Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations

Autores
Murgida, Gustavo Ezequiel; Ganduglia Pirovano, Maria Veronica
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Oxygen vacancies on ceria (CeO2) surfaces play a crucial role in catalytic applications, yet whether vacancies are at surface or subsurface sites on reduced CeO2 (111) , and whether vacancies agglomerate or repel each other, is still under discussion, with few and inconsistent experimental results. By combining density-functional theory (DFT) in the DFT+U (U is an effective onsite Coulomb interaction parameter) approach and statistical thermodynamics, we show that the energetically most stable near-surface oxygen vacancy structures for a broad range of vacancy concentrations, Θ (1/16 ≤ Θ ≤ 1 monolayer) have all vacancies at subsurface oxygen sites and predict that the thermodynamically stable phase for a wide range of reducing conditions is a (2×2) ordered subsurface vacancy structure (Θ=1/4). Vacancy-induced lattice relaxations effects are crucial for the interpretation of the repulsive interactions, which are at the basis of the vacancy spacing in the (2×2) structure. The findings provide theoretical data to support the interpretation of the most recent experiments, bringing us closer to solving the debate.
Fil: Murgida, Gustavo Ezequiel. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Constituyentes); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; España
Materia
Ceria
Vacancies
Surface
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/24610
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculationsMurgida, Gustavo EzequielGanduglia Pirovano, Maria VeronicaCeriaVacanciesSurfacehttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Oxygen vacancies on ceria (CeO2) surfaces play a crucial role in catalytic applications, yet whether vacancies are at surface or subsurface sites on reduced CeO2 (111) , and whether vacancies agglomerate or repel each other, is still under discussion, with few and inconsistent experimental results. By combining density-functional theory (DFT) in the DFT+U (U is an effective onsite Coulomb interaction parameter) approach and statistical thermodynamics, we show that the energetically most stable near-surface oxygen vacancy structures for a broad range of vacancy concentrations, Θ (1/16 ≤ Θ ≤ 1 monolayer) have all vacancies at subsurface oxygen sites and predict that the thermodynamically stable phase for a wide range of reducing conditions is a (2×2) ordered subsurface vacancy structure (Θ=1/4). Vacancy-induced lattice relaxations effects are crucial for the interpretation of the repulsive interactions, which are at the basis of the vacancy spacing in the (2×2) structure. The findings provide theoretical data to support the interpretation of the most recent experiments, bringing us closer to solving the debate.Fil: Murgida, Gustavo Ezequiel. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Constituyentes); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; EspañaAmerican Physical Society2013-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24610Murgida, Gustavo Ezequiel; Ganduglia Pirovano, Maria Veronica; Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations; American Physical Society; Physical Review Letters; 110; 24; 6-2013; 1-5; 2461010031-9007CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.110.246101info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevLett.110.246101info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:37:36Zoai:ri.conicet.gov.ar:11336/24610instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:37:37.08CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
title Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
spellingShingle Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
Murgida, Gustavo Ezequiel
Ceria
Vacancies
Surface
title_short Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
title_full Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
title_fullStr Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
title_full_unstemmed Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
title_sort Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations
dc.creator.none.fl_str_mv Murgida, Gustavo Ezequiel
Ganduglia Pirovano, Maria Veronica
author Murgida, Gustavo Ezequiel
author_facet Murgida, Gustavo Ezequiel
Ganduglia Pirovano, Maria Veronica
author_role author
author2 Ganduglia Pirovano, Maria Veronica
author2_role author
dc.subject.none.fl_str_mv Ceria
Vacancies
Surface
topic Ceria
Vacancies
Surface
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Oxygen vacancies on ceria (CeO2) surfaces play a crucial role in catalytic applications, yet whether vacancies are at surface or subsurface sites on reduced CeO2 (111) , and whether vacancies agglomerate or repel each other, is still under discussion, with few and inconsistent experimental results. By combining density-functional theory (DFT) in the DFT+U (U is an effective onsite Coulomb interaction parameter) approach and statistical thermodynamics, we show that the energetically most stable near-surface oxygen vacancy structures for a broad range of vacancy concentrations, Θ (1/16 ≤ Θ ≤ 1 monolayer) have all vacancies at subsurface oxygen sites and predict that the thermodynamically stable phase for a wide range of reducing conditions is a (2×2) ordered subsurface vacancy structure (Θ=1/4). Vacancy-induced lattice relaxations effects are crucial for the interpretation of the repulsive interactions, which are at the basis of the vacancy spacing in the (2×2) structure. The findings provide theoretical data to support the interpretation of the most recent experiments, bringing us closer to solving the debate.
Fil: Murgida, Gustavo Ezequiel. Comisión Nacional de Energía Atómica. Gerencia del Área de Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Constituyentes); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; España
description Oxygen vacancies on ceria (CeO2) surfaces play a crucial role in catalytic applications, yet whether vacancies are at surface or subsurface sites on reduced CeO2 (111) , and whether vacancies agglomerate or repel each other, is still under discussion, with few and inconsistent experimental results. By combining density-functional theory (DFT) in the DFT+U (U is an effective onsite Coulomb interaction parameter) approach and statistical thermodynamics, we show that the energetically most stable near-surface oxygen vacancy structures for a broad range of vacancy concentrations, Θ (1/16 ≤ Θ ≤ 1 monolayer) have all vacancies at subsurface oxygen sites and predict that the thermodynamically stable phase for a wide range of reducing conditions is a (2×2) ordered subsurface vacancy structure (Θ=1/4). Vacancy-induced lattice relaxations effects are crucial for the interpretation of the repulsive interactions, which are at the basis of the vacancy spacing in the (2×2) structure. The findings provide theoretical data to support the interpretation of the most recent experiments, bringing us closer to solving the debate.
publishDate 2013
dc.date.none.fl_str_mv 2013-06
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/24610
Murgida, Gustavo Ezequiel; Ganduglia Pirovano, Maria Veronica; Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations; American Physical Society; Physical Review Letters; 110; 24; 6-2013; 1-5; 246101
0031-9007
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24610
identifier_str_mv Murgida, Gustavo Ezequiel; Ganduglia Pirovano, Maria Veronica; Evidence for subsurface ordering of oxygen vacancies on the reduced CeO2 (111) surface using density-functional and statistical calculations; American Physical Society; Physical Review Letters; 110; 24; 6-2013; 1-5; 246101
0031-9007
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.110.246101
info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevLett.110.246101
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Physical Society
publisher.none.fl_str_mv American Physical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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