A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes

A mechanistic understanding of electro- and photocatalytic CO2 reduction is crucial to develop strategies to overcome catalytic bottlenecks. In this regard, for a new CO2-to-CO reduction cobalt aminopyridine catalyst, a detailed experimental and theoretical mechanistic study is herein presented towa...

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Autores: Fernández, Sergio, Franco, Federico, Casadevall, Carla, Martin-Diaconescu, Vlad, Luis, Josep María, Lloret-Fillol, Julio
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
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:2072/368580
Acceso en línea:http://hdl.handle.net/2072/368580
https://doi.org/10.1021/jacs.9b06633
Access Level:acceso abierto
Palabra clave:54
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spelling A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt ComplexesFernández, SergioFranco, FedericoCasadevall, CarlaMartin-Diaconescu, VladLuis, Josep MaríaLloret-Fillol, Julio54A mechanistic understanding of electro- and photocatalytic CO2 reduction is crucial to develop strategies to overcome catalytic bottlenecks. In this regard, for a new CO2-to-CO reduction cobalt aminopyridine catalyst, a detailed experimental and theoretical mechanistic study is herein presented toward the identification of bottlenecks and potential strategies to alleviate them. The combination of electrochemistry and in situ spectroelectrochemistry together with spectroscopic techniques led us to identify elusive key electrocatalytic intermediates derived from complex [LN4Co(OTf)2] (1) (LN4 = 1-[2-pyridylmethyl]-4,7-dimethyl-1,4,7-triazacyclononane) such as a highly reactive cobalt(I) (1(I)) and a cobalt(I) carbonyl (1(I)-CO) species. The combination of spectroelectrochemical studies under CO2, 13CO2, and CO with DFT disclosed that 1(I) reacts with CO2 to form the pivotal 1(I)-CO intermediate at the 1(II/I) redox potential. However, at this reduction potential, the formation of 1(I)-CO restricts the electrocatalysis due to the endergonicity of the CO release step. In agreement with the experimentally observed CO2-to-CO electrocatalysis at the CoI/0 redox potential, computational studies suggested that the electrocatalytic cycle involves striking metal carbonyls. In contrast, under photochemical conditions, the catalysis smoothly proceeds at the 1(II/I) redox potential. Under the latter conditions, it is proposed that the electron transfer to form 1(I)-CO from 1(II)-CO is under diffusion control. Then, the CO release from 1(II)-CO is kinetically favored, facilitating the catalysis. Finally, we have found that visible-light irradiation has a positive impact under electrocatalytic conditions. We envision that light irradiation can serve as an effective strategy to circumvent the CO poisoning and improve the performance of CO2 reduction molecular catalysts.2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion120 p.application/pdfhttp://hdl.handle.net/2072/368580https://doi.org/10.1021/jacs.9b06633RECERCAT (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)InglésERCCG- 2014-648304DIUE 2014SGR931CTQ2016- 80038-RPGC2018-098212-B-C22L'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2072/3685802026-05-29T05:05:01Z
dc.title.none.fl_str_mv A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
title A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
spellingShingle A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
Fernández, Sergio
54
title_short A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
title_full A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
title_fullStr A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
title_full_unstemmed A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
title_sort A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
dc.creator.none.fl_str_mv Fernández, Sergio
Franco, Federico
Casadevall, Carla
Martin-Diaconescu, Vlad
Luis, Josep María
Lloret-Fillol, Julio
author Fernández, Sergio
author_facet Fernández, Sergio
Franco, Federico
Casadevall, Carla
Martin-Diaconescu, Vlad
Luis, Josep María
Lloret-Fillol, Julio
author_role author
author2 Franco, Federico
Casadevall, Carla
Martin-Diaconescu, Vlad
Luis, Josep María
Lloret-Fillol, Julio
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv 54
topic 54
description A mechanistic understanding of electro- and photocatalytic CO2 reduction is crucial to develop strategies to overcome catalytic bottlenecks. In this regard, for a new CO2-to-CO reduction cobalt aminopyridine catalyst, a detailed experimental and theoretical mechanistic study is herein presented toward the identification of bottlenecks and potential strategies to alleviate them. The combination of electrochemistry and in situ spectroelectrochemistry together with spectroscopic techniques led us to identify elusive key electrocatalytic intermediates derived from complex [LN4Co(OTf)2] (1) (LN4 = 1-[2-pyridylmethyl]-4,7-dimethyl-1,4,7-triazacyclononane) such as a highly reactive cobalt(I) (1(I)) and a cobalt(I) carbonyl (1(I)-CO) species. The combination of spectroelectrochemical studies under CO2, 13CO2, and CO with DFT disclosed that 1(I) reacts with CO2 to form the pivotal 1(I)-CO intermediate at the 1(II/I) redox potential. However, at this reduction potential, the formation of 1(I)-CO restricts the electrocatalysis due to the endergonicity of the CO release step. In agreement with the experimentally observed CO2-to-CO electrocatalysis at the CoI/0 redox potential, computational studies suggested that the electrocatalytic cycle involves striking metal carbonyls. In contrast, under photochemical conditions, the catalysis smoothly proceeds at the 1(II/I) redox potential. Under the latter conditions, it is proposed that the electron transfer to form 1(I)-CO from 1(II)-CO is under diffusion control. Then, the CO release from 1(II)-CO is kinetically favored, facilitating the catalysis. Finally, we have found that visible-light irradiation has a positive impact under electrocatalytic conditions. We envision that light irradiation can serve as an effective strategy to circumvent the CO poisoning and improve the performance of CO2 reduction molecular catalysts.
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/368580
https://doi.org/10.1021/jacs.9b06633
url http://hdl.handle.net/2072/368580
https://doi.org/10.1021/jacs.9b06633
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv ERCCG- 2014-648304
DIUE 2014SGR931
CTQ2016- 80038-R
PGC2018-098212-B-C22
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 120 p.
application/pdf
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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score 15.811543

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