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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/24610
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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 Técnicas2025-09-03T10:08:36Zoai: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:34982025-09-03 10:08:36.729CONICET 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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1842270051528343552 |
score |
13.13397 |