What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?

The photocatalytic O–H dissociation of water absorbed on a rutile TiO2(110) surface in ultrahigh vacuum (UHV) is studied with spin-polarized density functional theory and a hybrid exchange-correlation functional (HSE06), treating the excited-state species as excitons with triplet multiplicity. This...

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Detalles Bibliográficos
Autores: Migani, Annapaola, Blancafort San José, Lluís
Tipo de recurso: artículo
Estado:Versión publicada
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:10256/16786
Acceso en línea:http://hdl.handle.net/10256/16786
Access Level:acceso abierto
Palabra clave:Funcional de densitat, Teoria del
Density functionals
Fotocatàlisi
Photocatalysis
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spelling What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?Migani, AnnapaolaBlancafort San José, LluísFuncional de densitat, Teoria delDensity functionalsFotocatàlisiPhotocatalysisThe photocatalytic O–H dissociation of water absorbed on a rutile TiO2(110) surface in ultrahigh vacuum (UHV) is studied with spin-polarized density functional theory and a hybrid exchange-correlation functional (HSE06), treating the excited-state species as excitons with triplet multiplicity. This system is a model for the photocatalytic oxidation of water by TiO2 in an aqueous medium, which is relevant for the oxygen evolution reaction and photodegradation of organic pollutants. We provide a comprehensive mechanistic picture where the most representative paths correspond to excitonic configurations with the hole located on three- and two-coordinate surface oxygen atoms (O3s and O2s). Our picture explains the formation of the species observed experimentally. At near band gap excitation, the O3s path leads to the generation of hydroxyl anions which diffuse on the surface, without net oxidation. In contrast, free hydroxyl radicals are formed at supra band gap excitation (e.g., 266 nm) from an interfacial exciton that undergoes O–H dissociation. The oxidation efficiency is low because the path associated with the O2s exciton, which is the most favored one thermodynamically, is unreactive because of a high propensity for charge recombination. Our results are also relevant to understand the reactivity in the liquid phase. We assign the photoluminescence measured for atomically flat TiO2(110) surfaces in an aqueous medium to the O3s exciton, in line with the proposal based on experiments, and we have identified a species derived from the O2s exciton with an activated O2s–Ti bond that may be relevant in photocatalytic applications in an aqueous mediumWe acknowledge financial support from the Spanish Ministerio de Economıá y Competitividad (Grants UNGI10-4E-801, RYC-2011-09582, and CTQ-2015-69363-P) and Generalitat de Catalunya (Grant 2014SGR-1202, XRQTC) and computational time from the BSC Red Espanola de Supercomputación and Consorci de Serveis Universitaris de CatalunyaElsevierMinisterio de Economía y Competitividad (Espanya)2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/16786http://hdl.handle.net/10256/16786© Journal of the American Chemical Society, 2017, vol. 139, núm. 34, p. 11845-11856Articles 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/jacs.7b05121info:eu-repo/semantics/altIdentifier/issn/0002-7863info:eu-repo/semantics/altIdentifier/eissn/1520-5126info:eu-repo/grantAgreement/MINECO//CTQ2015-69363-PTots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/167862026-05-29T05:05:01Z
dc.title.none.fl_str_mv What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
title What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
spellingShingle What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
Migani, Annapaola
Funcional de densitat, Teoria del
Density functionals
Fotocatàlisi
Photocatalysis
title_short What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
title_full What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
title_fullStr What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
title_full_unstemmed What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
title_sort What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
dc.creator.none.fl_str_mv Migani, Annapaola
Blancafort San José, Lluís
author Migani, Annapaola
author_facet Migani, Annapaola
Blancafort San José, Lluís
author_role author
author2 Blancafort San José, Lluís
author2_role author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Funcional de densitat, Teoria del
Density functionals
Fotocatàlisi
Photocatalysis
topic Funcional de densitat, Teoria del
Density functionals
Fotocatàlisi
Photocatalysis
description The photocatalytic O–H dissociation of water absorbed on a rutile TiO2(110) surface in ultrahigh vacuum (UHV) is studied with spin-polarized density functional theory and a hybrid exchange-correlation functional (HSE06), treating the excited-state species as excitons with triplet multiplicity. This system is a model for the photocatalytic oxidation of water by TiO2 in an aqueous medium, which is relevant for the oxygen evolution reaction and photodegradation of organic pollutants. We provide a comprehensive mechanistic picture where the most representative paths correspond to excitonic configurations with the hole located on three- and two-coordinate surface oxygen atoms (O3s and O2s). Our picture explains the formation of the species observed experimentally. At near band gap excitation, the O3s path leads to the generation of hydroxyl anions which diffuse on the surface, without net oxidation. In contrast, free hydroxyl radicals are formed at supra band gap excitation (e.g., 266 nm) from an interfacial exciton that undergoes O–H dissociation. The oxidation efficiency is low because the path associated with the O2s exciton, which is the most favored one thermodynamically, is unreactive because of a high propensity for charge recombination. Our results are also relevant to understand the reactivity in the liquid phase. We assign the photoluminescence measured for atomically flat TiO2(110) surfaces in an aqueous medium to the O3s exciton, in line with the proposal based on experiments, and we have identified a species derived from the O2s exciton with an activated O2s–Ti bond that may be relevant in photocatalytic applications in an aqueous medium
publishDate 2017
dc.date.none.fl_str_mv 2017
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/10256/16786
http://hdl.handle.net/10256/16786
url http://hdl.handle.net/10256/16786
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/jacs.7b05121
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
info:eu-repo/grantAgreement/MINECO//CTQ2015-69363-P
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv © Journal of the American Chemical Society, 2017, vol. 139, núm. 34, p. 11845-11856
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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