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A Bioinspired Molybdenum-Copper Molecular Catalyst for CO2 Electroreduction

preprint
submitted on 21.02.2020 and posted on 24.02.2020 by Ahmed Mouchfiq, Tanya K. Todorova, Subal Dey, Marc Fontecave, Victor Mougel
Non‐noble metal molecular catalysts mediating the electrocatalytic reduction of carbon dioxide are still scarce. This work reports the electrochemical reduction of CO2 to formate catalyzed by the bimetallic complex [(bdt)MoVI(O)S2CuICN]2‐ (bdt = benzenedithiolate), a mimic of the active site of the Mo‐Cu carbon monoxide dehydrogenase enzyme (CODH2). Infrared spectroelectrochemical (IR‐SEC) studies coupled with density functional theory (DFT) computations revealed that the complex is only a pre‐catalyst, the active catalyst being generated upon reduction in the presence of CO2. We found that the two‐electron reduction of [(bdt)MoVI(O)S2CuICN]2‐ triggers the transfer of the oxo moiety to CO2 forming CO3 2‐and the complex [(bdt)MoIVS2CuICN]2– and that a further oneelectron reduction is needed to generate the active catalyst. Its protonation yields a reactive MoVH hydride intermediate which reacts with CO2 to produce formate. These findings are particularly relevant to the design of catalysts from metal oxo precursors.

History

Email Address of Submitting Author

mougel@inorg.chem.ethz.ch

Institution

ETH Zürich

Country

Switzerland

ORCID For Submitting Author

0000-0003-4136-7442

Declaration of Conflict of Interest

no conflict of interest

Version Notes

Submitted manuscript on 21/02/2020

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