Electroreduction of CO2 to Formate with Low Overpotential using Cobalt Pyridine Thiolate Complexes

Angewandte Chemie
Subal DeyVictor Mougel

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.

References

Aug 4, 1999·Proceedings of the National Academy of Sciences of the United States of America·H DobbekR Huber
Jul 10, 2001·Inorganic Chemistry·K J FranzS J Lippard
Dec 12, 2002·Proceedings of the National Academy of Sciences of the United States of America·Holger DobbekOrtwin Meyer
May 20, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Maria João Romão
Dec 15, 2011·Chemical Society Reviews·Jacob SchneiderEtsuko Fujita
Mar 7, 2012·Journal of the American Chemical Society·Peng KangMaurice Brookhart
Oct 9, 2012·Science·Cyrille CostentinJean-Michel Savéant
Dec 13, 2012·Chemical Society Reviews·Cyrille CostentinJean-Michel Savéant
Jan 12, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Souvik RoyAnne K Jones
Feb 20, 2013·Inorganic Chemistry·Jonathan M SmiejaClifford P Kubiak
Jan 29, 2014·Chemical Reviews·Russ HillePartha Basu
Apr 30, 2014·Inorganic Chemistry·David C LacyJonas C Peters
Dec 6, 2014·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Luisa B MaiaIsabel Moura
Feb 26, 2015·Journal of the American Chemical Society·Jesse D Froehlich, Clifford P Kubiak
Jun 19, 2015·Journal of the American Chemical Society·Charles W MachanClifford P Kubiak
Aug 28, 2015·Journal of the American Chemical Society·Biswajit MondalAbhishek Dey
Nov 10, 2015·Chemistry : a European Journal·Marcello GennariCarole Duboc
Apr 20, 2016·Journal of the American Chemical Society·Alon ChapovetskySmaranda C Marinescu
Oct 22, 2016·Nature Chemistry·Deborah BrazzolottoCarole Duboc
Jan 25, 2017·Journal of the American Chemical Society·Ken T NgoJonathan Rochford
Feb 17, 2017·Journal of the American Chemical Society·Souvik RoyVincent Artero
May 4, 2017·Journal of the American Chemical Society·Moritz F KuehnelErwin Reisner
Feb 1, 2018·Inorganic Chemistry·Asa W NicholsCharles W Machan
Nov 23, 2018·Proceedings of the National Academy of Sciences of the United States of America·Bianca M Ceballos, Jenny Y Yang
Dec 11, 2019·Journal of the American Chemical Society·Sergio FernándezJulio Lloret-Fillol
Apr 9, 2020·Inorganic Chemistry·Md Estak AhmedAbhishek Dey

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