Electroreduction of CO2 to Formate with Low Overpotential using Cobalt Pyridine Thiolate Complexes
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Date
2020-09-01Type
- Journal Article
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. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Show more
Publication status
publishedExternal links
Journal / series
Angewandte Chemie. International EditionVolume
Pages / Article No.
Publisher
WileySubject
CO2 reduction; cobalt thiolate complexes; electrocatalysis; formate; overpotentialOrganisational unit
09654 - Mougel, Victor / Mougel, Victor
Related publications and datasets
Is original form of: http://hdl.handle.net/20.500.11850/438630
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