hybrid nanomaterials consisting of two or more different nanoscale functionalities have attracted much attention due to their novel combined properties and technological applications . among them , iron oxide  au ( fe3o4au , /-fe2o3au ) nanocomposites are of great importance for their combined optical and magnetic properties and potential applications in the fields of biotechnologies and catalysts [ 3 - 8 ] . up to now , many methods have been developed to synthesize various fe3o4au and /-fe2o3au nanocomposites [ 9 - 19 ] . for example , yu et al .   reported the synthesis of dumbbell - like fe3o4au nanoparticles using decomposition of fe(co)5 on the surface of the au nanoparticles followed by oxidation in 1-octadecene . fe3o4au core  shell nanoparticles could be prepared with room - temperature coating of au on the surface of fe3o4 nanoparticles by reducing haucl4 in a chloroform solution of oleylamine . wu et al .   prepared magnetic fe3o4au nanoparticles by the controlling a combination of chemically tunable chelating layer modifications for magnetic core and further deposition of au on the amine - functionalized fe3o4 surface . reported the synthesis of -fe2o3au nanoparticles with different au shell thickness by reducing haucl4 on the surface of -fe2o3 nanoparticles . moreover , the synthesis and transformation of 1d nanostructures and their hybrids are of particular interest due to their immense applications [ 20 - 22 ] . however , to the best of our knowledge , there is no report for the controllable synthesis of fe2o3au and fe3o4au hybrid 1d nanostructures . layer - by - layer technique is based on the electrostatic attraction between charge species , and it has been widely used to synthesize nanocomposites [ 23 - 28 ] . more recently , this technique has been realized to prepare hybrid 1d nanostructures [ 29 - 36 ] . herein , we use layer - by - layer technique to synthesize uniform feooh  au hybrid nanorods that can be controllably transformed into fe2o3au and fe3o4au hybrid nanorods . the magnetic and optical properties of as - synthesized fe2o3au and fe3o4au hybrid nanorods have been investigated . poly ( sodium 4-styrenesulfonate ) ( pss ) and poly ( allylamine hydrochloride ) ( pah ) were purchased from alfa aesar co. ltd . second , the pristine feooh nanorods were modified by polyelectrolyte ( pah / pss / pah ) in sequence via layer - by - layer assembly . briefly , 10 mg feooh nanorods was sonicated for 1 h in 50 ml 1 m nacl solution , and 80 mg pah was added and stirred for 0.5 h. subsequently , the excess pah was removed by six repeated centrifugation / wash cycles . similarly , the pss and pah layers were then coated on the surface of the pah - modified feooh nanorods to obtain the pah / pss / pah - modified feooh nanorods . third , feooh  au nanorods were fabricated by chemical reaction using haucl4 , trisodium citrate , and nabh4 as reactants on pah / pss / pah modified feooh nanorod templates . the resulting solid products were centrifuged , washed with distilled water and ethanol to remove the ions possibly remaining in the final products , and finally dried at 80c in air . for the synthesis of -fe2o3au nanorods , the as - prepared feooh au nanorods were heated to 500c for 3 h in air . while for the synthesis of fe3o4au nanorods , the as - prepared feooh au nanorods were heated to 400c for 3 h under h2/ar ( 10% h2 ) atmosphere . the obtained samples were characterized by x - ray powder diffraction ( xrd ) using a rigaku d / max - ga x - ray diffractometer with graphite monochromatized cu k radiation (  = 1.54178  ) . the morphology and structure of the samples were examined by transmission electron microscopy ( tem , jem-200 cx , 160 kv ) , field emission scanning electron microscopy ( fesem , hitachi s-4800 ) and high - resolution transmission electron microscopy ( hrtem , jeol jem-2010 ) . the infrared ( ir ) spectra were measured with a nicolet nexus ftir 670 spectrophotometer . magnetization measurements were carried out using a physical