, towards the hydrogen storage reaction of MgH2 were demonstrated. The 5 wt% Ti3C2-containing MgH2 releases 6.2 wt% H2 within 1 min at 300 °C and absorbs 6.1 wt% H2 within 30 s at 150 °C, exhibiting excellent dehydrogenation/hydrogenation kinetics.
Micro-Cu4I4-MOF: reversible iodine adsorption and catalytic properties for tandem reaction of Friedel-Crafts alkylation of indoles with acetals.
Zhu, Neng-Xiu; Zhao, Chao-Wei; Wang, Jian-Cheng; Li, Yan-An; Dong, Yu-Bin
We report a convenient approach, the first of its kind, to construct a microscale non-metal@MOF composite catalytic host-guest system for an organic tandem reaction. The reported porous Cu4I4-MOF is able to reversibly adsorb molecular iodine at room temperature. The obtained I2@Cu4I4-MOF host-guest system can be a highly heterogeneous catalyst to promote the Friedel-Crafts alkylation of indoles with acetals in a one-pot two-step fashion under solvent-free conditions at room temperature.
Immobilization of cobalt(II) Schiff base complexes on polystyrene resin and a study of their catalytic activity for the aerobic oxidation of alcohols.
Jain, Suman; Reiser, Oliver
The copper-catalyzed [3+2] azide-alkyne cycloaddition and the Staudinger ligation are readily applicable and highly efficient for the immobilization of cobalt Schiff base complexes onto polystyrene resins. Stepwise synthesis of polymer-bound Schiff bases followed by their subsequent complexation with metal ions were successfully carried out. Direct covalent attachment of preformed homogeneous cobalt Schiff base complexes to the resins was also possible. The catalytic efficiency of the so-prepared polystyrene-bound cobalt Schiff bases was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were highly efficient and even more reactive than the corresponding homogenous analogues, thus affording better yields of oxidized products within shorter reaction times. The supported catalysts could easily be recovered from the reaction mixture by simple filtration and reused for subsequent experiments with consistent catalytic activity.
[In situ FTIR spectroscopic studies of the catalytic combustion of acid red B on CuFe2O4 in the presence and absence of O2].
Wu, Rong-cheng; Qu, Jiu-hui; Yu, Yun-bo; He, Hong
The reaction process of catalytic combustion of ARB on CuFe2O4 in the presence and absence of O2 was studied by in situ DRIFT spectroscopy. The results showed that the decomposition of the sulfonic group of ARB molecule was not affected by the reaction atmosphere, but the decompositions of azo group and aromatic ring were markedly affected by the presence or absence of O2. The catalytic combustion of ARB was faster in air atmosphere than that in N2 atmosphere, and ARB could be completely oxidized to CO2 and nitrate at 300 degrees C. But in N2 atmosphere, it was very difficult for the decomposition of ARB to complete at 300 degrees C, even though air was introduced following this process. The temperature required for the rapid and complete decomposition would be as high as 500 degrees C.
Study on catalysis effect of TEPB on the curing reaction of HTPB binder system
NASA Astrophysics Data System (ADS)
Chang, S. J.; Tang, J.; Liu, X.; Yan, W.
The catalysis effect of tri (exhoxyphenyl) bismuthine (TEPB) on the curing reaction of HTPB binder system was studied by using DSC method. The curing peak temperatures of the catalyst systems were measured to calculate kinetic parameters by using Kissinger and Crane methods, respectively. Two curing reaction kinetic equations were established. The results show that TEPB has high catalytic activity and can decrease the curing temperature of HTPB binder system, down to 35 °C, in which the optimum volume of TEPB is 0.5% of HTPB binder system.
Catalytic property of fiber media supported palladium containing alloy nanoparticles and electrospun ceramic fibers biodurability study
NASA Astrophysics Data System (ADS)
Shin, Hyeon Ung
The nanoscale of the supporting fibers may provide enhancements such as restricting the migration of metal catalyst particles. In this work, palladium nanoparticle doped alumina fibers were electrospun into template submicron fibers. These fibers were calcined at temperatures between 650°C and 1150°C to vary the crystal structures of the calcined fibers with the Pd particle size. Higher calcination temperatures led to higher reaction temperatures from 250 to about 450°C for total conversion, indicating the effective reactivity of the fiber-supported catalysts decreased with increase in calcination temperature. Pd-Au alloy nanoparticle doped titania fibers were also fabricated using an electrospinning method and assembled into a fibrous porous medium structure by a vacuum molding process. In reactor tests, the fiber media with Pd-Au alloy nanoparticle catalyst had greater reactivity in conversion of NO and CO gases than that of fiber media with Pd monometallic catalyst alone, attributed to a lower activation energy of the Pd-Au catalyst particles. In carbon monoxide oxidation reaction tests, the results showed that the performance was optimal for a catalyst of composition Pd2Au1 molar ratio that was active at 125°C, which had higher dispersion of active components and better catalytic performance compared to monometallic particle Au/TiO 2 and Pd/TiO2 fiber media. Moreover, the improved reaction activity of Pd2Au1/TiO2 fiber medium was attributed to a decreased in the activation energy. Further experiments were conducted using the electrospun ceramic fibers biodurability study. The properties of nano-sized fiber structures have attracted the attention of recent research on ceramic nanostructures as nonwoven media for applications in hazardous chemical and high temperature environments. However, health and safety concerns of micro and nano scale ceramic materials have not been fully investigated. Little is known about the physicochemical effects of the properties
Influence of sp(3)-sp(2) Carbon Nanodomains on Metal/Support Interaction, Catalyst Durability, and Catalytic Activity for the Oxygen Reduction Reaction.
Campos-Roldán, Carlos A; Ramos-Sánchez, Guadalupe; Gonzalez-Huerta, Rosa G; Vargas García, Jorge R; Balbuena, Perla B; Alonso-Vante, Nicolas
In this work, platinum nanoparticles were impregnated by two different techniques, namely the carbonyl chemical route and photodeposition, onto systematically surface-modified multiwalled carbon nanotubes. The different interactions between platinum nanoparticles with sp(2)-sp(3) carbon nanodomains were investigated. The oxidation of an adsorbed monolayer of carbon monoxide, used to probe electronic catalytic modification, suggests a selective nucleation of platinum nanoparticles onto sp(2) carbon nanodomains when photodeposition synthesis is carried out. XPS attests the catalytic center electronic modification obtained by photodeposition. DFT calculations were used to determine the interaction energy of a Pt cluster with sp(2) and sp(3) carbon surfaces as well as with oxidized ones. The interaction energy and electronic structure of the platinum cluster presents dramatic changes as a function of the support surface chemistry, which also modifies its catalytic properties evaluated by the interaction with CO. The interaction energy was calculated to be 8-fold higher on sp(3) and oxidized surfaces in comparison to sp(2) domains. Accelerated Stability Test (AST) was applied only on the electronic-modified materials to evaluate the active phase degradation and their activity toward oxygen reduction reaction (ORR). The stability of photodeposited materials is correlated with the surface chemical nature of supports indicating that platinum nanoparticles supported onto multiwalled carbon nanotubes with the highest sp(2) character show the higher stability and activity toward ORR.
The mechanism of selective catalytic reduction of NOx on Cu-SSZ-13 - a computational study.
Crandell, Douglas W; Zhu, Haiyang; Yang, Xiaofan; Hochmuth, John; Baik, Mu-Hyun
The copper-exchanged aluminosilicate zeolite SSZ-13 is a leading catalyst for the selective catalytic reduction of NO. Density functional theory calculations are used to construct a complete catalytic cycle of this process paying special attention to the coordination geometries and redox states of copper. N2 can be produced in the reduction half-cycle via a nitrosamine intermediate generated from the reaction of the additive reductant NH3 with a NO(+) intermediate stabilized by the zeolite lattice. The decomposition of this nitrosamine species can be assisted by incipient Brønsted acid sites generated during catalysis. Our calculations also suggest that the reoxidation of Cu(i) to Cu(ii) requires the addition of both NO and O2. The production of a second equivalent of N2 during the oxidation half-cycle proceeds through a peroxynitrite intermediate to form a Cu-nitrite intermediate, which may react with an acid, either HNO2 or NH4(+) to close the catalytic cycle. Models of copper neutralized by an external hydroxide ligand are also examined. These calculations form a key basis for understanding the mechanism of NO reduction in Cu-SSZ-13 in order to develop strategies for rationally optimizing the performance in future experiments.
Molecular beam studies of reaction dynamics
Lee, Y.T.
The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.
Molecular beam studies of reaction dynamics
Lee, Yuan T.
The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.
A theoretical study on the reaction of ozone with aqueous iodide.
Gálvez, Óscar; Baeza-Romero, M Teresa; Sanz, Mikel; Pacios, Luis F
Atmospheric iodine chemistry plays a key role in tropospheric ozone catalytic destruction, new particle formation, and as one of the possible sinks of gaseous polar elemental mercury. Moreover, it has been recently proposed that reaction of ozone with iodide on the sea surface could be the major contributor to the chemical loss of atmospheric ozone. However, the mechanism of the reaction between aqueous iodide and ozone is not well known. The aim of this paper is to improve the understanding of such a mechanism. In this paper, an ab initio study of the reaction of aqueous iodide and ozone is presented, evaluating thermodynamic data of the different reactions proposed in previous experimental studies. In addition, the structures, energetics and possible evolution of the key IOOO(-) intermediate are discussed for the first time.
FALP and CRESU studies of ionic reactions
NASA Astrophysics Data System (ADS)
Rowe, B. R.; Canosa, A.; Le Page, V.
Results obtained from the study of ionic reactions at the University of Rennes are reviewed. A brief description of the apparatus available in our laboratory is given. The historical evolution of the flowing afterglow device is emphasized as it is directly connected to one of the major puzzling questions in dissociative recombination studies: what is the rate coefficient for the dissociative recombination of H3+ in its ground state? Special attention is given to the dissociative recombination process which until recently was the main topic studied in Rennes. A compilation of our measurements of branching ratios and rate coefficients is presented. Results from other authors are also outlined with particular attention paid to H3+. Electron attachment and ion/molecule reactions studied with the flowing afterglow Langmuir probe mass spectrometer are presented. The first results of ion/molecule reactions at very low temperatures have been recently obtained with the CRESU apparatus available in Rennes. Comparison with measurements carried out in Meudon at lower pressures is made and discussed.
Theoretical Studies of the HO/HO2 Catalytic Cycle for Ozone Destruction
NASA Technical Reports Server (NTRS)
Walch, Stephen P.; Langhoff, Steve R. (Technical Monitor)
Recently it has been determined that the HO/HO2 catalytic cycle accounts for nearly one-half of the total ozone depletion in the lower stratosphere. The catalytic cycle is: (1) HO + O3 yields HO2 + O2; (2) HO2 + O3 yields HO + O2 + O2. The net reaction is 2O3 yields 3O2. The rate limiting step in this process is the reaction of HO2 with ozone. There is a problem extending the experimental measurement of the rate of this reaction over the range 233-400 K down to stratospheric temperatures of 210-220 K. Therefore we have undertaken a project to determine the temperature dependence of the rate constant for this reaction in the low temperature region. The first step in this project, which is described in this poster, is the determination of the relevant potential energy surfaces. The calculations use CASSCF/derivative methods to define the pathways followed by CASSCF/ACPF to determine the energetics. The HO + O3 reaction is found to proceed through an HO4 complex, which is unstable with respect to HO2 + O2. The HO2 +O3 reaction is more complex. One pathway, which has been characterized, is the formation of an HO5 complex which decomposes to HO3 + O2 and subsequently to HO + O2 + O2. Another pathway, which is believed to also play a role, is hydrogen abstraction to give O2 + HO3 and subsequent decomposition of HO3 to HO + O2. Isotopic labeling experiments indicate that the later pathway is dominant. However, so far attempts to locate the saddle point for this pathway have not been successful. We have also characterized the potential energy surfaces for a number of species involved in these reactions, including HO3 and triplet O4. The triplet O4 species is probably involved in the reaction of vibrationally excited O2 with ground state O2 leading to O3 + O. The latter reaction is believed to be important as an additional source of stratospheric ozone.
Computational Study of a Model System of Enzyme-Mediated [4+2] Cycloaddition Reaction
A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reac-tion was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation. PMID:25853669
Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems
Contreras, Anthony Marshall
In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.
A General Catalytic Enantioselective Transfer Hydrogenation Reaction of β,β-Disubstituted Nitroalkenes Promoted by a Simple Organocatalyst.
Bernardi, Luca; Fochi, Mariafrancesca
Given its synthetic relevance, the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes has received a great deal of attention. Several bio-, metal-, and organo-catalytic methods have been developed, which however are usually applicable to single classes of nitroalkene substrates. In this paper, we present an account of our previous work on this transformation, which implemented with new disclosures and mechanistic insights results in a very general protocol for nitroalkene reductions. The proposed methodology is characterized by (i) a remarkably broad scope encompassing various nitroalkene classes; (ii) Hantzsch esters as convenient (on a preparative scale) hydrogen surrogates; (iii) a simple and commercially available thiourea as catalyst; (iv) user-friendly procedures. Overall, the proposed protocol gives a practical dimension to the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes, offering a useful and general platform for the preparation of nitroalkanes bearing a stereogenic center at the β-position in a highly enantioenriched form. A transition state model derived from control kinetic experiments combined with literature data is proposed and discussed. This model accounts and justifies the observed experimental results.
