Efficient Electrochemical Reduction of CO(2) to Formate in Methanol Solutions by Mn‐Functionalized Electrodes in the Presence of Amines

Carbon cloth electrode modified by covalently attaching a manganese organometallic catalyst is used as cathode for the electrochemical reduction of CO(2) in methanol solutions. Six different industrial amines are employed as co‐catalyst in millimolar concentrations to deliver a series of new reactive system. While such absorbents were so far believed to provide a CO(2) reservoir and act as sacrificial proton source, we herein demonstrate that this role can be played by methanol, and that the adduct formed between CO(2) and the amine can act as an effector or inhibitor toward the catalyst, thereby enhancing or reducing the production of formate. Pentamethyldiethylentriamine (PMDETA), identified as the best effector in our series, converts CO(2) in wet methanolic solution into bisammonium bicarbonate. Computational studies revealed that this adduct is responsible for a barrierless transformation of CO(2) to formate by the reduced form of the Mn catalyst covalently bonded to the electrode surface. As a consequence, selectivity can be switched on demand from CO to formate anion, and in the case of (PMDETA) an impressive TON(HCOO−) of 2.8×10(4) can be reached. This new valuable knowledge on an integrated capture and utilization system paves the way toward more efficient transformation of CO(2) into liquid fuel.