The development of efficient catalysts for the electrochemical reduction of CO2, a very active research topic, should not be envisaged in the sole framework of CO2 utilization, but rather as a brick of an entire carbon capture, utilization and storage (CCUS) value chain. Recent reports pointed out that an integrated approach, wherein the capture, utilization and storage technologies are designed to operate synergistically, may represent one of most effective options for viable and scalable GHG (Green House Gases) mitigation. Post-combustion CO2 capture is the most mature technology for flue gas treatment, and it is already implemented into existing power plants. To process diluted and low-pressure streams, such as those emitted by fossil-fired power plants, chemical absorption with aqueous amine solutions, called aminescrubbing, is the most appropriate technology. Amines spontaneously react with CO2 affording equilibrated mixtures of ammonium carbamates (Scheme 1, eq. 1) and bicarbonate (in the presence of water, Scheme 1, eq. 2). Captured CO2 can be released by thermally reversing these reactions, but the associated energetic cost is one of the major drawbacks. In situ direct transformation of captured CO2 (in the form of ammonium carbamate or bicarbonate) is a challenging alternative, which fits into the aforementioned process integration paradigm. Although most CO2 utilization processes reported to date operate from purified CO2, there has been a growing interest for the direct conversion of capture products in the past decade. These examples include the utilization of carbamates as metal extractants , as vehicles for mineral carbonation , or their conversion into renewable fuels such as methanol. The latter is a true transformation, not a utilization but it raises the issue of the electron source needed to produce hydrogen, itself required for CO2 reduction. Using renewable electrical energy (i.e. photochemical or electrochemical reductions ) for CO2 reduction surely represents a step further toward true sustainable CCUS but also an additional challenge. Yet, photochemical or electrochemical reduction strategies enabling to produce C1 and C2 chemicals from flue gases will certainly be one of the essential bricks of the next industrial revolution. The main products of CO2 electrolysis are usually CO, CH4, C2H4, formate, CH3OH and CH3CH2OH, which are valuable feedstocks for the chemical industry and for energy storage. A large array of transition metal complexes containing macrocyclic, (e.g. porphyrins, phthalocyanines, corroles and cyclams), polydentate, (e.g. 2,2'-bipyridine (bpy), 1,10phenantroline (phen), etc.) and phosphine ligands (e.g. 1,2bis(diphenylphosphino)ethane (dppe), triphenylphosphine (PPh3), etc.) have been tested as molecular electrocatalysts in solutions, wherein CO2 was injected as a pure gas. Re-and Mn-polypyridine complexes were shown to be among the most promising catalysts, displaying high reaction rates and selectivity. As a consequence, their reduction mechanisms were extensively explored. By fine-tuning electronic properties and steric hindrance around the metal centre, the selectivity and the activity of the electrocatalyst can be controlled. The availability of local proton sources is known to greatly impact these two parameters, potentially enabling to shift the CO2 reduction process from the production of CO to formate. In particular, polypyridyl Mn(I) catalysts (e.g. [Mn(pdbpy)(CO)3Br] (pdbpy = 4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine) containing two acidic OH groups in proximity of the purported metal binding site for CO2 redox catalysis show enhanced catalytic activity towards HCOOH production. As mentioned earlier, examples of electrochemical CO2 reduction integrated to its absorption remain scarce. To our knowledge, only two studies to date reported the reduction of CO2 with a Mn-based soluble electrocatalyst, in the presence of amines (in solution or bound to the metal chelating unit). Amine moieties were proposed not only to provide binding sites, hence a reservoir of CO2 under the form of carbamates, but also to stabilize and promote the formation of the hydride catalytic intermediate (HMn), thereby favouring formate production instead of CO. These amines, which are supposed to work as proton shuttle, were either introduced in large excess with respect the catalyst or upon an elaborated synthetic procedure as a side-arm of the Mn catalyst (Figure ). Hydride transfer to CO2 requires a proton source, a role which was endorsed by acidic alcohols such as phenols or perfluoroalcohols. None of this class of sacrificial proton donors seems eligible for potential implementation into a cost-effective industrial process, while water suffers from low CO2 solubility. To enable the industrial utilization of CO2 for energy production, liquid fuels (i.e. formate) rather than gas precursors (i.e. CO) should be preferred for safety, storage and transportation reasons. In the same perspective of deployment, the immobilization of organometallic complexes onto a conductive support (via van der Waals interactions or by the formation of a covalent bond between the electrode surface and the intact transition metal catalysts ) is highly desirable. It enables to envisage a broader scope of solvents, including carbon