Silver nanocluster catalytic microreactors for water purification
NASA Astrophysics Data System (ADS)
Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.
A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.
On the structural context and identification of enzyme catalytic residues.
Chien, Yu-Tung; Huang, Shao-Wei
Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.
On the Structural Context and Identification of Enzyme Catalytic Residues
Chien, Yu-Tung; Huang, Shao-Wei
Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods. PMID:23484160
Epitaxial Growth of Multimetallic Pd@PtM (M = Ni, Rh, Ru) Core-Shell Nanoplates Realized by in Situ-Produced CO from Interfacial Catalytic Reactions.
Yan, Yucong; Shan, Hao; Li, Ge; Xiao, Fan; Jiang, Yingying; Yan, Youyi; Jin, Chuanhong; Zhang, Hui; Wu, Jianbo; Yang, Deren
Pt-based multimetallic core-shell nanoplates have received great attention as advanced catalysts, but the synthesis is still challenging. Here we report the synthesis of multimetallic Pd@PtM (M = Ni, Rh, Ru) nanoplates including Pd@Pt nanoplates, in which Pt or Pt alloy shells with controlled thickness epitaxially grow on plate-like Pd seeds. The key to achieve high-quality Pt-based multimetallic nanoplates is in situ generation of CO through interfacial catalytic reactions associated with Pd nanoplates and benzyl alcohol. In addition, the accurate control in a trace amount of CO is also of great importance for conformal growth of multimetallic core-shell nanoplates. The Pd@PtNi nanoplates exhibit substantially improved activity and stability for methanol oxidation reaction (MOR) compared to the Pd@Pt nanoplates and commercial Pt catalysts due to the advantages arising from plate-like, core-shell, and alloy structures.
Spectrophotometric reaction rate method for the determination of trace amounts of vanadium(V) by its catalytic effect on the oxidation of Nile blue with bromate
Ensafi, A.A.; Amini, M.K.; Mazloum, M.
A kinetic spectrophotometric method for the determination of trace amounts of vanadium(V) is described. It is based on the catalytic action of this ion on the oxidation of Nile blue by bromate, which yields a colorless product in acidic media. The reaction is followed spectrophotometrically by measuring the rate of decrease in absorbance at 585 nm and 30 C. A fixed time method of 4.0 min from initiation of the reaction was used. Vanadium(V) in the range of 0.004--0.520 {micro}g/ml can be determined. The proposed method is hardly subject to interference. The parameters affecting the sensitivity were optimized. The proposed method was used for the determination of vanadium in water and in milk samples.
The catalytic effect of water, water dimers and water trimers on H2S + (3)O2 formation by the HO2 + HS reaction under tropospheric conditions.
Zhang, Tianlei; Yang, Chen; Feng, Xukai; Kang, Jiaxin; Song, Liang; Lu, Yousong; Wang, Zhiyin; Xu, Qiong; Wang, Wenliang; Wang, Zhuqing
In this article, the reaction mechanisms of H2S + (3)O2 formation by the HO2 + HS reaction without and with catalyst X (X = H2O, (H2O)2 and (H2O)3) have been investigated theoretically at the CCSD(T)/6-311++G(3df,2pd)//B3LYP/6-311+G(2df,2p) level of theory, coupled with rate constant calculations by using conventional transition state theory. Our results show that in the presence of catalyst X (X = H2O, (H2O)2 and (H2O)3) into the channel of H2S + (3)O2 formation, the reactions between the SH radical and HO2(H2O)n (n = 1-3) complexes are more favorable than the corresponding reactions of the HO2 radical with HS(H2O)n (n = 1-3) complexes due to the lower barrier of the former reactions and the higher concentrations of HO2(H2O)n (n = 1-3) complexes. Meanwhile, the catalytic effect of water, water dimers and water trimers is mainly taken from the contribution of a single water vapor molecule, since the total effective rate constant of HO2H2O + HS and H2OHO2 + HS reactions was, respectively, larger by 7-9 and 9-12 orders of magnitude than that of SH + HO2(H2O)2 and SH + HO2(H2O)3 reactions. Besides, the enhancement factor of water vapor is only 0.37% at 240 K, while at high temperatures, such as 425 K, the positive water vapor effect is enhanced up to 38.00%, indicating that at high temperatures the positive water effect is obvious under atmospheric conditions. Overall, these results show how water and water clusters catalyze the gas phase reactions under atmospheric conditions.
Spectrophotometric evaluation of surface morphology dependent catalytic activity of biosynthesized silver and gold nanoparticles using UV-vis spectra: A comparative kinetic study
NASA Astrophysics Data System (ADS)
Ankamwar, Balaprasad; Kamble, Vaishali; Sur, Ujjal Kumar; Santra, Chittaranjan
The development of eco-friendly and cost-effective synthetic protocol for the preparation of nanomaterials, especially metal nanoparticles is an emerging area of research in nanotechnology. These metal nanoparticles, especially silver can play a crucial role in various catalytic reactions. The biosynthesized silver nanoparticles described here was very stable up to 6 months and can be further exploited as an effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. The silver nanoparticles were utilized as an efficient surface-enhanced Raman scattering (SERS) active substrate using Rhodamine 6G as Raman probe molecule. We have also carried out systematic comparative studies on the catalytic efficiency of both silver and gold nanoparticles using UV-vis spectra to monitor the above reaction spectrophotometrically. We find that the reaction follows pseudo-first order kinetics and the catalytic activity can be explained by a simple model based on Langmuir-Hinshelwood mechanism for heterogeneous catalysis. We also find that silver nanoparticles are more efficient as a catalyst compare to gold nanoparticles in the reduction of 4-nitrophenol to 4-aminophenol, which can be explained by the morphology of the nanoparticles as determined by transmission electron microscopy.
Exploring reaction pathways for O-GlcNAc transferase catalysis. A string method study.
Kumari, Manju; Kozmon, Stanislav; Kulhánek, Petr; Štepán, Jakub; Tvaroška, Igor; Koča, Jaroslav
The inverting O-GlcNAc glycosyltransferase (OGT) is an important post-translation enzyme, which catalyzes the transfer of N-acetylglucosamine from UDP-N-acetylglucosamine (UDP-GlcNAc) to the hydroxyl group of the Ser/Thr of cytoplasmic, nuclear, and mitochondrial proteins. In the past, three different catalytic bases were proposed for the reaction: His498, α-phosphate, and Asp554. In this study, we used hybrid quantum mechanics/molecular mechanics (QM/MM) Car-Parrinello molecular dynamics to investigate reaction paths using α-phosphate and Asp554 as the catalytic bases. The string method was used to calculate the free-energy reaction profiles of the tested mechanisms. During the investigations, an additional mechanism was observed. In this mechanism, a proton is transferred to α-phosphate via a water molecule. Our calculations show that the mechanism with α-phosphate acting as the base is favorable. This reaction has a rate-limiting free-energy barrier of 23.5 kcal/mol, whereas reactions utilizing Asp554 and water-assisted α-phosphate have barriers of 41.7 and 40.9 kcal/mol, respectively. Our simulations provide a new insight into the catalysis of OGT and may thus guide rational drug design of transition-state analogue inhibitors with potential therapeutic use.
Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation
NASA Astrophysics Data System (ADS)
Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi
Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol-1), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.
A novel green one-step synthesis of silver nanoparticles using chitosan: catalytic activity and antimicrobial studies
NASA Astrophysics Data System (ADS)
Venkatesham, Maragoni; Ayodhya, Dasari; Madhusudhan, Alle; Veera Babu, Nagati; Veerabhadram, Guttena
Stable silver nanoparticles were synthesized using chitosan acting as both reducing and stabilizing agent without using any toxic chemicals. This reaction was carried out in an autoclave at a pressure of 15 psi and 120 °C temperature by varying the time. The influence of different parameters such as time, change of concentration of silver nitrate and concentration of chitosan on the formation of silver nanoparticles were studied. The synthesized silver nanoparticles were characterized by UV-visible spectroscopy, Fourier transform infrared, X-ray diffraction and transmission electron microscopy. The results of catalytic reduction of 4-nitrophenol by sodium borohydride in the presence of green synthesized silver nanoparticles were presented. The antimicrobial activity of silver nanoparticles was tested against Escherichia coli and Micrococcus luteus and was found to be possessing inhibiting property.
Catalytic distillation structure
Smith, L.A. Jr.
Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.
Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays
Grunes, Jeffrey Benjamin
In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al2O3) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum
Activation of organozinc reagents with t-Bu-P4 base for transition metal-free catalytic SN2' reaction.
Kobayashi, Koji; Ueno, Masahiro; Naka, Hiroshi; Kondo, Yoshinori
The t-Bu-P4 base was found to be an excellent catalyst for activating organozinc reagents and was used to promote the S(N)2' reaction of alpha,beta-unsaturated esters bearing a gamma-chloride using various organozinc reagents: these reactions proceeded in high yields with excellent chemo-and regioselectivity.
Catalytic asymmetric tandem Friedel-Crafts alkylation/Michael addition reaction for the synthesis of highly functionalized chromans.
Peng, Jiahuan; Du, Da-Ming
The enantioselective tandem Friedel-Crafts alkylation/Michael addition reaction of indoles with nitroolefin enoates catalyzed by a diphenylamine-linked bis(oxazoline)-Zn(OTf)2 complex was investigated. This tandem reaction afforded functionalized chiral chromans in good yields with moderate to high stereoselectivities (up to 95:5 dr, up to 99% ee).
Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations
NASA Astrophysics Data System (ADS)
Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul
High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.
Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations
Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul
High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results. PMID:28120896
Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations.
Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul
High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.
Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction
NASA Astrophysics Data System (ADS)
Park, Jisu; Cha, Song-Hyun; Cho, Seonho; Park, Youmie
In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of -41.98 mV for the gold nanoparticles and -53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV-visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7-99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.
DRIFT study of manganese/ titania-based catalysts for low-temperature selective catalytic reduction of NO with NH3.
Wu, Zhongbiao; Jiang, Boqiong; Liu, Yue; Wang, Haiqiang; Jin, Ruiben
Manganese oxides and iron-manganese oxides supported on TiO2 were prepared by the sol-gel method and used for low-temperature selective catalytic reduction (SCR) of NO with NH3. Base on the previous study, Mn(0.4)/ TiO2 and Fe(0.1)-Mn(0.4)/TiO2 were then selected to carry out the in situ diffuse reflectance infrared transform spectroscopy (DRIFT) investigation for revealing the reaction mechanism. The DRIFT spectroscopy for the adsorption of NH3 indicated the presence of coordinated NH3 and NH4+ on both of the two catalysts. When NO was introduced, the coordinated NH3 on the catalyst surface was consumed rapidly, indicating these species could react with NO effectively. When NH3 was introduced into the sample preadsorbed with NO + O2, SCR reaction would not proceed on Mn(0.4)/TiO2. However, for Fe(0.1)-Mn(0.4)/ TiO2 the bands due to coordinated NH3 on Fe2O3 were formed. Simultaneously, the bidentate nitrates were transformed to monodentate nitrates and NH4+ was detected. And NO2 from the oxidation of NO on catalyst could react with NH4+ leading to the reduction of NO. Therefore, it was suggested that the SCR reaction on Fe(0.1)-Mn(0.4)/TiO2 could also take place in a different way from the reactions on Mn(0.4)/TiO2 proposed by other researchers. Furthermore, the SCR reaction steps for these two kinds of catalysts were proposed.
A pulse-radiolysis study of the catalytic mechanism of the iron-containing superoxide dismutase from Photobacterium leiognathi.
Lavelle, F; McAdam, M E; Fielden, E M; Roberts, P B
The mechanism of the enzymic reaction of an iron-containing superoxide dismutase purified from the marine bacterium Photobacterium leiognathi was studied by using pulse radiolysis. Measurements of activity were done with two different preparations of enzyme containing either 1.6 or 1.15 g-atom of iron/mol. In both cases, identical values of the second-order rate constant for reaction between superoxide dismutase and the superoxide ion in the pH range 6.2-9.0 (k=5.5 X 10(8) M-1-S-1 at pH 8.0) were found. As with the bovine erythrocuprein, there was no evidence for substrate saturation. The effects of reducing agents (H2O2, sodium ascorbate or CO2 radicals) on the visible and the electron-paramagnetic-resonance spectra of the superoxide dismutase containing 1.6 g-atom of ferric iron/mol indicate that this enzyme contains two different types of iron. Turnover experiments demonstrate that only that fraction of the ferric iron that is reduced by H2O2 is involved in the catalysis, being alternately oxidized and reduced by O2; both the oxidation and the reduction steps have a rate constant equal to that measured under turnover conditions. These results are interpreted by assuming that the superoxide dismutase isolated from the organism contains 1 g-atom of catalytic iron/mol and a variable amount of non-catalytic iron. This interpretation is discused in relation to the stoicheiometry reported for iron-containing superoxide dismutases prepared from several other organisms.
Ab initio study for the hydrogen abstraction reactions on toluene and tetralin.