property measurement system ( ppms-9 , quantum design ) . poly ( sodium 4-styrenesulfonate ) ( pss ) and poly ( allylamine hydrochloride ) ( pah ) were purchased from alfa aesar co. ltd . second , the pristine feooh nanorods were modified by polyelectrolyte ( pah / pss / pah ) in sequence via layer - by - layer assembly . briefly , 10 mg feooh nanorods was sonicated for 1 h in 50 ml 1 m nacl solution , and 80 mg pah was added and stirred for 0.5 h. subsequently , the excess pah was removed by six repeated centrifugation / wash cycles . similarly , the pss and pah layers were then coated on the surface of the pah - modified feooh nanorods to obtain the pah / pss / pah - modified feooh nanorods . third , feooh  au nanorods were fabricated by chemical reaction using haucl4 , trisodium citrate , and nabh4 as reactants on pah / pss / pah modified feooh nanorod templates . the resulting solid products were centrifuged , washed with distilled water and ethanol to remove the ions possibly remaining in the final products , and finally dried at 80c in air . for the synthesis of -fe2o3au nanorods , the as - prepared feooh au nanorods were heated to 500c for 3 h in air . while for the synthesis of fe3o4au nanorods , the as - prepared feooh au nanorods were heated to 400c for 3 h under h2/ar ( 10% h2 ) atmosphere . the obtained samples were characterized by x - ray powder diffraction ( xrd ) using a rigaku d / max - ga x - ray diffractometer with graphite monochromatized cu k radiation (  = 1.54178  ) . the morphology and structure of the samples were examined by transmission electron microscopy ( tem , jem-200 cx , 160 kv ) , field emission scanning electron microscopy ( fesem , hitachi s-4800 ) and high - resolution transmission electron microscopy ( hrtem , jeol jem-2010 ) . the infrared ( ir ) spectra were measured with a nicolet nexus ftir 670 spectrophotometer . magnetization measurements were carried out using a physical property measurement system ( ppms-9 , quantum design ) . it can be seen that all diffraction peaks can be assigned to tetragonal feooh ( jcpds no . 65 - 2870 ) , indicating the synthesis of pure feooh  au hybrid nanorods . moreover , the xrd peaks were considerably broad , which implied that au existed in the form of small size . figure 1b shows the sem image of as - synthesized feooh  au hybrid nanorods . as observed , the surface of hybrid nanorods turn into rough compared to pure feooh nanorods , which confirm the deposition of au nanoparticles . moreover , no isolated au nanoparticles can be detected , indicating that all au nanoparticles have been deposited onto feooh nanorods ( fig . it can be clearly observed that au nanoparticles with diameters of about 5 nm have been homogenously deposited onto the surface of feooh nanorod . ir , bet surface area and pore volume analysis were examined to confirm the successful surface modification of pah / pss / pah by the layer - by - layer technique . as shown in fig . 2a , 2b , the additional peaks at 1008 , 1035 and 1180 cm after layer - by - layer assembly can be attributed to benzyl ring in pss , so3 symmetric stretching , and so3 asymmetric stretching , respectively , which confirms the successful surface modification of polyelectrolyte . figure 2 shows nitrogen adsorption and desorption isotherms of feooh nanorods ( c ) before layer - by - lay assembly and ( e ) after layer - by - lay assembly at 77 k with corresponding pore - size distribution calculated by bjh method from desorption branch ( d ) and ( f ) . before layer - by - lay assembly , the feooh nanorods have a bet surface area of 13.8 m g with an average barretl - joyner - halenda ( bjh ) pore diameter of 23.1 nm . after layer - by - lay assembly , the values are 11.9 m g , 37.7 nm , respectively . from the result of bet analysis , we can find that the bet surface area decrease after the layer - by - lay assembly . the possible reason for this phenomenon is that the polyelectrolyte deposited on the surface of feooh nanorods makes the surface smoother and leads to the reduction of the bet surface area . in order to confirm the effect of layer - by - layer process on the formation of the uniform feooh  au hybrid nanorods , comparative experiments have been done . in the absence of polyelectrolyte , only some oh or cooh functional groups on feooh could act as anchoring sites for au nanoparticles growth , which resulted in the sparse deposition of inhomogenous au nanoparticles on feooh nanorods ( fig . 