Accessing and Photo-Accelerating Low-Overpotential Pathways for CO2 Reduction: A Bis-Carbene Ruthenium Terpyridine Catalyst
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Otros documentos de la autoría: Assaf, Eric A.; Gonell, Sergio; Chen, Chun-Hsing; Miller, Alexander
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https://doi.org/10.1021/acscatal.2c03651 |
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Título
Accessing and Photo-Accelerating Low-Overpotential Pathways for CO2 Reduction: A Bis-Carbene Ruthenium Terpyridine CatalystFecha de publicación
2022-10-21Editor
American Chemical SocietyISSN
2155-5435Cita bibliográfica
Assaf, E. A.; Gonell, S.; Chen, C. H.; Miller, A. J. Accessing and Photo-Accelerating Low-Overpotential Pathways for CO2 Reduction: A Bis-Carbene Ruthenium Terpyridine Catalyst. ACS Catal. 2022, 12, 20, 12596-12606. DOI: 10.1021/acscatal.2c03651Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://pubs.acs.org/doi/full/10.1021/acscatal.2c03651Versión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
A ruthenium catalyst bearing a bidentate bis(carbene) ligand is prepared and studied as a catalyst for CO2 electroreduction. The catalyst [Ru(tpy)(bis-mim)(MeCN)][PF6]2 (tpy) is 2,2′,:6′,2″-terpyridine; bis-mim is ... [+]
A ruthenium catalyst bearing a bidentate bis(carbene) ligand is prepared and studied as a catalyst for CO2 electroreduction. The catalyst [Ru(tpy)(bis-mim)(MeCN)][PF6]2 (tpy) is 2,2′,:6′,2″-terpyridine; bis-mim is (methylenebis(N-methylimidazol-2-ylidene)) mediates reduction of CO2 into CO with a turnover frequency of 630 s–1 and Faradaic efficiency (FE) of 30% at an overpotential of 730 mV. The strongly donating bis(carbene) ligand also enables access to a pathway operating at a lower overpotential of ca. 310 mV. While low-overpotential catalysis is slow in the dark (TOF = 0.01 s–1), visible light illumination increases the rate 10-fold (TOF = 0.11 s–1). A full mechanistic picture is developed using kinetic analysis from cyclic voltammetry, spectroelectrochemistry, and computational methods, with the bis-mim ligand facilitating rapid CO2 activation at low overpotentials. Comparisons with other ruthenium catalysts yield insight into the ability to tune the rate of chemical steps (e.g., ligand dissociation and CO2 nucleophilic attack) and the overpotential by tailoring the primary coordination sphere while retaining the “redox-active” tpy ligand. [-]
Publicado en
Catalyst. ACS Catalysis, 2022, vol. 12, no 20Entidad financiadora
United States Department of Energy (DOE) | National Science Foundation (NSF)
Código del proyecto o subvención
DE-SC0021173 | DE-SC0001011 | CHE-1828183 | CHE-1726291
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Copyright © American Chemical Society
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