Beste, Ariana; Harrison, Robert J; Britt, Phillip F; Buchanan III, A C
Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are investigated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE pyrolysis through comparison of the reaction barriers with reliable experimental values. We used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. We recomputed selected energy barriers at the B3LYP geometries with the coupled cluster singles and doubles (CCSD) method. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment and the corresponding CCSD energy barriers. The flat potential energy surface around the saddle points causes numerical inaccuracies. We observe the break down of the harmonic approximation in the calculation of low frequencies.
Study of Single Catalytic Events at Copper-in-Charcoal: Localization of Click Activity Through Subdiffraction Observation of Single Catalytic Events.
Decan, Matthew R; Scaiano, Juan C
Single molecule fluorescence microscopy reveals that copper-in-charcoal--a high performance click catalyst- has remarkably few catalytic sites, with 90% of the charcoal particles being inactive, and for the catalytic ones the active sites represent a minute fraction (∼0.003%) of the surface. The intermittent nature of the catalytic events enables subdiffraction resolution and mapping of the catalytic sites.
Allosteric modulation of the RNA polymerase catalytic reaction is an essential component of transcription control by rifamycins.
Artsimovitch, Irina; Vassylyeva, Marina N; Svetlov, Dmitri; Svetlov, Vladimir; Perederina, Anna; Igarashi, Noriyuki; Matsugaki, Naohiro; Wakatsuki, Soichi; Tahirov, Tahir H; Vassylyev, Dmitry G
Rifamycins, the clinically important antibiotics, target bacterial RNA polymerase (RNAP). A proposed mechanism in which rifamycins sterically block the extension of nascent RNA beyond three nucleotides does not alone explain why certain RNAP mutations confer resistance to some but not other rifamycins. Here we show that unlike rifampicin and rifapentin, and contradictory to the steric model, rifabutin inhibits formation of the first and second phosphodiester bonds. We report 2.5 A resolution structures of rifabutin and rifapentin complexed with the Thermus thermophilus RNAP holoenzyme. The structures reveal functionally important distinct interactions of antibiotics with the initiation sigma factor. Strikingly, both complexes lack the catalytic Mg2+ ion observed in the apo-holoenzyme, whereas an increase in Mg2+ concentration confers resistance to rifamycins. We propose that a rifamycin-induced signal is transmitted over approximately 19 A to the RNAP active site to slow down catalysis. Based on structural predictions, we designed enzyme substitutions that apparently interrupt this allosteric signal.
Experimental studies of gas-aerosol reactions
NASA Astrophysics Data System (ADS)
Gupta, Anand
The aqueous phase oxidation of SO2 by H2O2 is believed to the principle mechanism for atmospheric sulfate formation in cloud droplets. However, no studies in noncloud aerosol systems have been reported. The objective is to quantify the importance of the noncloud liquid phase reactions of SO2 by H2O2 in the atmosphere. Growth rates of submicron droplets exposed to SO2 and H2O2 were measured using the tandem differential mobility analyzer (TDMA) technique (Rader and McMurry, 1986). The technique uses differential mobility analyzers (DMA's) to generate monodisperse particles and to measure particle size after the reaction. To facilitate submicron monodisperse droplet production with the DMA, a low-ion-concentration charter capable of generating singly charged particles up to 1.0 microns was developed and experimentally evaluated. The experiments were performed using dry and deliquesced (NH4)2SO4 particles with SO2 and H2O2 concentrations from 0-860 ppb and 0-150 ppb, respectively. No growth was observed for dry particles. For droplets greater than or equal to 0.3 microns, the fractional diameter growth was independent of particle size and for droplets less than or equal to 0.2 microns, it decreased as particle size decreased. The observed decrease is due to NH3 evaporation. As ammonia evaporates, droplet pH decreases causing the oxidation rate to decrease, leading to a lower growth rate. To predict the size-dependent growth rates, a theoretical model was developed using solution thermodynamics, gas/particle equilibrium, and chemical kinetics. The experimental and theoretical results are in reasonable agreement. For dry (NH4)2SO4 particles exposed to SO2, H2O2, NH3, and H2O vapor, surface reaction-controlled growth was observed. Particle growth was very sensitive to particle composition. No growth was observed for Polystyrene latex particles, whereas (NH4)2SO4 particles doped with catalysts (Fe(2+), Fe(3+), Mn(2+) and Cu(2+)) in a molar ratio of 1:500 grew slower than
Experimental Studies of Gas-Aerosol Reactions
NASA Astrophysics Data System (ADS)
Gupta, Anand
The aqueous phase oxidation of SO_2 by H_2O_2 is believed to be the principle mechanism for atmospheric sulfate formation in cloud droplets. However, no studies in noncloud aerosol systems have been reported. The objective of this thesis is to quantify the importance of the noncloud liquid phase reactions of SO_2 by H_2O_2 in the atmosphere. In this thesis growth rates of submicron droplets exposed to SO_2 and H_2 O_2 were measured using the tandem differential mobility analyzer (TDMA) technique (Rader and McMurry, 1986). The technique uses differential mobility analyzers (DMAs) to generate monodisperse particles and to measure particle size after the reaction. To facilitate submicron monodisperse droplet production with the DMA, a low-ion-concentration charger capable of generating singly charged particles up to 1.0 μm was developed and experimentally evaluated. The experiments were performed using dry and deliquesced (NH_4)_2SO _4 particles with SO_2 and H_2O_2 concentrations from 0-860 ppb and 0-150 ppb, respectively. No growth was observed for dry particles. For droplets >=0.3 mum, the fractional diameter growth was independent of particle size and for droplets <=0.2 mum, it decreased as particle size decreased. The observed decrease is due to NH_3 evaporation. As ammonia evaporates, droplet pH decreases causing the oxidation rate to decrease, leading to a lower growth rate. To predict the size-dependent growth rates, a theoretical model was developed using solution thermodynamics, gas/particle equilibrium and chemical kinetics. The experimental and theoretical results are in reasonable agreement. For dry (NH_4) _2SO_4 particles exposed to SO_2, H_2O _2, NH_3 and H_2O vapor, surface reaction-controlled growth was observed. Particle growth was very sensitive to particle composition. No growth was observed for Polystyrene latex particles, whereas (NH_4) _2SO_4 particles doped with catalysts (Fe^{2+} , Fe^{3+}, Mn ^{2+}, Cu^{2+ }) in a molar ratio of 1:500 grew
Quantification and evaluation of kinetic bio-catalytic pathway of horseradish peroxidase in an electron mediated reaction system and its applications in plant extracts
NASA Astrophysics Data System (ADS)
Krishna, Honnur; Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Chamaraja, Nelligere A.; Aradhana, Narayan
The intermolecular coupling of 2,5-dimethoxyaniline (DMA) as mediated electron transfer reaction in presence of H2O2 and peroxidase in acetate buffer of pH 4.2 resulting green colored product having maximum absorption at λmax = 740 nm was investigated by spectrophotometer. Under optimum conditions, linearity range for the quantification of H2O2 was 2.0-288.0 μM and for peroxidase were 0.59-9.46 and 0.443-9.46 nM by kinetic and fixed-time method, respectively. The catalytic efficiency and catalytic power were KeffD = 2.354 × 105 M-1 min-1 and KpowD = 4.59 × 10-4 min-1, respectively. From the plot of d(1/Do) vs d(1/Vo) and d(1/Ho) vs d(1/Vo), Michaelis-Menten constants for DMA and H2O2were found that KmD = 1458 μM and KmHO = 301 μM. Applicability of the method was tested for peroxidase activity in some plant extracts and compared with guaiacol/peroxidase system. Regarding superiority of the method, it is suggested that DMA/peroxidase system can be a better hydrogen donor for HRP assay than guaiacol system as evident from kinetic data.
The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction
Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.
The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria
The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction
Divins, N. J.; Senanayake, S. D.; Casanovas, A.; ...
The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less
Synthesis, characterization and photo catalytic studies of the composites by tantalum oxide and zinc oxide nanorods
NASA Astrophysics Data System (ADS)
Chennakesavulu, K.; Reddy, M. Madhusudhana; Reddy, G. Ramanjaneya; Rabel, A. M.; Brijitta, J.; Vinita, V.; Sasipraba, T.; Sreeramulu, J.
In-situ synthesis of ZnO:Ta2O5 composites in basic medium by using tantalum chloride and zinc chloride as precursors. The prepared composites were characterized by Fourier Transform Infrared spectroscopy (FTIR), confocal Raman spectroscopy, diffuse reflectance UV-Vis spectrophotometer (DRS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, N2-sorption isotherms, Thermo Gravimetric Analysis (TGA), High Resolution Transmission Electron Microscope (HRTEM), X-ray Photoelectron Spectroscopy (XPS), and Field Emission Scanning Electron Microscopy (FESEM/EDS). The composite materials were used as photocatalyst in the degradation Rhodamine-B (RhB) dye under visible light irradiation. The catalytic activity and removal percentage of the dye was determined by the spectrophotometric method. This indicates the percentage of degradation was more for the ZnO:Ta2O5 composites. The kinetic parameter obeys pseudo-first order reaction. It may be due to fixed amount the catalysts and concentration of dye solution. The catalytic activity of the recycled ZnO:Ta2O5 catalyst was compared with fresh catalyst.
Brønsted acid-controlled [3 + 2] coupling reaction of quinone monoacetals with alkene nucleophiles: a catalytic system of perfluorinated acids and hydrogen bond donor for the construction of benzofurans.
Hu, Yinjun; Kamitanaka, Tohru; Mishima, Yusuke; Dohi, Toshifumi; Kita, Yasuyuki
We have developed an efficient Brønsted acid-controlled strategy for the [3 + 2] coupling reaction of quinone monoacetals (QMAs) with nucleophilic alkenes, which is triggered by the particular use of a specific acid promoter, perfluorinated acid, and a solvent, fluoroalcohol. This new coupling reaction smoothly proceeded with high regiospecificity in regard with QMAs for introducing π-nucleophiles to only the carbon α to the carbonyl group, thereby providing diverse dihydrobenzofurans and derivatives with high yields, up to quantitative, under mild conditions in short reaction times. The choice of Brønsted acid enabled us to avoid hydrolysis of the QMAs, which gives quinones, and the formation of discrete cationic species from the QMAs. Notably, further investigations in this study with regard to the acid have led to the findings that the originally stoichiometrically used acid could be reduced to a catalytic amount of 5 mol % loading or less and that the stoichiometry of the alkenes could be significantly improved down to only 1.2 equiv. The facts that only a minimal loading (5 mol %) of perfluoroterephthalic acid is required, readily available substrates can be used, and the regioselectivity can be controlled by the acid used make this coupling reaction very fascinating from a practical viewpoint.
Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.
Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba
We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.
N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd–NHC complexes: synthesis, characterization and catalytic activity in carbon–carbon bond-forming reactions
Gök, Yetkin; İlhan, İlhan Özer
Summary A series of novel benzimidazolium salts (1–4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5–8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of 1H and 13C{1H} NMR, UV–vis (for 5–8), ESI-FTICR-MS (for 2, 4, 6–8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki–Miyaura cross-coupling (for 1–8) and arylation (for 5–8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C–C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810
Synthesis of 19-oxygenated 4beta,5beta-epoxy derivatives of 16alpha-hydroxyandrostenedione as mechanistic and catalytic probes for aromatase reaction.
Numazawa, M; Yoshimura, A
4Beta,5beta-epoxy derivatives of 16alpha-hydroxyandrostenedione (2), one of the natural substrates for aromatase, and its 19-oxygenated compounds 4 and 5 were synthesized as mechanistic and catalytic probes for the enzyme reaction. Treatment of 16alpha-bromoandrostenedione (13) or its 19-hydroxy analog 19 which was prepared from 3beta-hydroxy-19-(tert-butyldimethylsiloxy)androst-5-en-17-one (16) in three steps, with H2O2 and NaOH followed by controlled alkaline hydrolysis with NaOH in aqueous pyridine stereospecifically yielded 4beta,5beta-epoxy-16alpha-ol 15 or 4beta,5beta-epoxy-16alpha,19-diol 22, respectively. Oxidation of 16beta-bromo-4beta,5beta-epoxy-19-ol 21 with pyridinium dichromate followed by controlled alkaline hydrolysis produced 4beta,5beta-epoxy-16alpha-hydroxy-19-al 24.
A study of switchgrass pyrolysis: Product variability and reaction kinetics
NASA Astrophysics Data System (ADS)
Bovee, Jonathan Matthew
Samples of the same cultivar of cave-in-rock switchgrass were harvested from plots in Frankenmuth, Roger City, Cass County, and Grand Valley, Michigan. It was determined that variation exists, between locations, among the pyrolytic compounds which can lead to variability in bio-oil and increased processing costs at bio-refineries to make hydrocarbon fuels. Washed and extractives-free switchgrass samples, which contain a lower alkali and alkaline earth metals content than untreated samples, were shown to produce lower amounts of acids, esters, furans, ketones, phenolics, and saccharides and also larger amounts of aldehydes upon pyrolysis. Although the minerals catalyzed pyrolytic reactions, there was no evidence indicating their effect on reducing the production of anhydrosugars, specifically levoglucosan. To further link minerals present in the biomass to a catalytic pathway, mathematic models were employed to determine the kinetic parameters of the switchgrass. While the calculated activation energies of switchgrass, using the FWO and KAS methods, were 227.7 and 217.8 kJ/mol, correspondingly, it was concluded that the activation energies for the switchgrass hemicellulose and cellulose peaks were 115.5 and 158.2 kJ/mol, respectively, using a modified model-fitting method. The minerals that effect the production of small molecules and levoglucosan also have an observable catalytic effect on switchgrass reaction rate, which may be quantifiable through the use of reaction kinetics so as to determine activation energy.
