Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines

The electrochemical reduction of CO2 (CO2RR) into value-added chemicals offers a promising route toward a circular carbon economy and a reduced reliance on fossil fuels. A detailed understanding of the structural and electronic factors that govern the performance of molecular CO2RR electrocatalysts...

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Autores: Abudayyeh, Abdullah M., De Kreijger, Simon, Grau, Sergi, Eryılmaz, Eren, Robeyns, Koen, Ertem, Mehmed Z., Llobet, Antoni, Elias, Benjamin, Troian-Gautier, Ludovic
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/489076
Acceso en línea:http://hdl.handle.net/2072/489076
https://doi.org/10.1021/acscatal.5c06871
Access Level:acceso embargado
Palabra clave:Química
54
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spelling Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-BipyridinesAbudayyeh, Abdullah M.De Kreijger, SimonGrau, SergiEryılmaz, ErenRobeyns, KoenErtem, Mehmed Z.Llobet, AntoniElias, BenjaminTroian-Gautier, LudovicQuímica54The electrochemical reduction of CO2 (CO2RR) into value-added chemicals offers a promising route toward a circular carbon economy and a reduced reliance on fossil fuels. A detailed understanding of the structural and electronic factors that govern the performance of molecular CO2RR electrocatalysts is essential for designing efficient and tunable systems. Here, we report a series of rhenium(I) complexes, fac-[ReI(6,6′-(R)2-bpy)(CO)3Cl] (bpy = 2,2′-bipyridine; R = mesityl (mes), 2,4,6-triisopropylphenyl (trip), or isophthalic acid (phth)) and evaluate their electrocatalytic activity. Among these, fac-[ReI(6,6′-(mes)2-bpy)(CO)3Cl] exhibited the highest performance, enabling selective CO2-to-CO conversion for 1 h with Faradaic efficiency (FE) >97%, representing an enhanced activity level for Rebpy catalysts. Single-crystal X-ray diffraction and density functional theory (DFT) calculations indicated that favorable CO2 binding can be promoted by tilting the 6,6′-(mes)2-bpy ligand (from the Re–CO coordination plane), providing mechanistic insight into the observed enhancement. The study consequently demonstrates a rational correlation between the CO2 electrocatalytic performance of Rebpy catalysts and their structural variations, as derived from X-ray data and corroborated by computational modeling.info:eu-repo/semantics/acceptedVersionACS Publications2025info:eu-repo/semantics/article14 p.application/pdfhttp://hdl.handle.net/2072/489076https://doi.org/10.1021/acscatal.5c06871RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésFonds de la Recherche Scientifique (F.R.S.-FNRS) under grant CDR no. 40020332This publication benefited from the support of the Walloon Region as part of the financing of the FRFS-WEL-T strategic axisL.T.-G. is a Chercheur Qualifié of the Fonds de la Recherche Scientifique – FNRS. A.M.A., S.D.K., K.R., B.E., and L.T.-G. gratefully acknowledge the UCLouvain for financial supportDE-SC0012704 with the U.S. Department of Energy, Office of Science, Office of Basic Energy SciencesCERCA Program/Generalitat de CatalunyaSevero Ochoa Excellence Accreditation CEX2024-001469-S, funded by MCIU/AEI/10.13039/501100011033MICINN through project PID2022-140143OB-I00Generalitat de Catalunya through project 2021 SGR 01583Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/embargoedAccessoai:recercat.cat:2072/4890762026-05-29T05:05:01Z
dc.title.none.fl_str_mv Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
title Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
spellingShingle Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
Abudayyeh, Abdullah M.
Química
54
title_short Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
title_full Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
title_fullStr Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
title_full_unstemmed Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
title_sort Enhanced Electrocatalytic and Selective CO2-to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines
dc.creator.none.fl_str_mv Abudayyeh, Abdullah M.
De Kreijger, Simon
Grau, Sergi
Eryılmaz, Eren
Robeyns, Koen
Ertem, Mehmed Z.
Llobet, Antoni
Elias, Benjamin
Troian-Gautier, Ludovic
author Abudayyeh, Abdullah M.
author_facet Abudayyeh, Abdullah M.
De Kreijger, Simon
Grau, Sergi
Eryılmaz, Eren
Robeyns, Koen
Ertem, Mehmed Z.
Llobet, Antoni
Elias, Benjamin
Troian-Gautier, Ludovic
author_role author
author2 De Kreijger, Simon
Grau, Sergi
Eryılmaz, Eren
Robeyns, Koen
Ertem, Mehmed Z.
Llobet, Antoni
Elias, Benjamin
Troian-Gautier, Ludovic
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Química
54
topic Química
54
description The electrochemical reduction of CO2 (CO2RR) into value-added chemicals offers a promising route toward a circular carbon economy and a reduced reliance on fossil fuels. A detailed understanding of the structural and electronic factors that govern the performance of molecular CO2RR electrocatalysts is essential for designing efficient and tunable systems. Here, we report a series of rhenium(I) complexes, fac-[ReI(6,6′-(R)2-bpy)(CO)3Cl] (bpy = 2,2′-bipyridine; R = mesityl (mes), 2,4,6-triisopropylphenyl (trip), or isophthalic acid (phth)) and evaluate their electrocatalytic activity. Among these, fac-[ReI(6,6′-(mes)2-bpy)(CO)3Cl] exhibited the highest performance, enabling selective CO2-to-CO conversion for 1 h with Faradaic efficiency (FE) >97%, representing an enhanced activity level for Rebpy catalysts. Single-crystal X-ray diffraction and density functional theory (DFT) calculations indicated that favorable CO2 binding can be promoted by tilting the 6,6′-(mes)2-bpy ligand (from the Re–CO coordination plane), providing mechanistic insight into the observed enhancement. The study consequently demonstrates a rational correlation between the CO2 electrocatalytic performance of Rebpy catalysts and their structural variations, as derived from X-ray data and corroborated by computational modeling.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/489076
https://doi.org/10.1021/acscatal.5c06871
url http://hdl.handle.net/2072/489076
https://doi.org/10.1021/acscatal.5c06871
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Fonds de la Recherche Scientifique (F.R.S.-FNRS) under grant CDR no. 40020332
This publication benefited from the support of the Walloon Region as part of the financing of the FRFS-WEL-T strategic axis
L.T.-G. is a Chercheur Qualifié of the Fonds de la Recherche Scientifique – FNRS. A.M.A., S.D.K., K.R., B.E., and L.T.-G. gratefully acknowledge the UCLouvain for financial support
DE-SC0012704 with the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
CERCA Program/Generalitat de Catalunya
Severo Ochoa Excellence Accreditation CEX2024-001469-S, funded by MCIU/AEI/10.13039/501100011033
MICINN through project PID2022-140143OB-I00
Generalitat de Catalunya through project 2021 SGR 01583
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv 14 p.
application/pdf
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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