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Electroreduction of CO2 to Formate with Low Overpotential using Cobalt Pyridine Thiolate Complexes
Authors:Subal Dey  Tanya K. Todorova  Marc Fontecave  Victor Mougel
Affiliation:1. Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1–5, 8093 Zürich, Switzerland;2. Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Paris, Sorbonne Université, PSL Research University, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
Abstract:Electrocatalytic CO2 reduction to value-added products provides a viable alternative to the use of carbon sources derived from fossil fuels. Carrying out these transformations at reasonable energetic costs, for example, with low overpotential, remains a challenge. Molecular catalysts allow fine control of activity and selectivity via tuning of their coordination sphere and ligand set. Herein we investigate a series of cobalt(III) pyridine-thiolate complexes as electrocatalysts for CO2 reduction. The effect of the ligands and proton sources on activity was examined. We identified bipyridine bis(2-pyridinethiolato) cobalt(III) hexaflurophosphate as a highly selective catalyst for formate production operating at a low overpotential of 110 mV with a turnover frequency (TOF) of 10 s−1. Electrokinetic analysis coupled with density functional theory (DFT) computations established the mechanistic pathway, highlighting the role of metal hydride intermediates. The catalysts deactivate via the formation of stable cobalt carbonyl complexes, but the active species could be regenerated upon oxidation and release of coordinated CO ligands.
Keywords:CO2 reduction  cobalt thiolate complexes  electrocatalysis  formate  overpotential
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