NH3-SCR performance of fresh and hydrothermally aged Fe-ZSM-5 in standard and fast selective catalytic reduction reactions.
Shi, Xiaoyan; Liu, Fudong; Xie, Lijuan; Shan, Wenpo; He, Hong
Hydrothermal stability is one of the challenges for the practical application of Fe-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with NH3 (NH(3)-SCR) for diesel engines. The presence of NO(3) in the exhaust gases can enhance the deNOx activity because of the fast SCR reaction. In this work, a Fe-ZSM-5 catalyst was prepared by a solid-state ion-exchange method and was hydrothermally deactivated at 800 °C in the presence of 10% H(2)O. The activity of fresh and hydrothermal aged Fe-ZSM-5 catalysts was investigated in standard SCR (NO(2)/NOx = 0) and in fast SCR with NO(2)/NOx = 0.3 and 0.5. In standard SCR, hydrothermal aging of Fe-ZSM-5 resulted in a significant decrease of low-temperature activity and a slight increase in high-temperature activity. In fast SCR, NOx conversion over aged Fe-ZSM-5 was significantly increased but was still lower than that over fresh catalyst. Additionally, production of N(2)O in fast SCR was much more apparent over aged Fe-ZSM-5 than over fresh catalyst. We propose that, in fast SCR, the rate of key reactions related to NO is slower over aged Fe-ZSM-5 than over fresh catalyst, thus increasing the probabilities of side reactions involving the formation of N(2)O.
Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions-Influence of Fe(II)/Fe(III) ratio on catalytic performance.
Rusevova, Klara; Kopinke, Frank-Dieter; Georgi, Anett
Nano-sized Fe(II, III) oxides with various Fe(II)/Fe(III) ratios were characterized and tested as catalysts for the oxidative degradation of phenol via Fenton-like reactions at neutral pH. Under conditions typically applied for wet peroxide oxidation, Fe(II) in magnetite is oxidized to Fe(III), successively converting the mineral into maghemite. The residual Fe(II) content in the catalyst core is of only minor benefit for the catalytic activity in phenol oxidation, i.e. magnetite is not superior to maghemite. Achievable reaction rates for phenol degradation appeared to be rather low, e.g. phenol half-life of about 12 h when 3 g L(-1) magnetite and 5 g L(-1) H(2)O(2) were applied. Preceding surface-reduction of maghemite by NaBH(4), leading to an over-stoichiometric Fe(II) content compared to magnetite, only enhanced the non-productive decomposition of H(2)O(2) rather than the rate of phenol degradation. Reaction rates were shown to be relatively insensitive to catalyst concentration in the range of 1-10 g L(-1), probably resulting from a scavenging of reactive species by the catalyst surface, whereby particle agglomeration seems to play a key role. Degradation experiments with various structurally distinct compounds were carried out, indicating a similar selectivity of the heterogeneous Fenton-like system to that known for oxidation with ·OH.
Synthesis and characterization of Sn/zeolite and catalytic activity test in the esterification reaction of sludge oil
NASA Astrophysics Data System (ADS)
Alimuddin, Andi Hairil; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Prawatya, Yopa Eka; Astar, Ismail; Yustira, Yudi
Synthesis of Sn-Zeolite has been made to use for esterification reaction of free fatty acids in sludge oil. Catalyst characterization was accomplished using X-Ray Diffraction (XRD), X-Ray Flourecence (XRF), and Fourier Transform Infra Red (FTIR). Catalyst Sn/zeolite was synthesized by impregnated Sn of SnCl2 into the zeolite. The amount of Sn impregnated base on the value of cation exchange capacity (CEC) of zeolites. Esterification reaction of fatty acids from sludge oil using Sn/Zeolite catalyst was did by variated the reaction time. XRD analysis results showed that the catalyst Sn/zeolite was dominated by modernit and quartz. XRF analysis results was increasing amount of Sn metal and the Si/Al ratio on Sn/zeolite catalyst along with addition of Sn metal. FTIR analysis results showed that the catalyst synthesized had Bronsted acid side (the spectrum 1639.4; 1656.7; 1654.8 cm-1) and the Lewis acid (spectrum 1400.2 and 1402.2 cm-1). The results showed that the optimum conditions of esterification reaction in 4 hours reaction time, 5% concentration of the catalyst, and molar ratio was about 1:10 with a conversion percentage of products reached 96.00%, which can be achieved with a ratio was about 4:1 between Sn and zeolite on Sn/zeolite catalyst.
Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling.
Schaefer, C; Jansen, A P J
We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.
Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling
Schaefer, C.; Jansen, A. P. J.
We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.
Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling
NASA Astrophysics Data System (ADS)
Schaefer, C.; Jansen, A. P. J.
We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.
Ruthenium(II) hydrazone Schiff base complexes: Synthesis, spectral study and catalytic applications
NASA Astrophysics Data System (ADS)
Manikandan, R.; Viswanathamurthi, P.; Muthukumar, M.
Ruthenium(II) hydrazone Schiff base complexes of the type [RuCl(CO)(B)(L)] (were B = PPh 3, AsPh 3 or Py; L = hydrazone Schiff base ligands) were synthesized from the reactions of hydrazone Schiff base ligand (obtained from isonicotinoylhydrazide and different hydroxy aldehydes) with [RuHCl(CO)(EPh 3) 2(B)] (where E = P or As; B = PPh 3, AsPh 3 or Py) in 1:1 molar ratio. All the new complexes have been characterized by analytical and spectral (FT-IR, electronic, 1H, 13C and 31P NMR) data. They have been tentatively assigned an octahedral structure. The synthesized complexes have exhibited catalytic activity for oxidation of benzyl alcohol to benzaldehyde and cyclohexanol to cyclohexanone in the presence of N-methyl morpholine N-oxide (NMO) as co-oxidant. They were also found to catalyze the transfer hydrogenation of aliphatic and aromatic ketones to alcohols in KOH/Isopropanol.
Chemical redox reactions in ES-MS: Study of electrode reactions
Zhou, Feimeng; VAn Berkel, G.J.
The authors previously demonstrated that chemical redox reactions can be used to ionize neutral commpounds for electrospray mass spectrometric (ES-MS) detection. Two different compounds, viz, C{sub 60}F{sub 48} and {beta}-carotene were used to demonstrate the utility of chemical redox reactions with on-line ES-MS for the elucidation of mechanisms of complicated electron transfer reactions and for the kinetic study of electrode reactions in which relatively short-lived intermediates are involved.
Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions.
Ayala Quezada, Alejandro; Ohara, Keisuke; Ratanawimarnwong, Nuanlaor; Nacapricha, Duangjai; Murakami, Hiroya; Teshima, Norio; Sakai, Tadao
An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures.
Treatment of aniline by catalytic wet air oxidation: comparative study over CuO/CeO2 and NiO/Al2O3.
Ersöz, Gülin; Atalay, Süheyda
The treatment of aniline by catalytic wet air oxidation (CWAO) was studied in a bubble reactor. The experiments were performed to investigate the effects of catalyst loading, temperature, reaction time, air flow rate, and pressure on aniline removal. The catalytic effects of the prepared nanostructured catalysts, CuO/CeO(2) (10% wt) and NiO/Al(2)O(3) (10% wt), on the CWAO treatment efficiency were also examined and compared. The prepared catalysts seem to be active having an aniline removal of 45.7% with CuO/CeO(2) and 41.9% with NiO/Al(2)O(3). The amount of N(2) formed was approximately the same for both of the catalysts.
Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid.
Su, Chia-Hung
The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse.
In vitro effect of H2O 2, some transition metals and hydroxyl radical produced via fenton and fenton-like reactions, on the catalytic activity of AChE and the hydrolysis of ACh.
Méndez-Garrido, Armando; Hernández-Rodríguez, Maricarmen; Zamorano-Ulloa, Rafael; Correa-Basurto, José; Mendieta-Wejebe, Jessica Elena; Ramírez-Rosales, Daniel; Rosales-Hernández, Martha Cecilia
It is well known that the principal biomolecules involved in Alzheimer's disease (AD) are acetylcholinesterase (AChE), acetylcholine (ACh) and the amyloid beta peptide of 42 amino acid residues (Aβ42). ACh plays an important role in human memory and learning, but it is susceptible to hydrolysis by AChE, while the aggregation of Aβ42 forms oligomers and fibrils, which form senile plaques in the brain. The Aβ42 oligomers are able to produce hydrogen peroxide (H2O2), which reacts with metals (Fe(2+), Cu(2+), Cr(3+), Zn(2+), and Cd(2+)) present at high concentrations in the brain of AD patients, generating the hydroxyl radical ((·)OH) via Fenton (FR) and Fenton-like (FLR) reactions. This mechanism generates high levels of free radicals and, hence, oxidative stress, which has been correlated with the generation and progression of AD. Therefore, we have studied in vitro how AChE catalytic activity and ACh levels are affected by the presence of metals (Fe(3+), Cu(2+), Cr(3+), Zn(2+), and Cd(2+)), H2O2 (without Aβ42), and (·) OH radicals produced from FR and FLR. The results showed that the H2O2 and the metals do not modify the AChE catalytic activity, but the (·)OH radical causes a decrease in it. On the other hand, metals, H2O2 and (·)OH radicals, increase the ACh hydrolysis. This finding suggests that when H2O2, the metals and the (·)OH radicals are present, both, the AChE catalytic activity and ACh levels diminish. Furthermore, in the future it may be interesting to study whether these effects are observed when H2O2 is produced directly from Aβ42.
Catalytic Asymmetric Reactions of 4‐Substituted Indoles with Nitroethene: A Direct Entry to Ergot Alkaloid Structures
Romanini, Simone; Galletti, Emilio; Caruana, Lorenzo; Mazzanti, Andrea; Himo, Fahmi
Abstract A domino Friedel–Crafts/nitro‐Michael reaction between 4‐substituted indoles and nitroethene is presented. The reaction is catalyzed by BINOL‐derived phosphoric acid catalysts, and delivers the corresponding 3,4‐ring‐fused indoles with very good results in terms of yields and diastereo‐ and enantioselectivities. The tricyclic benzo[cd]indole products bear a nitro group at the right position to serve as precursors of ergot alkaloids, as demonstrated by the formal synthesis of 6,7‐secoagroclavine from one of the adducts. DFT calculations suggest that the outcome of the reaction stems from the preferential evolution of a key nitronic acid intermediate through a nucleophilic addition pathway, rather than to the expected "quenching" through protonation. PMID:26486074
Resonance scattering spectral detection of catalase activity using Au@Ag nanoparticle as probe and coupling catalase catalytic reaction with Fenton reaction.
Liang, Aihui; Liang, Yueyuan; Jiang, Zhiliang; Jiang, Hesheng
The Au(core)Ag(shell) (Au@Ag) nanoparticles in size of 30 nm were prepared using 10 nm gold nanoparticles as seeds at 90 degrees C, and were purified by high-speed centrifugation to remove the excess trisodium citrate to obtain Au@Ag nanoprobe. In the medium of pH 4.0 acetate buffer solution--7.2 micromol/L H2O2--67 micromol/L Fe(II), Au@Ag nanoparticles exhibited a resonance scattering (RS) peak at 538 nm. Upon addition of Catalase (Ct), the system produced hydroxyl radical that oxidized the Au@Ag nanoprobe to form the AuAg nanoparticles with partly bare nanogold. Those AuAg nanoparticles aggregated to large nanoclusters that led to the RS peak wavelength red-shift and its RS peak intensity enhanced. The catalase activity (C) is linear to the enhanced RS intensity (DeltaI) in the range of 6 to 2,800 U/L, with regression equation of DeltaI = 0.168 C-0.2, the correlation coefficient of 0.9952, and detection limit of 2.8 U/L. This method was applied to the detection of serum samples, and the results were agreement with that of the spectrophotometry. A new catalytic mechanism of catalase was proposed with oxywater principle that was agreement with the results of resonance scattering spectroscopy, absorption spectrophotometry, transmission electron microscopy and laser scattering.
Quantum Mechanics and Molecular Mechanics Study of the Catalytic Mechanism of Human AMSH-LP Domain Deubiquitinating Enzymes.
Zhu, Wenyou; Liu, Yongjun; Ling, Baoping
Deubiquitinating enzymes (DUBs) catalyze the cleavage of the isopeptide bond in polyubiquitin chains to control and regulate the deubiquitination process in all known eukaryotic cells. The human AMSH-LP DUB domain specifically cleaves the isopeptide bonds in the Lys63-linked polyubiquitin chains. In this article, the catalytic mechanism of AMSH-LP has been studied using a combined quantum mechanics and molecular mechanics method. Two possible hydrolysis processes (Path 1 and Path 2) have been considered. Our calculation results reveal that the activation of Zn(2+)-coordinated water molecule is the essential step for the hydrolysis of isopeptide bond. In Path 1, the generated hydroxyl first attacks the carbonyl group of Gly76, and then the amino group of Lys63 is protonated, which is calculated to be the rate limiting step with an energy barrier of 13.1 kcal/mol. The energy barrier of the rate limiting step and the structures of intermediate and product are in agreement with the experimental results. In Path 2, the protonation of amino group of Lys63 is prior to the nucleophilic attack of activated hydroxyl. The two proton transfer processes in Path 2 correspond to comparable overall barriers (33.4 and 36.1 kcal/mol), which are very high for an enzymatic reaction. Thus, Path 2 can be ruled out. During the reaction, Glu292 acts as a proton transfer mediator, and Ser357 mainly plays a role in stabilizing the negative charge of Gly76. Besides acting as a Lewis acid, Zn(2+) also influences the reaction by coordinating to the reaction substrates (W1 and Gly76).
Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process.
Zhang, Yanwen; Cai, Ningsheng; Yang, Jingbiao; Xu, Bo
The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000 ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000 ppm methane and 0.051 g min(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100 ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000 ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.
Cross-hetero-dehydrogenative coupling reaction of phosphites: a catalytic metal-free phosphorylation of amines and alcohols.
Dhineshkumar, Jayaraman; Prabhu, Kandikere Ramaiah
Phosphorylation of amines, alcohols, and sulfoximines are accomplished using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions. This method provides an easy route for synthesizing a variety of phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates which are of biological importance.
Catalytic effects in the reaction of polypropylene with benzoyl peroxide and structural-kinetic model of the polymer
Mikheev, Yu.A.; Guseva, L.N.; Toptygin, D.Ya.
The kinetic peculiarities of the chain arylation of polypropylene with benzoyl peroxide and the yields of the transformation products (arylated polypropylene benzene, and benzoic acid) were established. The equation of the reaction rate depends on the way in which the samples were prepared and on the benzoyl peroxide concentration in the polymer. The kinetic peculiarities found were explained by a heterophase mechanism.
Rh nanoparticles supported on ultrathin carbon nanosheets for high-performance oxygen reduction reaction and catalytic hydrogenation.
Lin, Chong; Wu, Guanghao; Li, Huiqin; Geng, Yanmin; Xie, Gang; Yang, Jianhui; Liu, Bin; Jin, Jian
We reported a facile and scalable salt-templated approach to produce monodisperse Rh nanoparticles (NPs) on ultrathin carbon nanosheets with the assistance of calcination under inert gas. More importantly, in spite of the essentially poor ORR activity of Rh/C, the acquired Rh/C hybrid nanosheets display a comparable ORR activity to the optimal commercial Pt/C catalyst, which may be due to the extra-small size of Rh NPs and the 2D defect-rich amorphous carbon nanosheets that can facilitate the charge transfer and reactive surface exposure. Moreover, Rh/C nanosheets present the optimal current density and best durability with the minimum decline during the entire test, so that ∼93% activity after 20 000 s is achieved, indicating a good lifetime for ORR. In contrast, commercial Pt/C and commercial Rh/C exhibited worse durability, so that ∼74% and ∼85% activities after 20 000 s are maintained. What's more, in the model system of reduction of 4-nitrophenol (4-NP), the kinetic constant k for Rh/C nanosheets is 3.1 × 10(-3), which is 4.5 times than that of the commercial Rh/C catalyst, revealing that our Rh/C hybrid nanosheets can be potentially applied in industrial catalytic hydrogenation. This work opens a novel and facile way for the rest of the precious metal NPs to be supported on ultrathin carbon nanosheets for heterogeneous catalysis.
Eco-friendly green synthesis of silver nanoparticles using salmalia malabarica: synthesis, characterization, antimicrobial, and catalytic activity studies
NASA Astrophysics Data System (ADS)
Murali Krishna, I.; Bhagavanth Reddy, G.; Veerabhadram, G.; Madhusudhan, A.
An economically viable and "green" process has been developed for the synthesis of silver nanoparticles (AgNPs) with an average size of 7 nm using non-toxic and renewable salmalia malabarica gum (SMG) as reducing and capping agent without using any chemical reducing agent. The effect of various parameters such as concentration of SMG and silver nitrate and reaction time for the synthesis of AgNPs was studied. The synthesized AgNPs are systematically characterized by UV/Vis spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction and Transmission electron microscopy. The resultant SMG-capped AgNPs are highly stable and had significant antibacterial action on both Escherichia coli ( E. coli) and Staphylococcus aureus ( S. aureus). The catalytic action of the SMG-capped AgNPs to initiate the reduction of 4-nitrophenol (4-NP) in the presence of NaBH4 has also been reported. The kinetics of the reaction was found to be of pseudo-first-order with respect to the 4-NP.
Pathways of electrophilic aromatic substitution reactions catalyzed by group 13 trihalides: An ab initio study
NASA Astrophysics Data System (ADS)
Volkov, Alexey N.; Timoshkin, Alexey Y.; Suvorov, Andrew V.
An ab initio study of the two possible pathways of ectrophilic aromatic substitution reaction catalyzed by monomeric and dimeric forms of group 13 metal halides has been performed. Optimized geometries of π, σ-complexes and corresponding transition states have been obtained at second-order Møller-Plesset/ LANL2DZ(d)+ level of theory. It is found that operation of the dimeric pathway is more favorable both thermodynamically and kinetically. Thus, it is expected that catalytical activity of the metal halide will be greatly increased if the stoichiometric ratio 2:1 is employed. Obtained results are in qualitative agreement with available experimental data.
Preparation of zeolite supported TiO2, ZnO and ZrO2 and the study on their catalytic activity in NOx reduction and 1-pentanol dehydration
NASA Astrophysics Data System (ADS)
Fatimah, Is
Preparation of zeolite supported TiO2, ZnO and ZrO2 and their catalytic activity was studied. Activated natural zeolite from Indonesia was utilized for the preparation and catalytic activity test on NOx reduction by NH3 and also 1-pentanol dehydration were examined. Physicochemical characterization of materials was studied by x-ray diffraction (XRD) measurement, scanning electron microscope, solid acidity determination and also gas sorption analysis. The results confirmed that the preparation gives some improvements on physicochemical characters suitable for catalysis mechanism in those reactions. Solid acidity and specific surface area contributed significantly to the activity.
An Arylation Strategy to Propargylamines: Catalytic Asymmetric Friedel-Crafts-type Arylation Reactions of C-Alkynyl Imines.
Wang, Yingcheng; Jiang, Liang; Li, Long; Dai, Jun; Xiong, Dan; Shao, Zhihui
The first arylation strategy for the synthesis of enantioenriched propargylamines is disclosed. This approach, which is complementary to previous alkynylation and alkylation strategies, involves a C(sp(2) )-C(sp(3) ) bond formation, and is based on the first asymmetric Friedel-Crafts-type arylation reaction of C-alkynyl imines. Asymmetric Friedel-Crafts reactions with electron-deficient phenols, a longstanding unsolved challenge, have thus been realized for the first time, enabled by the combination of our recently introduced C-alkynyl N-Boc-protected N,O-acetals as electrophiles and chiral phosphoric acids as catalysts. The synthetic utility of the resulting structurally diverse and polyfunctional chiral propargylamines was demonstrated by a series of selective transformations, including controlled reduction of the alkynyl group and iterative cross-couplings.
Composite polymer/oxide hollow fiber contactors: versatile and scalable flow reactors for heterogeneous catalytic reactions in organic synthesis.
Moschetta, Eric G; Negretti, Solymar; Chepiga, Kathryn M; Brunelli, Nicholas A; Labreche, Ying; Feng, Yan; Rezaei, Fateme; Lively, Ryan P; Koros, William J; Davies, Huw M L; Jones, Christopher W
Flexible composite polymer/oxide hollow fibers are used as flow reactors for heterogeneously catalyzed reactions in organic synthesis. The fiber synthesis allows for a variety of supported catalysts to be embedded in the walls of the fibers, thus leading to a diverse set of reactions that can be catalyzed in flow. Additionally, the fiber synthesis is scalable (e.g. several reactor beds containing many fibers in a module may be used) and thus they could potentially be used for the large-scale production of organic compounds. Incorporating heterogeneous catalysts in the walls of the fibers presents an alternative to a traditional packed-bed reactor and avoids large pressure drops, which is a crucial challenge when employing microreactors.
Ab initio study of the kinetics of hydrogen abstraction reactions on toluene and tetralin
Beste, Ariana; Britt, Phillip F; Buchanan III, A C; Harrison, Robert J; Hathorn, Bryan C
Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the reaction barriers and rate constants for the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are calculated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. Thermolysis of PPE occurs by a free radical chain mechanism in which the product selectivity arises from competitive hydrogen abstraction at the benzylic and nonbenzylic methylen sites by chain carrying benzyl and phenoxyl radicals. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE through comparison of the rate constants and the reaction enthalpies with reliable experimental values. In this study, we used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment. Absolute and relative rate constants were calculated using transition state theory. We found that the relative rate constant using the B3LYP functional agrees within a factor of 2.0 with experiment at the experimental temperature of 333 K, indicating that the B3LYP functional will be successful in predicting relative rate constants for hydrogen abstraction reactions participating in the pyrolysis of PPE.
Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation
NASA Astrophysics Data System (ADS)
Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.
The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.
Green synthesis of palladium nanoparticles mediated by black tea leaves (Camellia sinensis) extract: Catalytic activity in the reduction of 4-nitrophenol and Suzuki-Miyaura coupling reaction under ligand-free conditions.
Lebaschi, Sadaf; Hekmati, Malak; Veisi, Hojat
The present study was conducted to synthesize palladium nanoparticles (Pd NPs) through a facile and green route using non-toxic and renewable natural black tea leaves (Camellia sinensis) extract, as the reducing and stabilizing agent. The as-prepared firstname.lastname@example.com NPs catalyst was characterized by UV-vis spectroscopy, X-ray diffraction (XRD), fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The firstname.lastname@example.com NPs catalyst could be used as an efficient and heterogeneous catalyst for Suzuki coupling reactions between phenylboronic acid and a range of aryl halides (X=I, Br, Cl) and also the reduction of 4-nitrophenol (4-NP) using sodium borohydride in an environmental friendly medium. Excellent yields of products were obtained with a wide range of substrates and the catalyst was recycled 7 times without any significant loss of its catalytic activity.
Study of char gasification in a reaction/adsorption apparatus
Sotirchos, S.V.; Crowley, J.A.
The reaction of an activated carbon (coconut char) with CO/sub 2/ was studied in a reaction/adsorption apparatus which allows successive reactivity and physical adsorption measurements to be made on the same solid sample. Reaction and surface area evolution data were obtained in the temperature range from 800 to 900/sup 0/C. All reaction rate trajectories obtained in this study showed a maximum in the reaction rate, 2-3 times higher than the initial rate, at about 85% conversion. There was no correlation between these results and the evolution of the internal surface area although the reaction appeared to take place initially in the kinetically controlled regime.
Effects of N{sub 2}O gas addition on the properties of ZnO films grown by catalytic reaction-assisted chemical vapor deposition
Yasui, Kanji Morioka, Makoto; Kanauchi, Shingo; Ohashi, Yuki; Kato, Takahiro; Tamayama, Yasuhiro
The influence of N{sub 2}O gas addition on the properties of zinc oxide (ZnO) films grown on a-plane (11–20) sapphire (a-Al{sub 2}O{sub 3}) substrates was investigated, using a chemical vapor deposition method based on the reaction between dimethylzinc and high-temperature H{sub 2}O produced by a catalytic H{sub 2}-O{sub 2} reaction on platinum (Pt) nanoparticles. The addition of N{sub 2}O was found to increase the size of the crystalline facets and to improve the crystal orientation along the c-axis. The electron mobility at 290 K was also increased to 234 cm{sup 2}/Vs following the addition of N{sub 2}O gas at a pressure of 3.2 × 10{sup −3 }Pa. In addition, the minimum full width at half maximum of the most intense photoluminescence peak derived from neutral donor bound excitons at 10 K decreased to 0.6 meV by the addition of N{sub 2}O gas at a pressure of 3.1 × 10{sup −2 }Pa.
Catalytic role of TiO(2) terminal oxygen atoms in liquid-phase photocatalytic reactions: oxidation of aromatic compounds in anhydrous acetonitrile.
Montoya, Juan F; Bahnemann, Detlef W; Peral, José; Salvador, Pedro
On the basis of experiments carried out with controlled amounts of residual oxygen and water, or by using oxygen-isotope-labeled Ti(18) O2 as the photocatalyst, we demonstrate that (18) Os atoms behave as real catalytic species in the photo-oxidation of acetonitrile-dissolved aromatic compounds such as benzene, phenol, and benzaldehyde with TiO2 . The experimental evidence allows a terminal-oxygen indirect electron-transfer (TOIET) mechanism to be proposed, which is a new pathway that involves the trapping of free photogenerated valence-band holes at Os species and their incorporation into the reaction products, with simultaneous generation of oxygen vacancies at the TiO2 surface and their subsequent healing with oxygen atoms from either O2 or H2 O molecules that are dissolved in the liquid phase. According to the TOIET mechanism, the TiO2 surface is not considered to remain stable, but is continuously changing in the course of the photocatalytic reaction, challenging earlier interpretations of TiO2 photocatalytic phenomena.
Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions
Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun
Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550
Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism.
Rossin, Andrea; Bottari, Giovanni; Lozano-Vila, Ana M; Paneque, Margarita; Peruzzini, Maurizio; Rossi, Andrea; Zanobini, Fabrizio
Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH(2)-NR(2)](n) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-borane equivalent. The processes were followed through multinuclear ((31)P, (1)H, (11)B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.
