Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues

The complex α-[Fe(mcp)(OTf)2] (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-diamine and OTf = trifluoromethanesulfonate anion) was reported in 2011 by some of us as an active water oxidation (WO) catalyst in the presence of sacrificial oxidants. However, because chemical oxidants...

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Autores: D'Agostini, Silvia, Kottrup, Konstantin G., Casadevall, Carla, Gamba, Ilaria, Dantignana, Valeria, Bucci, Alberto, Costas Salgueiro, Miquel, Lloret Fillol, Julio, Hetterscheid, Dennis G.H.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
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:10256/19194
Acceso en línea:http://hdl.handle.net/10256/19194
Access Level:acceso abierto
Palabra clave:Oxidació electrolítica
Electrolytic oxidation
Electrocatàlisi
Electrocatalysis
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spelling Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and AnaloguesD'Agostini, SilviaKottrup, Konstantin G.Casadevall, CarlaGamba, IlariaDantignana, ValeriaBucci, AlbertoCostas Salgueiro, MiquelLloret Fillol, JulioHetterscheid, Dennis G.H.Oxidació electrolíticaElectrolytic oxidationElectrocatàlisiElectrocatalysisThe complex α-[Fe(mcp)(OTf)2] (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-diamine and OTf = trifluoromethanesulfonate anion) was reported in 2011 by some of us as an active water oxidation (WO) catalyst in the presence of sacrificial oxidants. However, because chemical oxidants are likely to take part in the reaction mechanism, mechanistic electrochemical studies are critical in establishing to what extent previous studies with sacrificial reagents have actually been meaningful. In this study, the complex α-[Fe(mcp)(OTf)2] and its analogues were investigated electrochemically under both acidic and neutral conditions. All the systems under investigation proved to be electrochemically active toward the WO reaction, with no major differences in activity despite the structural changes. Our findings show that WO-catalyzed by mcp–iron complexes proceeds via homogeneous species, whereas the analogous manganese complex forms a heterogeneous deposit on the electrode surface. Mechanistic studies show that the reaction proceeds with a different rate-determining step (rds) than what was previously proposed in the presence of chemical oxidants. Moreover, the different kinetic isotope effect (KIE) values obtained electrochemically at pH 7 (KIE ∼ 10) and at pH 1 (KIE = 1) show that the reaction conditions have a remarkable effect on the rds and on the mechanism. We suggest a proton-coupled electron transfer (PCET) as the rds under neutral conditions, whereas at pH 1 the rds is most likely an electron transfer (ET)NWO Echo grant 717.014.008. PGC2018-101737-B-I00 and 2017 SGR 00264 grantsAmerican Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/19194http://hdl.handle.net/10256/19194ACS Catalysis, 2021, vol. 11, p. 2583–2595Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.0c05439info:eu-repo/semantics/altIdentifier/issn/2155-5435info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-101737-B-I00Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/191942026-05-29T05:05:01Z
dc.title.none.fl_str_mv Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
title Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
spellingShingle Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
D'Agostini, Silvia
Oxidació electrolítica
Electrolytic oxidation
Electrocatàlisi
Electrocatalysis
title_short Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
title_full Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
title_fullStr Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
title_full_unstemmed Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
title_sort Electrocatalytic Water Oxidation with α-[Fe(mcp)(OTf)2] and Analogues
dc.creator.none.fl_str_mv D'Agostini, Silvia
Kottrup, Konstantin G.
Casadevall, Carla
Gamba, Ilaria
Dantignana, Valeria
Bucci, Alberto
Costas Salgueiro, Miquel
Lloret Fillol, Julio
Hetterscheid, Dennis G.H.
author D'Agostini, Silvia
author_facet D'Agostini, Silvia
Kottrup, Konstantin G.
Casadevall, Carla
Gamba, Ilaria
Dantignana, Valeria
Bucci, Alberto
Costas Salgueiro, Miquel
Lloret Fillol, Julio
Hetterscheid, Dennis G.H.
author_role author
author2 Kottrup, Konstantin G.
Casadevall, Carla
Gamba, Ilaria
Dantignana, Valeria
Bucci, Alberto
Costas Salgueiro, Miquel
Lloret Fillol, Julio
Hetterscheid, Dennis G.H.
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Oxidació electrolítica
Electrolytic oxidation
Electrocatàlisi
Electrocatalysis
topic Oxidació electrolítica
Electrolytic oxidation
Electrocatàlisi
Electrocatalysis
description The complex α-[Fe(mcp)(OTf)2] (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-diamine and OTf = trifluoromethanesulfonate anion) was reported in 2011 by some of us as an active water oxidation (WO) catalyst in the presence of sacrificial oxidants. However, because chemical oxidants are likely to take part in the reaction mechanism, mechanistic electrochemical studies are critical in establishing to what extent previous studies with sacrificial reagents have actually been meaningful. In this study, the complex α-[Fe(mcp)(OTf)2] and its analogues were investigated electrochemically under both acidic and neutral conditions. All the systems under investigation proved to be electrochemically active toward the WO reaction, with no major differences in activity despite the structural changes. Our findings show that WO-catalyzed by mcp–iron complexes proceeds via homogeneous species, whereas the analogous manganese complex forms a heterogeneous deposit on the electrode surface. Mechanistic studies show that the reaction proceeds with a different rate-determining step (rds) than what was previously proposed in the presence of chemical oxidants. Moreover, the different kinetic isotope effect (KIE) values obtained electrochemically at pH 7 (KIE ∼ 10) and at pH 1 (KIE = 1) show that the reaction conditions have a remarkable effect on the rds and on the mechanism. We suggest a proton-coupled electron transfer (PCET) as the rds under neutral conditions, whereas at pH 1 the rds is most likely an electron transfer (ET)
publishDate 2021
dc.date.none.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/19194
http://hdl.handle.net/10256/19194
url http://hdl.handle.net/10256/19194
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.0c05439
info:eu-repo/semantics/altIdentifier/issn/2155-5435
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-101737-B-I00
dc.rights.none.fl_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv ACS Catalysis, 2021, vol. 11, p. 2583–2595
Articles publicats (D-Q)
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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