capture media, and provides the reduction systems with increased durability, efficiency, recyclability and processability. Herein we investigate the role and impact of amines in millimolar concentration on the electroreduction of CO2 by a Mn bipyridyl complex (fac-Mn(apbpy)(CO)3Br [apbpy=4-(4aminophenyl)-2,2'-bipyridine)]) covalently bound to a Carbon Cloth (CC) surface. CC is a relatively cheap material of low electrical resistance and large surface area, widely exploited for the preparation of electrodes for low temperature fuel cells. The functionalized electrode (Mn/CC) was tested as a catalyst for CO2 electrochemical reduction in a three-electrode cell with two gastight compartments, with methanol as a solvent. Its performance was studied in the presence of a panel of industrial amines (Figure ) by means of Controlled Potential Electrolysis (CPE). By a combination of theoretical and experimental investigations, we herein show that methanol acts at the same time as a carbon solvent, enhancing CO2 solubility compared to water, and as an affordable sacrificial proton source. In our system, amines rather play the role of homogeneous cocatalysts or co-factors during the reduction process. Combining a heterogeneous catalysis approach and a more accessible sacrificial proton source may also pave the way toward scalable capture and integrated electroreduction processes. Results and discussion fac-Mn(apbpy)(CO)3Br was anchored to a carbon cloth (CC) electrode surface via the formation of C-C bonds. The presence of the aniline moiety on the bipyridyl ligand enables the grafting of the complex onto carbon surfaces via the in situ formation of the corresponding diazonium salt (see supporting section 4). This method advantageously bypasses the isolation and purification of the diazonium reactive intermediate. Electrochemical reduction is performed to trigger C-C bond formation and N2 evolution. To assess the amount of electrocatalyst covalently bound on CC, a comparative ICP analysis was performed on the pristine CC starting material and on Mn/CC (see supporting section 4). A surface coverage Γ of 1.67×10 -9 mol cmECSA -2 was obtained, in reasonable agreement with the previously reported value (1.4×10 -9 mol cmECSA -2 ), determined via the indirect method of charge integration of the CV data collected from CC bonded nitroaniline. C0 (mM) 1 50 175 At such a low amine concentration (1 mM), at least three orders of magnitude lower than what is commonly used for CO2 capture (MEA 5 M, 30% w/w), most of the captured CO2 is absorbed by physical dissolution (see Table ). In fact, at room temperature and under a partial pressure p(CO2) = 1 atm, this gas has a solubility of 0.007 in MeOH, which translates into a concentration around 175 mM. Although our amine solutions are rather diluted (1 mM), the values of carbamation and carbonation equilibrium constants (Scheme 1) suggest that these processes remain quantitative in our operational conditions (see supporting section 5 for the relationship between binding constant per nitrogen site and per absorbent molecule). This was experimentally verified by 1 H NMR for DEA, DETA and PMDETA, which cover the scope of primary to tertiary amines, bearing between one and three binding sites and either undergoing preferentially carbamation or carbonation (see SI section 7). As Gibb's free energy of carbonation is lower compared to carbamation, we herein used a 50-fold excess of water with respect to the amine, which enables the former process to be as favoured as the latter (Table and Scheme 1, eq. 2). In our operating conditions, amines are stoichiometrically loaded with CO2. Yet, these adducts cannot be realistically considered as substrates for CO2 conversion, as they are 100 times less abundant than dissolved CO2. In addition, and as reported in Table , they are also substantially more stabilized than the dissolved gas. In such conditions, the scenario wherein ammonium carbamates and carbonates (more stable and less abundant than dissolved CO2) act as substrates during electroreduction can eventually be ruled out, allowing us to focus on the potential role of these CO2-amine derivatives in the very catalytic process. We have recently shown that industrial polyamines used for CO2 capture are powerful metal chelators which can effectively be employed for metal extraction in methanolic medium. In agreement with this previous study, we observed that 20 minutes of CO2 flow were required to fully pre-load the amine solution and further enable the electrolysis to proceed properly. Any attempt to directly contact the unloaded diluted amine and the catalyst, systematically resulted in a detrimental effect on the reduction activity. In addition, DFT calculations also suggests that the real catalyst (i.e. the Mn pentacoordinate anion [Mn(bpy)(CO)3] -, Mn -, see Scheme 2 below) prefers to coordinate the free amine rather than CO2 or MeOH (see supporting section 8). After the preliminary CO2 saturation, Mn/CC was inserted in solution, continuously supplied with CO2 while the electrolysis was conducted with a set potential of -1.35 V vs. Ag/AgCl. Karl-Fischer titrations were performed at the beginning and at the end of the process, confirming that a constant amount of H2O was present in the medium, around 0.96 mg/mL (i.e. 0.1 % w/w or 50 mM).