Interaction Induced High Catalytic Activities of CoO Nanoparticles Grown on Nitrogen-Doped Hollow Graphene Microspheres for Oxygen Reduction and Evolution Reactions
Jiang, Zhong-Jie; Jiang, Zhongqing
Nitrogen doped graphene hollow microspheres (NGHSs) have been used as the supports for the growth of the CoO nanoparticles. The nitrogen doped structure favors the nucleation and growth of the CoO nanoparticles and the CoO nanoparticles are mostly anchored on the quaternary nitrogen doped sites of the NGHSs with good monodispersity since the higher electron density of the quaternary nitrogen favors the nucleation and growth of the CoO nanoparticles through its coordination and electrostatic interactions with the Co2+ ions. The resulting NGHSs supported CoO nanoparticles (CoO/NGHSs) are highly active for the oxygen reduction reaction (ORR) with activity and stability higher than the Pt/C and for the oxygen evolution reaction (OER) with activity and stability comparable to the most efficient catalysts reported to date. This indicates that the CoO/NGHSs could be used as efficient bi-functional catalysts for ORR and OER. Systematic analysis shows that the superior catalytic activities of the CoO/NGHSs for ORR and OER mainly originate from the nitrogen doped structure of the NGHSs, the small size of the CoO nanoparticles, the higher specific and electroactive surface area of the CoO/NGHSs, the good electric conductivity of the CoO/NGHSs, the strong interaction between the CoO nanoparticles and the NGHSs, etc. PMID:27255562
Scaling up of continuous-flow, microwave-assisted, organic reactions by varying the size of Pd-functionalized catalytic monoliths.
He, Ping; Haswell, Stephen J; Fletcher, Paul D I; Kelly, Stephen M; Mansfield, Andrew
A product-scalable, catalytically mediated flow system has been developed to perform Suzuki-Miyaura reactions under a microwave heating regime, in which the volumetric throughput of a Pd-supported silica monolith can be used to increase the quantity of the product without changing the optimal operating conditions. Two silica monoliths (both 3 cm long), with comparable pore diameters and surface areas, were fabricated with diameters of 3.2 and 6.4 mm to give volumetric capacities of 0.205 and 0.790 mL, respectively. The two monoliths were functionalized with a loading of 4.5 wt % Pd and then sealed in heat-shrinkable Teflon(®) tubing to form a monolithic flow reactor. The Pd-supported silica monolith flow reactor was then placed into the microwave cavity and connected to an HPLC pump and a backpressure regulator to minimize the formation of gas bubbles. The flow rate and microwave power were varied to optimize the reactant contact time and temperature, respectively. Under optimal reaction conditions the quantity of product could be increased from 31 mg per hour to 340 mg per hour simply by changing the volumetric capacity of the monolith.
Intramolecular catalytic asymmetric carbon-hydrogen insertion reactions. Synthetic advantages in total synthesis in comparison with alternative approaches.
Doyle, Michael P; Ratnikov, Maxim; Liu, Yu
The synthetic potential of highly directional formal insertion of a carbene between carbon and hydrogen of a carbon-hydrogen bond has recently been developed for intramolecular reactions that lead to compounds of biological and medicinal interest. Stereoselective and regiocontrolled intramolecular processes from diazoacetate reactants, catalyzed by dirhodium(II) compounds with chiral carboxamidate ligands, provide efficient and selective access to compounds as diverse as enterolactone, baclofen, imperanene, xylolactone, and rolipram. A comparison of the C-H insertion methodology with alternative approaches is presented.
Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide
NASA Technical Reports Server (NTRS)
Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.
Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.
[Progress in study of the structure, catalytic mechanism and inhibitors of aromatase].
Fu, Jing; Shen, Zhong-Hua; Cheng, Fei-Xiong; Liu, Gui-Xia; Li, Wei-Hua; Tang, Yun
Aromatase is a key enzyme responsible for in vivo estrogen biosynthesis. Inhibition of the activity of the aromatase has become an alterative way for treatment of breast cancer. In this review, the structure and catalytic mechanism of the aromatase is briefly introduced followed by thorough review of the progress in the study of the steroidal and non-steroidal aromatase inhibitors. This review is focused on the natural compounds that exhibit the aromatase inhibition, which include flavonoids, xanthones, coumarins, and sesquiterpenes. The structure-activity relationship of these compounds is also discussed.
Density functional study of chemical reaction equilibrium for dimerization reactions in slit and cylindrical nanopores
NASA Astrophysics Data System (ADS)
Malijevský, Alexandr; Lísal, Martin
We present a theoretical study of the effects of confinement on chemical reaction equilibrium in slit and cylindrical nanopores. We use a density functional theory (DFT) to investigate the effects of temperature, pore geometry, bulk pressure, transition layering, and capillary condensation on a dimerization reaction that mimics the nitric oxide dimerization reaction, 2NO⇌(NO)2, in carbonlike slit and cylindrical nanopores in equilibrium with a vapor reservoir. In addition to the DFT calculations, we also utilize the reaction ensemble Monte Carlo method to supplement the DFT results for reaction conversion. This work is an extension of the previous DFT study by Tripathi and Chapman [J. Chem. Phys. 118, 7993 (2003)] on the dimerization reactions confined in the planar slits.
Surface structure of crystalline and amorphous chromia catalysts for the selective catalytic reduction of nitric oxide. 1. Characterization by temperature-programmed reaction and desorption
Curry-Hyde, H.E.; Musch, H.; Baiker, A. ); Schraml-Marth, M.; Wokaun, A. )
Amorphous and crystalline chromia catalysts used for the selective catalytic reduction (SCR) of NO by NH{sub 3} have been characterized using temperature-programmed reaction and desorption of preadsorbed NO and NH{sub 3}. The acidity of the Lewis acid sites and the associated labile oxygen species are investigated using NH{sub 3} as a probe molecule. The degree of coordinative unsaturation of these sites is inferred from the reactions of NO. The effects of reduction, oxidation, and SCR treatment on the state of the Lewis acid sites and the labile oxygen are discussed. Lewis acid sites on crystalline chromia are more acidic than those on amorphous chromia. Different labile oxygen species are discernible based on their oxidizing strengths and the products formed. All labile oxygen is readily removed by reduction; SCR treatment leads to the partial removal of labile oxygen from both morphologies of chromia. The degree of lability of the different oxygen species is related to the morphology of the chromia. The proportions of one- and twofold coordinatively unsaturated sites (1 and 2 c.u.s.) depends strongly on the morphology of the chromia and its pretreatment. Both types of sites show distinct differences in the acidity dependent on the morphology of the chromia. The most significant difference between the two morphologies is seen after SCR treatment. Crystalline chromia shows a very high density of 1 c.u.s. compared to amorphous chromia. These sites are generated from 2 c.u.s. by abstraction of oxygen from NO. Implications of these results on the SCR reaction are discussed.
The strong catalytic effect of Pb(II) on the oxygen reduction reaction on 5 nm gold nanoparticles.
Wang, Ying; Laborda, Eduardo; Plowman, Blake J; Tschulik, Kristina; Ward, Kristopher R; Palgrave, Robert G; Damm, Christine; Compton, Richard G
Citrate-capped gold nanoparticles (AuNPs) of 5 nm in diameter are synthesized via wet chemistry and deposited on a glassy carbon electrode through electrophoresis. The kinetics of the oxygen reduction reaction (ORR) on the modified electrode is determined quantitatively in oxygen-saturated 0.5 M sulphuric acid solution by modelling the cathode as an array of interactive nanoelectrodes. Quantitative analysis of the cyclic voltammetry shows that no apparent ORR electrocatalysis takes place, the kinetics on AuNPs being effectively the same as on bulk gold. Contrasting with the above, a strong ORR catalysis is found when Pb(2+) is added to the oxygen saturated solution or when the modified electrode is cycled in lead alkaline solution such that lead dioxide is repeatedly electrodeposited and stripped off on the nanoparticles. In both cases, the underpotential deposition of lead on the gold nanoparticles is found to be related to the catalysis.
Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions.
Wang, Meihua; Gao, Zhe; Zhang, Bin; Yang, Huimin; Qiao, Yan; Chen, Shuai; Ge, Huibin; Zhang, Jiankang; Qin, Yong
Metal-support interfaces play a prominent role in heterogeneous catalysis. However, tailoring the metal-support interfaces to realize full utilization remains a major challenge. In this work, we propose a graceful strategy to maximize the metal-oxide interfaces by coating confined nanoparticles with an ultrathin oxide layer. This is achieved by sequential deposition of ultrathin Al2 O3 coats, Pt, and a thick Al2 O3 layer on carbon nanocoils templates by atomic layer deposition (ALD), followed by removal of the templates. Compared with the Pt catalysts confined in Al2 O3 nanotubes without the ultrathin coats, the ultrathin coated samples have larger Pt-Al2 O3 interfaces. The maximized interfaces significantly improve the activity and the protecting Al2 O3 nanotubes retain the stability for hydrogenation reactions of 4-nitrophenol. We believe that applying ALD ultrathin coats on confined catalysts is a promising way to achieve enhanced performance for other catalysts.
Raman spectroscopic study of reaction dynamics
NASA Astrophysics Data System (ADS)
MacPhail, R. A.
The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.
Molecular beam studies of reaction dynamics
Lee, Y.T.
Purpose of this research project is two-fold: (1) to elucidate detailed dynamics of simple elementary reactions which are theoretically important and to unravel the mechanism of complex chemical reactions or photo chemical processes which play an important role in many macroscopic processes and (2) to determine the energetics of polyatomic free radicals using microscopic experimental methods. Most of the information is derived from measurement of the product fragment translational energy and angular distributions using unique molecular beam apparati designed for these purposes.
Soot Reaction Properties (Ground-Based Study)
NASA Technical Reports Server (NTRS)
Dai, Z.; El-Leathy, A. M.; Lin, K.-C.; Sunderland, P. B.; Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)
Three major soot reaction processes are needed to predict soot properties in flame environments: soot growth, or the formation of soot on soot nuclei and soot particles; soot oxidation, or the reaction of soot with oxidizing species to yield the combustion products of soot oxidation; and soot nucleation, or the formation of soot nuclei from soot precursors having large molecular weights (generally thought to be large and particularly stable PAH molecules in flame environments, called stabilomers). These processes are addressed in the following, considering soot growth, oxidation and nucleation, in turn, by exploiting the soot and flame structure results for premixed and diffusion flames already discussed in Section 2.
Kinetic Study of the Heck Reaction: An Interdisciplinary Experiment
ERIC Educational Resources Information Center
Gozzi, Christel; Bouzidi, Naoual
The aim of this experiment is to study and calculate the kinetic constant of a Heck reaction: the arylation of but-3-en-2-ol by iodobenzene catalyzed by palladium acetate in presence of triethylamine in DMF. The reaction leads to a mixture of two ketones. Students use GC analysis to quantify reagents and products of reaction. They control the…
Catalytic hydrotreating process
Karr, Jr., Clarence; McCaskill, Kenneth B.
Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.
Study of Reaction Mechanism in Tracer Munitions
Regression Rates (Furnished by Frankford Arsenal) 35 13 Calculated Heat Fluxes and Energy Partitions 43 4 I NOMENCLATURE B = preexponential factor... anhydride disproportionates in a fast step: N2 0 3 - 2 + NO (4) so that the resulting dioxide can react with more nitrite in another fast reaction: Sr
Catalytic destruction of chloramine to nitrogen using chlorination and activated carbon--case study.
Kochany, J; Lipczynska-Kochany, E
The paper presents the results of laboratory and pilot studies on the removal of chloramine from potable water using chlorination with a less-than-breakpoint dosage of chlorine, followed by treatment with catalytic activated carbon. The effect of the chlorine-to-nitrogen ratio, temperature, and carbon contact time were investigated to optimize conditions for chloramines removal and minimize the production of ammonia. Results demonstrated that prechlorination of water, followed by treatment with catalytic activated carbon, can degrade monochloramine to nitrogen gas as a main product. For all chlorine-to-ammonia ratios studied, the observed rates of monochloramine removal were higher at a temperature of 20 degrees C than they were at 5 degrees C. Generation of ammonia was slightly higher at the lower temperature. However, at both temperatures, practically all monochloramine was destroyed, and only insignificant amounts of ammonia were formed when a chlorine-to-ammonia ratio of 7:1 was applied. The described method is simple and cost-effective, because it eliminates the requirement of removal of ammonia, typically formed during the treatment of chloramines with activated carbon.
Catalytic seawater flue gas desulfurization process: an experimental pilot plant study
F. Vidal B.; P. Ollero; F.J. Gutierrez Ortiz; A. Villanueva
In previous articles by the authors on seawater S(IV) oxidation kinetics, a significant catalytic effect was demonstrated by means of a commercially available activated carbon. The aims of this study carried out at pilot plant scale were to assess the use of high-efficiency structured packing and to validate the positive results obtained previously in laboratory studies. A comparison between a packed tower and a spray column was made by maintaining the same desulfurization efficiency. A 47% reduction in seawater flow can be obtained with a packed tower. This option seems to be more economical, with a reduction in operation costs of least of 33%. With the appropriate activated carbon, it is possible to reach a greater oxidation rate at a low pH level than by operating conventionally at a high pH level without a catalyst. A preliminary technical and financial comparison between the advanced seawater desulfurization process (equipped with a packed tower and a catalytic oxidation plant) and the conventional process (spray tower and noncatalytic oxidation) was carried out. 18 refs., 4 figs., 4 tabs.