3a ) . when feooh nanorods were modified by two - layer polyelectrolyte ( pah / pss ) , au nanoparticles accumulated and were rarely deposited onto the surface of feooh nanorods . the above - mentioned analysis indicates that the strong electrostatic attraction between aucl4 and polyelectrolyte - modified feooh nanorods plays the most important role in the uniform deposition of au nanoparticles . morphological and structural characterizations of feooh  au hybrid nanorods synthesized via layer - by - layer assembly : a xrd pattern ; b sem image ; c , d tem image a , b infrared spectra of feooh nanorods ( curve a ) before layer - by - lay assembly and ( curve b ) after layer - by - lay assembly ; nitrogen adsorption and desorption isotherms of feooh nanorods c before layer - by - lay assembly and e after layer - by - lay assembly at 77 k with corresponding pore - size distribution calculated by bjh method from desorption branch ( d ) and ( f ) sem images of feooh  au hybrid nanorods synthesized without layer - by - layer process ( a ) and with two - layer ( pah / pss ) assembly ( b ) figure 4 shows the morphological and structural characterizations of the products synthesized by annealing of feooh  au hybrid nanorods under air atmosphere at 500c . it can be seen that all diffraction peaks can be assigned to -fe2o3 ( jcpds no . 33 - 0664 ) and au ( fig . however , the diameter of au nanoparticles in -fe2o3au hybrid nanorods is larger than that in feooh there are two lattice fringes with lattice spacings of 0.235 and 0.252 nm corresponding to the au { 111 } and -fe2o3 { 110 } planes from different grains , respectively , which further confirm the synthesis of -fe2o3au hybrid nanorods . au hybrid nanorods were annealing under h2/ar ( 10% h2 ) atmosphere at 400c , fe3o4au hybrid nanorods can be obtained . figure 5a shows the xrd pattern of as - synthesized products , which confirm the synthesis of pure fe3o4 ( jcpds no . it can be seen that au nanoparticles have been homogenously deposited onto the surface of fe3o4 nanorods , which is similar to -fe2o3au hybrid nanorods . however , the diameter of au nanoparticles in fe3o4au hybrid nanorods is smaller than that in -fe2o3au hybrid nanorods due to the relatively low annealing temperature ( 400c ) . it can be seen that there are two lattice fringes with lattice spacings of 0.235 and 0.296 nm corresponding to the au { 111 } and fe3o4 { 220 } planes from different grains , respectively , which further confirm the synthesis of fe3o4au hybrid nanorods . ir analysis was employed to further confirm the synthesis of -fe2o3au and fe3o4au hybrid nanorods ( fig . it can be seen that there is only one peak at 570 cm for fe3o4 , while -fe2o3 shows two or three peaks , which is related to its structure and size . moreover , -fe2o3 also exhibit three peaks between 500 and 700 cm , which is different from fe3o4 . the ir analysis combined with tem images and xrd pattern can confirm the synthesis of -fe2o3au and fe3o4au hybrid nanorods . morphological and structural characterizations of fe2o3au hybrid nanorods synthesized by annealing of feooh  au hybrid nanorods under air atmosphere : a xrd pattern ; b sem image ; c tem image ; d hrtem image morphological and structural characterizations of fe3o4au hybrid nanorods synthesized by annealing of feooh  au hybrid nanorods under ar atmosphere : a xrd pattern ; b sem image ; c tem image ; d hrtem image infrared spectra of fe2o3au and fe3o4au hybrid nanorods fe3o4au and -fe2o3au hybrid nanorods show the combined magnetic and optical