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.