Effect of Sb Segregation on Conductance and Catalytic Activity at Pt/Sb-Doped SnO2 Interface: A Synergetic Computational and Experimental Study.
Fu, Qiang; Colmenares Rausseo, Luis César; Martinez, Umberto; Dahl, Paul Inge; García Lastra, Juan Maria; Vullum, Per Erik; Svenum, Ingeborg-Helene; Vegge, Tejs
Antimony-doped tin dioxide (ATO) is considered a promising support material for Pt-based fuel cell cathodes, displaying enhanced stability over carbon-based supports. In this work, the effect of Sb segregation on the conductance and catalytic activity at Pt/ATO interface was investigated through a combined computational and experimental study. It was found that Sb-dopant atoms prefer to segregate toward the ATO/Pt interface. The deposited Pt catalysts, interestingly, not only promote Sb segregation, but also suppress the occurrence of Sb(3+) species, a charge carrier neutralizer at the interface. The conductivity of ATO was found to increase, to a magnitude close to that of activated carbon, with an increment of Sb concentration before reaching a saturation point around 10%, and then decrease, indicating that Sb enrichment at the ATO surface may not always favor an increment of the electric current. In addition, the calculation results show that the presence of Sb dopants in ATO has little effect on the catalytic activity of deposited three-layer Pt toward the oxygen reduction reaction, although subsequent alloying of Pt and Sb could lower the corresponding catalytic activity. These findings help to support future applications of ATO/Pt-based materials as possible cathodes for proton exchange membrane fuel cell applications with enhanced durability under practical applications.
In situ DRIFTS studies on MnOx nanowires supported by activated semi-coke for low temperature selective catalytic reduction of NOx with NH3
NASA Astrophysics Data System (ADS)
Chen, Yan; Zhang, Zuotai; Liu, Lili; Mi, Liang; Wang, Xidong
To mitigate the threat of NOx on the environment, MnOx nanowires were fabricated on activated semi-coke (MnOx NW/ASC) for the first time. The prepared MnOx NW/ASC was used for the low temperature selective catalytic reduction (SCR) of NOx with NH3, which achieved an efficiency of over 90% with a low loading content of 1.64 wt% at 150-210 °C. This high performance could be ascribed to synergistic effect between MnOx and ASC. Specifically, the large specific surface area and reducible property of ASC facilitated the dispersion of MnOx and the formation of Mn3+, respectively. Meanwhile, MnOx nanowires provided more redox sites and lattice oxygen species due to the coexistence of Mn3+ and Mn4+, which accelerated the catalytic cycle. The in situ DRIFTS studies revealed that ASC was conducive to the adsorption of NO and NH3. Most importantly, the existence of Mn3+ favored the formation of amide species and the subsequent reduction reaction. Furthermore, the Langmuir-Hinshelwood (L-H) route between coordinated NH3 and bidentate nitrate was predominating in the SCR process and responsible for the high catalytic activity at low temperature.
Study of the kinetics of catalytic decomposition of hydrazine vapors on palladium
NASA Technical Reports Server (NTRS)
Khomenko, A. A.; Apelbaum, L. O.
The decomposition rates of N2H4 on a palladium surface are studied. Experiments were conducted in a circulating unit at atmosphere pressure. The experimental method is described. The laws found for the reaction kinetics are explained by equations.
Surface-catalyzed air oxidation reactions of hydrazines: Tubular reactor studies
NASA Technical Reports Server (NTRS)
Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.
The surface-catalyzed air oxidation reactions of hydrazine, monomethylhydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine and tetramethylhydrazine were investigated in a metal-powder packed turbular flow reactor at 55 plus or minus 3 C. Hydrazine was completely reacted on all surfaces studied. The major products of monomethylhydrazine (MMH) oxidation were methanol, methane and methyldiazene. The di-, tri- and tetra-methyl hydrazines were essentially unreactive under these conditions. The relative catalytic reactivities toward MMH are: Fe greater than Al2O3 greater than Ti greater than Zn greater than 316 SS greater than Cr greater than Ni greater than Al greater than 304L SS. A kinetic scheme and mechanism involving adsorption, oxidative dehydrogenation and reductive elimination reactions on a metal oxide surface are proposed.
Reaction mechanism of zinc-dependent cytosine deaminase from Escherichia coli: a quantum-chemical study.
Manta, Bianca; Raushel, Frank M; Himo, Fahmi
The reaction mechanism of cytosine deaminase from Escherichia coli is studied using density functional theory. This zinc-dependent enzyme catalyzes the deamination of cytosine to form uracil and ammonia. The calculations give a detailed description of the catalytic mechanism and establish the role of important active-site residues. It is shown that Glu217 is essential for the initial deprotonation of the metal-bound water nucleophile and the subsequent protonation of the substrate. It is also demonstrated that His246 is unlikely to function as a proton shuttle in the nucleophile activation step, as previously proposed. The steps that follow are nucleophilic attack by the metal-bound hydroxide, protonation of the leaving group assisted by Asp313, and C-N bond cleavage. The calculated overall barrier is in good agreement with the experimental findings. Finally, the calculations reproduce the experimentally determined inverse solvent deuterium isotope effect, which further corroborates the suggested reaction mechanism.
Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces
NASA Astrophysics Data System (ADS)
Liu, Da-Jiang; Evans, James W.
A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental
The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. The authors have investigated the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. The silanation approach failed to stabilize Cu-ZSM-5 activity under hydrothermal condition. Silanation blocked the oxygen migration and inhibited oxygen desorption. Oxygen spillover was found to be an effective approach for promoting NO decomposition activity on Pt-based catalysts. Detailed mechanistic study revealed the oxygen inhibition in NO decomposition and reduction as the most critical issue in developing an effective catalytic approach for controlling NO emission.
Experimental Study of Stellar Reactions at CNS
Kubono, S.; Yamaguchi, H.; Wakabayashi, Y.; Amadio, G.; Hayakawa, S.; He, J. J.; Saito, A.; Teranishi, T.; Nishimura, S.; Fukunishi, N.; Iwasa, N.; Inafuku, K.; Kato, S.; Tanaka, M. H.; Fuchi, Y.; Moon, J. Y.; Kwon, K.; Lee, C. S.; Khiem, Le Hong; Chen, A.
After a brief review on low-energy RI beam production technology, nuclear astrophysics programs at CNS are presented including a scope of the field in the Wako campus. The CRIB project involves a total development of the whole facility to maximize the low-energy RI beam intensities, including the ion source, the AVF cyclotron and the low-energy RI beam separator CRIB, Some recent nuclear astrophysics experiments performed with the RI beams were discussed, including the measurement of the 14O({alpha},p)17F reaction, the key stellar reaction for the onset of the high-temperature rp-process. The first experiment performed with a newly installed high-resolution magnetic spectrograph PA of CNS was also presented. Collaboration possibilities for nuclear astrophysics in the RIKEN campus are also touched.
Theoretical study of chemical reactions in solution
Yokogawa, D.
Quantum chemical calculations in solution are becoming more and more important in chemistry. Reference interaction site model self-consistent field (RISM-SCF) is one of the powerful approaches to perform quantum chemical calculations in solution. In this work, we developed a new generation of RISM-SCF, where a robust fitting method was newly introduced. We applied the new method to tautomerization reaction of cytosine in aqueous phase. Our calculation reproduced experimentally obtained relative stabilities and relative free energies correctly.
Direct Reactions studies at RIBF new facility
NASA Astrophysics Data System (ADS)
Motobayashi, Tohru
The RIKEN RI Beam Factory (RIBF) is the firs realization of new-generation facilities with beams of unstable nuclei. It is based on heavy-ion primary beams accelerated to 345 MeV/nucleon for all elements up to uranium. When the goal intensity, 1 pμA, is reached, RIBF allows production of about thousand new isotopes with the yield higher than 1 particle par day. Since the RI beam energy after production by in-flight fission and/or projectile fragmentation is be around 200-300 MeV/nucleon, the direct reaction is one of the useful processes for spectroscopy of uncle very far from the stability. Several experiments were proposed and a few of them have been performed with intense (currently) ^48Ca primary beams. The ZeroDegree Spectrometer, which is already operational, can be used to identify the product of a direct reaction in inverse kinematics coupled with, for example, measurement of γ-rays from excited states in the product. Construction of SAMURAI, a large-acceptance spectrometer, has been started. Decays of unbound states or breakup products from various types of direct reaction will be measured in coincidence. Experimental and theoretical issues to be considered for the specific conditions in this new opportunity will be discussed together with brief overview of near-term research.
The reaction kinetics of 3-hydroxybenzoate 6-hydroxylase from Rhodococcus jostii RHA1 provide an understanding of the para-hydroxylation enzyme catalytic cycle.
Sucharitakul, Jeerus; Tongsook, Chanakan; Pakotiprapha, Danaya; van Berkel, Willem J H; Chaiyen, Pimchai
3-Hydroxybenzoate 6-hydroxylase (3HB6H) from Rhodococcus jostii RHA1 is an NADH-specific flavoprotein monooxygenase that catalyzes the para-hydroxylation of 3-hydroxybenzoate (3HB) to form 2,5-dihydroxybenzoate (2,5-DHB). Based on results from stopped-flow spectrophotometry, the reduced enzyme-3HB complex reacts with oxygen to form a C4a-peroxy flavin with a rate constant of 1.13 ± 0.01 × 10(6) m(-1) s(-1) (pH 8.0, 4 °C). This intermediate is subsequently protonated to form a C4a-hydroperoxyflavin with a rate constant of 96 ± 3 s(-1). This step shows a solvent kinetic isotope effect of 1.7. Based on rapid-quench measurements, the hydroxylation occurs with a rate constant of 36 ± 2 s(-1). 3HB6H does not exhibit substrate inhibition on the flavin oxidation step, a common characteristic found in most ortho-hydroxylation enzymes. The apparent kcat at saturating concentrations of 3HB, NADH, and oxygen is 6.49 ± 0.02 s(-1). Pre-steady state and steady-state kinetic data were used to construct the catalytic cycle of the reaction. The data indicate that the steps of product release (11.7 s(-1)) and hydroxylation (36 ± 2 s(-1)) partially control the overall turnover.
[Performance Study of Bromochloracetonitrile Degradation in Drinking Water by Fe/Cu Catalytic Reduction].
Ding, Chun-sheng; Ma, Hai-long; Fu, Yang-ping; Zhao, Shi-du; Li, Dong-bing
The paper used the method of iron copper catalyst reduction to degrade low concentrations of bromochloracetonitrile (BCAN) to lighten the damage to human being, which is a kind of disinfection by-products (DBPs) produced during the chlorination process of drinking water. The removal efficiency of BCAN and its influencing factors were investigated. The mechanism of degradation and kinetics were also explored. The results indicated that iron copper had a greater degradation ability towards BCAN, and the degradation rate of iron copper (mass ratio of 10:1) was 1.5 times that of the zero-valent iron. The removal of BCAN increased obviously with the increase of Fe/Cu dosage. When the initial concentration was set at 20 microg x L(-1), after a reaction time of 150 min, removal of BCAN was improved from 51.1% to 89.5% with the increase of iron copper (mass ratio of 10:1) dosage from 5 g x L(-1) to 10 g x L(-1). The temperature also had great impact on BCAN removal and the removal increased with the increase of temperature. However, BCAN removal did not change a lot with the variation of the initial concentration of BCAN when it was at a low level. The BCAN degradation by iron copper catalytic-reduction followed the first-order kinetics model.
Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions
NASA Astrophysics Data System (ADS)
Gold, Thomas; Gordon, Benjamin E.; Streett, William; Bilson, Elizabeth; Patnaik, Pradyot
In order to assess the possible role of methane in petroleum formation, we studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250°C in the presence of montmorillonite, a natural clay catalyst. Since we expected very slow reaction rates and thus low yields, we used 14C labeled methane to trace the reaction products. We report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C 2 addition occurred, although very small amounts of products corresponding to C 1 addition were also detected. We propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.
Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions
Gold, T.; Gordon, B.E.; Streett, W.; Bilson, E.; Patnaik, P.
In order to assess the possible role of methane in petroleum formation, they studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150-250/sup 0/C in the presence of montmorillonite, a natural clay catalyst. Since they expected very slow reaction rates and thus low yields, we used /sup 14/C labeled methane to trace the reaction products. They report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C/sub 2/ addition occurred, although very small amounts of products corresponding to C/sub 1/ addition were also detected. They propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.
Dynamics of Pickering Emulsions in the Presence of an Interfacial Reaction: A Simulation Study.