properties , which originate from iron oxide nanorods and au nanoparticles , respectively . figure 7 shows the room - temperature magnetization curves of fe3o4au and -fe2o3au hybrid nanorods . it can be seen that fe3o4au hybrid nanorods exhibit a typical ferromagnetic behavior , with a saturation magnetization , ms = 29.8 emu g ; remnant magnetization , mr = 1.7 emu g ; and coercive field , hc = 50.1 oe . the saturation magnetization of fe3o4au hybrid nanorods is lower than that of bulk fe3o4 ( 92 emu g )   due to the existence of non - magnetic au ; however , it is enough for biology and medicine application [ 3 - 6 ] . in contrast , -fe2o3au shows almost no magnetic property , which is similar to bulk -fe2o3 . therefore , fe3o4au hybrid nanorods can be applied in biotechnologies [ 3 - 6 ] , while -fe2o3au hybrid nanorods are more suitable for application in catalysts . figure 8 shows the room - temperature uv  vis spectra of fe3o4au and -fe2o3au hybrid nanorods dispersed in ethanol . it is known that for au nanoparticles with sizes ranging from 5 to 20 nm in diameter , the electrons are trapped in the small au metal box and show a characteristic collective oscillation frequency of plasmon resonance , giving rise to the plasmon resonance band at around 520 nm . the exact absorption varies with nanoparticles morphology and particle surface coating . herein , compared to pure fe3o4 and -fe2o3 nanorods , both fe3o4au and -fe2o3au hybrid nanorods show a broad peak located at about 525 nm , which is similar to previous reports [ 10 - 12 ] . deposition of au nanoparticles onto the surface of fe3o4 and -fe2o3 nanorods results in the broadening of the peak . room - temperature magnetization curves of fe3o4au ( a ) and fe2o3au ( b ) hybrid nanorods room - temperature uv  vis spectra of fe2o3au ( a ) and fe3o4au ( b ) hybrid nanorods feooh  au hybrid nanorods have been synthesized via layer - by - layer assembly , which can be transformed into -fe2o3au and fe3o4au hybrid nanorods by controllable annealing process . the strong electrostatic attraction between aucl4 and polyelectrolyte - modified feooh nanorods plays the most important role in the uniform deposition of au nanoparticles . the annealing atmosphere determines the phase transformation from feooh  au to -fe2o3au and fe3o4au . the as - synthesized fe3o4au hybrid nanorods show the high saturation magnetizations , and -fe2o3au hybrid nanorods show the low saturation magnetizations , respectively . the uv  vis analysis indicates that both fe3o4au and -fe2o3au hybrid nanorods show a broad peak located at about 525 nm . it is believed that the as - synthesized fe3o4au and -fe2o3au hybrid nanorods can be applied in biotechnologies and catalysts , respectively . the authors thank the doctoral science foundation of zhejiang sci - tech university ( no . 0803611-y ) and national natural science foundation of china ( no . this article is distributed under the terms of the creative commons attribution noncommercial license which permits any noncommercial use , distribution , and reproduction in any medium , provided the original author(s ) and source are credited . this article is distributed under the terms of the creative commons attribution noncommercial license which permits any noncommercial use , distribution , and reproduction in any medium , provided the original author(s ) and source are credited .
a layer - by - layer technique has been developed to synthesize feooh 
 au hybrid nanorods that can be transformed into fe2o3au and fe3o4au hybrid nanorods via controllable annealing process . 
 the homogenous deposition of au nanoparticles onto the surface of feooh nanorods can be attributed to the strong electrostatic attraction between metal ions and polyelectrolyte - modified feooh nanorods . 
 the annealing atmosphere controls the phase transformation from feooh  au to fe3o4au and -fe2o3au . 
 moreover , the magnetic and optical properties of as - synthesized fe2o3au and fe3o4au hybrid nanorods have been investigated .