Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes

The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate s...

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Autores: Hegner, Franziska Simone, Cardenas-Morcoso, Drialys, Giménez, Sixto, López, Núria, Galan-Mascaros, Jose Ramon
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
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:2072/359766
Acceso en línea:http://hdl.handle.net/2072/359766
https://doi.org/10.1002/cssc.201701538
Access Level:acceso abierto
Palabra clave:54
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spelling Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate PhotoanodesHegner, Franziska SimoneCardenas-Morcoso, DrialysGiménez, SixtoLópez, NúriaGalan-Mascaros, Jose Ramon54The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate synergy between light absorbers and active catalysts. No single material appears to combine both features. Many experimental parameters are key to achieve the needed synergy between both systems, without clear protocols for success. Herein, we show how computational chemistry can shed some light on this cumbersome problem. DFT calculations are useful to predict adequate energy-level alignment for thermodynamically favored hole transfer. As proof of concept, we experimentally confirmed the limited performance enhancement in hematite photoanodes decorated with cobalt hexacyanoferrate as a competent water-oxidation catalyst. Computational methods describe the misalignment of their energy levels, which is the origin of this mismatch. Photoelectrochemical studies indicate that the catalyst exclusively shifts the hematite surface state to lower potentials, which therefore reduces the onset for water oxidation. Although kinetics will still depend on interface architecture, our simple theoretical approach may identify and predict plausible semiconductor/catalyst combinations, which will speed up experimental work towards promising photoelectrocatalytic systems.2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion4552 p.application/pdfhttp://hdl.handle.net/2072/359766https://doi.org/10.1002/cssc.201701538RECERCAT (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)InglésL'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:2072/3597662026-05-29T05:05:01Z
dc.title.none.fl_str_mv Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
title Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
spellingShingle Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
Hegner, Franziska Simone
54
title_short Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
title_full Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
title_fullStr Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
title_full_unstemmed Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
title_sort Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes
dc.creator.none.fl_str_mv Hegner, Franziska Simone
Cardenas-Morcoso, Drialys
Giménez, Sixto
López, Núria
Galan-Mascaros, Jose Ramon
author Hegner, Franziska Simone
author_facet Hegner, Franziska Simone
Cardenas-Morcoso, Drialys
Giménez, Sixto
López, Núria
Galan-Mascaros, Jose Ramon
author_role author
author2 Cardenas-Morcoso, Drialys
Giménez, Sixto
López, Núria
Galan-Mascaros, Jose Ramon
author2_role author
author
author
author
dc.subject.none.fl_str_mv 54
topic 54
description The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate synergy between light absorbers and active catalysts. No single material appears to combine both features. Many experimental parameters are key to achieve the needed synergy between both systems, without clear protocols for success. Herein, we show how computational chemistry can shed some light on this cumbersome problem. DFT calculations are useful to predict adequate energy-level alignment for thermodynamically favored hole transfer. As proof of concept, we experimentally confirmed the limited performance enhancement in hematite photoanodes decorated with cobalt hexacyanoferrate as a competent water-oxidation catalyst. Computational methods describe the misalignment of their energy levels, which is the origin of this mismatch. Photoelectrochemical studies indicate that the catalyst exclusively shifts the hematite surface state to lower potentials, which therefore reduces the onset for water oxidation. Although kinetics will still depend on interface architecture, our simple theoretical approach may identify and predict plausible semiconductor/catalyst combinations, which will speed up experimental work towards promising photoelectrocatalytic systems.
publishDate 2017
dc.date.none.fl_str_mv 2017
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/2072/359766
https://doi.org/10.1002/cssc.201701538
url http://hdl.handle.net/2072/359766
https://doi.org/10.1002/cssc.201701538
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 4552 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
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