Zhao, Shuangliang; Zhan, Bicai; Hu, Yaofeng; Fan, Zhaoyu; Pera-Titus, Marc; Liu, Honglai
Pickering emulsions combining surface-active and catalytic properties offer a promising platform for conducting interfacial reactions between immiscible reagents. Despite the significant progress in the design of Pickering interfacial catalysts for a broad panel of reactions, the dynamics of Pickering emulsions under reaction conditions is still poorly understood. Herein, using benzene hydroxylation with aqueous H2O2 as a model system, we explored the dynamics of benzene/water Pickering emulsions during reaction by dissipative particle dynamics. Our study points out that the surface wettability of the silica nanoparticles is affected to a higher extent by the degree of polymer grafting rather than an increase of the chain length of hydrophobic polymer moieties. A remarkable decline of the oil-in-water (O/W) interfacial tension was observed when increasing the yield of the reaction product (phenol), affecting the emulsion stability. However, phenol did not alter to an important extent the distribution of immiscible reagents around the nanoparticles sitting at the benzene/water interface. A synergistic effect between phenol and silica nanoparticles on the O/W interfacial tension of the biphasic system could be ascertained.
Modeling study on the cleavage step of the self-splicing reaction in group I introns
NASA Technical Reports Server (NTRS)
Setlik, R. F.; Garduno-Juarez, R.; Manchester, J. I.; Shibata, M.; Ornstein, R. L.; Rein, R.
A three-dimensional model of the Tetrahymena thermophila group I intron is used to further explore the catalytic mechanism of the transphosphorylation reaction of the cleavage step. Based on the coordinates of the catalytic core model proposed by Michel and Westhof (Michel, F., Westhof, E. J. Mol. Biol. 216, 585-610 (1990)), we first converted their ligation step model into a model of the cleavage step by the substitution of several bases and the removal of helix P9. Next, an attempt to place a trigonal bipyramidal transition state model in the active site revealed that this modified model for the cleavage step could not accommodate the transition state due to insufficient space. A lowering of P1 helix relative to surrounding helices provided the additional space required. Simultaneously, it provided a better starting geometry to model the molecular contacts proposed by Pyle et al. (Pyle, A. M., Murphy, F. L., Cech, T. R. Nature 358, 123-128. (1992)), based on mutational studies involving the J8/7 segment. Two hydrated Mg2+ complexes were placed in the active site of the ribozyme model, using the crystal structure of the functionally similar Klenow fragment (Beese, L.S., Steitz, T.A. EMBO J. 10, 25-33 (1991)) as a guide. The presence of two metal ions in the active site of the intron differs from previous models, which incorporate one metal ion in the catalytic site to fulfill the postulated roles of Mg2+ in catalysis. The reaction profile is simulated based on a trigonal bipyramidal transition state, and the role of the hydrated Mg2+ complexes in catalysis is further explored using molecular orbital calculations.
DFT study on the effects of catalysis by β-cyclodextrin in the reaction of p-nitrophenyl acetate.
Cheng, Yamei; Wang, Xueye; Li, Weiwei; Chang, Dan
The reaction of p-nitrophenyl acetate and α-alanine can be improved apparently with β-cyclodextrin (β-CD) according to previous research, the interaction mechanism between β-cyclodextrin and p-nitrophenyl acetate is described in this paper. Density functional theory (DFT) method is used throughout the study. According to the energy (the binding energy, the deformation energy) and structural deformation, entry models and reaction process can be pinpointed, viz p-nitrophenyl acetate embed β-CD from the wide rim. Then frontier molecular orbital, dual descriptor, natural bonding orbital (NBO), and nuclear magnetic resonance (NMR) are employed to reveal the mechanism of electron transferring. The mechanism illustrates that β-CD plays a catalytic role during the synthesis reaction, improving the reactivity and selectivity of the process. Graphical Abstract DFT study on the effects of catalysis by β-cyclodextrin in the reaction of p-nitrophenyl acetate.
Investigation of structural, optical, catalytic, fluorescence studies of eco-friendly synthesized Bi2S3 nanostructures
NASA Astrophysics Data System (ADS)
Ayodhya, Dasari; Veerabhadram, Guttena
A simple solution phase method has been developed for the synthesis of ribonucleosides capped Bi2S3 nanostructures (NSs) with an average diameter of 15 nm and length of below 100 nm. Transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and X-ray diffraction (XRD) studies revealed that these NSs were grown from a colloidal dispersion of amorphous Bi2S3 particles, which was first formed through a thermal reaction at a temperature of 60 °C. The phase and structure of the Bi2S3 NSs have been identified by using X-ray powder diffraction. The crystal structure had orthorhombic structure. The surface properties and morphology have been investigated using scanning electron microscope (SEM) technique. The N2 sorption-desorption experiments showed that the surface area of the NSs was 6.35 m2 g-1 by Brunauer-Emmett-Teller (BET). The experiments showed that the Bi2S3 NSs prepared in the present work could be used as catalyst for the reduction of SO dye using a reducing agent. It was found that the as-obtained Bi2S3 NSs contributed to the best catalytic activity. Photoluminescence experiments showed a quenching of the Bi2S3 fluorescence with increasing L-cysteine (Cys) content in the solution. Furthermore, the proposed NSs as sensor were employed for the determination of metal ions with satisfactory results.
Studies on Pyridazine Azide Cyclisation Reactions
Allan, R.D.; Greenwood, J.; Hambley, T.; Hanrahan, J.R.; Hibbs, D.E.; Itani, S.; Tran, H.; Turner, P.
Reaction of sodium azide with 4-methyl-3,5,6-tribromopyridazine results in the formation of 3,5,6-triazide intermediate which could cyclise to give two possible bicyclic products while ab initio calculations show that the formation of a tricyclic compound is extremely energetically unfavourable. However, experimentally, only one major product is isolated. The structure of this unstable product has been conclusively established by X-ray crystallography as 3,5-diazido-4-methyl[1,5-b]tetrazolopyridazine confirming theoretical predictions.
Naphthalene degradation by catalytic ozonation based on nickel oxide: study of the ethanol as cosolvent.
Aguilar, C Marissa; Rodríguez, Julia L; Chairez, Isaac; Tiznado, Hugo; Poznyak, Tatyana
Naphthalene (NA) is a polycyclic aromatic hydrocarbon with toxic properties in aquatic systems. Ozonation (O3) and catalytic ozonation (O3-cat) processes are attractive alternatives of degradation for this kind of compound. NA (20 mg L(-1)) degradation by conventional and catalytic ozonation in the presence of a cosolvent (ethanol) was the aim of this study. This solution was proposed to simulate some aspects of real wastewaters where not only water acts as solvent. Two proportions of the mixture ethanol/water were selected (30:70 and 50:50) with the purpose of studying the cosolvent effect on NA degradation system by ozonation. O3-cat process used nickel oxide as catalyst (0.1 g L(-1)). The degradation analysis of NA by O3-cat in two different proportions of cosolvent showed that in the case of 30:70 (ethanol/water), a 95 % of NA elimination in 60 min was obtained, while in the case 50:50 (ethanol/water), only 55 % was achieved. The O3 process showed similar results of degradation to the initial compound in comparison with catalytic system. According to these results, there is an inhibition effect in pollutant removal by ethanol due to the higher ethanol concentration; the lower elimination rate of NA was obtained (by 40 % during the 60 min). The by-products analysis of ozonation process detected oxalic and formic acids. Treatments with NiO presented less production of organic acids in comparison with conventional ozonation process. The high concentration of ethanol has a relevant factor in the elimination of NA and formation of organic acids; samples with 50 % of cosolvent have showed a higher concentration of organic acids. X-ray photoelectron spectroscopy (XPS) study of O3-cat of diluent (O3-NiO control) and O3-NA-NiO showed the presence of -CO3 absorbed on catalyst due to ethanol decomposition.
Neutron-induced reaction studies using stored ions
NASA Astrophysics Data System (ADS)
Glorius, Jan; Litvinov, Yuri A.; Reifarth, René
Storage rings provide unique possibilities for investigations of nuclear reactions. Radioactive ions can be stored if the ring is connected to an appropriate facility and reaction studies are feasible at low beam intensities because of the recycling of beam particles. Using gas jet or droplet targets, charged particle-induced reactions on short-lived isotopes can be studied in inverse kinematics. In such a system a high-flux reactor could serve as a neutron target extending the experimental spectrum to neutron-induced reactions. Those could be studied over a wide energy range covering the research fields of nuclear astrophysics and reactor safety, transmutation of nuclear waste and fusion.
Effect of core-shell structure and chitosan addition on catalytic activities of copper-containing silica-aluminosilicate composites in deNO(x) reaction by H2.
Chamnankid, Busaya; Samanpratan, Rattanaporn; Kongkachuichay, Paisan
Mesoporous silica-aluminosilicate composites were used as supports for selective catalytic reduction of NO by H2 using copper catalyst. Effect of loading techniques and structures of the supports on the catalytic performance were investigated. The nature, the oxidation state of copper, the structural properties and the morphology of the catalysts were characterized by means of UV-vis spectra, Fourier Transform Infrared Spectroscopy (FTIR), nitrogen sorption, and transmission electron microscopy, respectively. By using substitution technique, the copper(II) species were introduced into the silica-aluminosilicate framework by replacing aluminum atoms that located in the tetrahedral coordination. On the other hand, by using incipient wetness impregnation method, the copper species were deposited on the surface of composite materials. Upon testing their performances in deNO(x) reaction, the catalysts prepared by incipient wetness impregnation method showed higher catalytic activity than those prepared by substitution technique in any copper content. The core-shell structure was able to enhance the catalytic performance. It was found that, among the tested catalysts, the 1.5% Cu loaded core-shell mesoporous silica aluminosilicate composites prepared by an incipient wetness impregnation yielded the highest NO conversion of approximately 59%. However, the addition of chitosan creating macroporosity and controlling the uniform small clusters did not improve the catalytic performance.
Decomposition of O,S-dimethyl methylphosphonothiolate by ammonia on magnesium oxide: a theoretical study of catalytic detoxification of a chemical warfare agent.
Sahu, Chandan; Ghosh, Deepanwita; Sen, Kaushik; Das, Abhijit K
The adsorption of a model nerve agent, O,S-dimethyl methylphosphonothiolate (DMPT), on the hydroxylated and unhydroxylated nano-crystalline magnesium oxide surface followed by the nucleophilic attack of ammonia (NH3) is investigated at the M06-2X/6-311++G(d,p) level of theory using the representative cluster models. The geometries of DMPT and NH3 are fully optimized, while the geometry of the oxide fragment is kept frozen. The main insight of this study is the incorporation of the Eley-Rideal mechanism for the first time in the detoxification process, where one of the reactant molecules (DMPT) is adsorbed and the other one (NH3) reacts with it directly impinging from the gas phase. There are two possible pathways of nucleophilic detoxification, either concerted or stepwise. The nature of the first transition state of nucleophilic attack in both pathways is the vital step for degradation. Our calculated results predict that the reaction of DMPT with NH3 gives rise to both P-S and P-O bond cleavage completely. Also, the P-S cleavage is found to be the favorable one over P-O bond breaking. The exploration of the overall reaction mechanism has established the catalytic activity of nano-crystalline MgO in nucleophilic DMPT degradation, as in all cases the activation barriers have reduced compared to the previously reported aminolysis of DMPT in the gas phase. Interestingly, the hydroxylated model has better catalytic performance than the unhydroxylated one.
A study of DNA/BSA interaction and catalytic potential of oxidovanadium(v) complexes with ONO donor ligands.
Dash, Subhashree P; Panda, Alok K; Dhaka, Sarita; Pasayat, Sagarika; Biswas, Ashis; Maurya, Mannar R; Majhi, Paresh Kumar; Crochet, Aurélien; Dinda, Rupam
The study of DNA/BSA interaction and the catalytic potential of four mononuclear oxidoalkoxido vanadium(v) [V(V)O(L(1-4))OEt] (1-4) and one dinuclear oxidoalkoxido mixed-ligand vanadium(v) [{VO(L(2))OEt}2(Q)]{Q = 4,4'-bipyridine}(5) complexes, with tridentate binegative aroylazine ligands are reported [where H2L(1) = anthranylhydrazone of 2-hydroxy-1-napthaldehyde, H2L(2) = salicylhydrazone of 2-hydroxy-1-napthaldehyde, H2L(3) = benzoylhydrazone of 2-hydroxy-1-acetonaphthone, H2L(4) = anthranylhydrazone of 2-hydroxy-1-acetonaphthone]. All the complexes are characterized by elemental analysis as well as various spectroscopic techniques. Single crystal X-ray diffraction crystallography of 2 reveals that the metal centre is in distorted square pyramidal geometry with O4N coordination spheres, whereas 5 exhibits a distorted octahedral geometry around the metal center. In addition, all the complexes (1-5) show moderate DNA binding propensity which is investigated using UV-vis absorption titration, circular dichroism, thermal denaturation and fluorescence spectral studies. The experimental results show that the complexes effectively interact with CT-DNA through both minor and major groove binding modes, with binding constants ranging from 10(4)-10(5) M(-1). Among 1-5, complexes 3 and 4 show higher binding affinity towards CT-DNA than others and at the same time also exhibit negative ΔTm values of about ∼1.5 and 1.0 °C which resembles the properties shown by cisplatin. All complexes show moderate photo-induced cleavage of pUC19 supercoiled plasmid DNA with complex 3 showing the highest photo induced DNA cleavage activity of ∼48%. In coherence with the DNA interaction studies, 3 and 4 also exhibit good binding affinity towards BSA in the range of 10(10)-10(11) M(-1), which is also supported by their ability to quench the tryptophan fluorescence emission spectra of BSA. All the complexes show remarkable photo-induced BSA cleavage activity (>90%) at a complex