A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
dc.contributor.author
dc.date.accessioned
2020-01-27T07:42:39Z
dc.date.available
2021-04-07T08:03:01Z
dc.date.issued
2020
dc.identifier.issn
0002-7863
dc.identifier.uri
dc.description.abstract
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
dc.description.sponsorship
We would like to thank the European Commission for the ERCCG-2014-648304 (J.Ll.-F) project. The Spanish Ministry of Science is acknowledged for a FPU fellowship to S.F. and C.C. We
also thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane. The financial support from ICIQ Foundation and
CELLEX Foundation through the CELLEX-ICIQ and the Starting
Career Program is gratefully acknowledged. We also thank
CERCA Programme and DIUE 2014SGR931 (Generalitat de Catalunya) for financial support and MINECO project CTQ2016-
80038-R and PGC2018-098212-B-C22
dc.format.extent
14 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22/ES/DESCOMPOSICION EN EL ESPACIO REAL DE PROPIEDADES OPTICAS NO LINEALES PARA EL DISEÑO RACIONAL DE MATERIALES OPTOELECTRONICOS/
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1021/jacs.9b06633
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© Journal of the American Chemical Society, 2020, vol. 142, núm. 1, p. 120-133
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
Fernández, Sergio Franco, Federico Casadevall, Carla Martin-Diaconescu, Vlad Luis Luis, Josep Maria Lloret Fillol, Julio 2019 A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes Journal of the American Chemical Society 142 1 120 133
dc.subject
dc.title
A Unified Electro- and Photocatalytic CO2 to CO Reduction Mechanism with Aminopyridine Cobalt Complexes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
2020-12-10T00:00:00Z
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2020-12-10
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
030936
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126