Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions

Autores
Garcia Pintos, Delfina; Juan, Alfredo; Irigoyen, Beatriz
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, we performed DFT+U periodic calculations to study the geometric and electronic properties of 12.5% Mn-doped CeO2 solid solution. The doping with Mn allowed some Mn2+ cations to substitute Ce4+ ions into the CeO2 lattice and thus drove the formation of a stable O-deficient bulk fluorite-type structure. The Mn-doped CeO2(1 1 1) surface, generated upon the cleavage of the O-deficient bulk, exhibits Mn cations in a (3+) oxidation state. Spin-polarized energy calculations and charge analysis also evidenced the effect of Mn-dopant in facilitating the creation of surface oxygen vacancies; which reflected in extended surface and subsurface ions relaxation and reduction of Mn atoms located on surface and inner cationic layers. Concerning the oxidation state of Ce, it remained unaltered as Ce4+ when an O atom was removed from the topmost anionic layer of the surface system. Reduction of a Ce4+ cation to Ce3+ was evidenced after the creation of a second surface O-vacancy. Our results indicate facilitated surface oxygen release, Mn3+/Mn2+ redox couples formation, and promoted anionic mobility and can help to better understand the effect of Mn in enhancing Mn-doped CeO2 catalytic performance in oxidation reactions.
Fil: Garcia Pintos, Delfina. Universidad de Buenos Aires. Facultad de Ingenierí­a. Departamento de Ingenierí­a Química; Argentina;
Fil: Juan, Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico - CONICET - Bahía Blanca. Instituto de Física del Sur; Argentina;
Fil: Irigoyen, Beatriz. Universidad de Buenos Aires. Facultad de Ingenierí­a. Departamento de Ingenierí­a Química; Argentina;
Materia
Ceo2
Mn
Vacancy
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:11336/2080
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/2080
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation ReactionsGarcia Pintos, DelfinaJuan, AlfredoIrigoyen, BeatrizCeo2MnVacancyhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1In this work, we performed DFT+U periodic calculations to study the geometric and electronic properties of 12.5% Mn-doped CeO2 solid solution. The doping with Mn allowed some Mn2+ cations to substitute Ce4+ ions into the CeO2 lattice and thus drove the formation of a stable O-deficient bulk fluorite-type structure. The Mn-doped CeO2(1 1 1) surface, generated upon the cleavage of the O-deficient bulk, exhibits Mn cations in a (3+) oxidation state. Spin-polarized energy calculations and charge analysis also evidenced the effect of Mn-dopant in facilitating the creation of surface oxygen vacancies; which reflected in extended surface and subsurface ions relaxation and reduction of Mn atoms located on surface and inner cationic layers. Concerning the oxidation state of Ce, it remained unaltered as Ce4+ when an O atom was removed from the topmost anionic layer of the surface system. Reduction of a Ce4+ cation to Ce3+ was evidenced after the creation of a second surface O-vacancy. Our results indicate facilitated surface oxygen release, Mn3+/Mn2+ redox couples formation, and promoted anionic mobility and can help to better understand the effect of Mn in enhancing Mn-doped CeO2 catalytic performance in oxidation reactions.Fil: Garcia Pintos, Delfina. Universidad de Buenos Aires. Facultad de Ingenierí­a. Departamento de Ingenierí­a Química; Argentina;Fil: Juan, Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico - CONICET - Bahía Blanca. Instituto de Física del Sur; Argentina;Fil: Irigoyen, Beatriz. Universidad de Buenos Aires. Facultad de Ingenierí­a. Departamento de Ingenierí­a Química; Argentina;American Chemical Society2013-08-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/2080Garcia Pintos, Delfina; Juan, Alfredo; Irigoyen, Beatriz; Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions; American Chemical Society; Journal Of Physical Chemistry C; 117; 35; 7-8-2013; 18063-180731932-7447enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp403911binfo:eu-repo/semantics/altIdentifier/doi/DOI:10.1021/jp403911binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:47:19Zoai:ri.conicet.gov.ar:11336/2080instacron: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 09:47:19.446CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
title Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
spellingShingle Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
Garcia Pintos, Delfina
Ceo2
Mn
Vacancy
title_short Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
title_full Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
title_fullStr Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
title_full_unstemmed Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
title_sort Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions
dc.creator.none.fl_str_mv Garcia Pintos, Delfina
Juan, Alfredo
Irigoyen, Beatriz
author Garcia Pintos, Delfina
author_facet Garcia Pintos, Delfina
Juan, Alfredo
Irigoyen, Beatriz
author_role author
author2 Juan, Alfredo
Irigoyen, Beatriz
author2_role author
author
dc.subject.none.fl_str_mv Ceo2
Mn
Vacancy
topic Ceo2
Mn
Vacancy
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work, we performed DFT+U periodic calculations to study the geometric and electronic properties of 12.5% Mn-doped CeO2 solid solution. The doping with Mn allowed some Mn2+ cations to substitute Ce4+ ions into the CeO2 lattice and thus drove the formation of a stable O-deficient bulk fluorite-type structure. The Mn-doped CeO2(1 1 1) surface, generated upon the cleavage of the O-deficient bulk, exhibits Mn cations in a (3+) oxidation state. Spin-polarized energy calculations and charge analysis also evidenced the effect of Mn-dopant in facilitating the creation of surface oxygen vacancies; which reflected in extended surface and subsurface ions relaxation and reduction of Mn atoms located on surface and inner cationic layers. Concerning the oxidation state of Ce, it remained unaltered as Ce4+ when an O atom was removed from the topmost anionic layer of the surface system. Reduction of a Ce4+ cation to Ce3+ was evidenced after the creation of a second surface O-vacancy. Our results indicate facilitated surface oxygen release, Mn3+/Mn2+ redox couples formation, and promoted anionic mobility and can help to better understand the effect of Mn in enhancing Mn-doped CeO2 catalytic performance in oxidation reactions.
Fil: Garcia Pintos, Delfina. Universidad de Buenos Aires. Facultad de Ingenierí­a. Departamento de Ingenierí­a Química; Argentina;
Fil: Juan, Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico - CONICET - Bahía Blanca. Instituto de Física del Sur; Argentina;
Fil: Irigoyen, Beatriz. Universidad de Buenos Aires. Facultad de Ingenierí­a. Departamento de Ingenierí­a Química; Argentina;
description In this work, we performed DFT+U periodic calculations to study the geometric and electronic properties of 12.5% Mn-doped CeO2 solid solution. The doping with Mn allowed some Mn2+ cations to substitute Ce4+ ions into the CeO2 lattice and thus drove the formation of a stable O-deficient bulk fluorite-type structure. The Mn-doped CeO2(1 1 1) surface, generated upon the cleavage of the O-deficient bulk, exhibits Mn cations in a (3+) oxidation state. Spin-polarized energy calculations and charge analysis also evidenced the effect of Mn-dopant in facilitating the creation of surface oxygen vacancies; which reflected in extended surface and subsurface ions relaxation and reduction of Mn atoms located on surface and inner cationic layers. Concerning the oxidation state of Ce, it remained unaltered as Ce4+ when an O atom was removed from the topmost anionic layer of the surface system. Reduction of a Ce4+ cation to Ce3+ was evidenced after the creation of a second surface O-vacancy. Our results indicate facilitated surface oxygen release, Mn3+/Mn2+ redox couples formation, and promoted anionic mobility and can help to better understand the effect of Mn in enhancing Mn-doped CeO2 catalytic performance in oxidation reactions.
publishDate 2013
dc.date.none.fl_str_mv 2013-08-07
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/11336/2080
Garcia Pintos, Delfina; Juan, Alfredo; Irigoyen, Beatriz; Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions; American Chemical Society; Journal Of Physical Chemistry C; 117; 35; 7-8-2013; 18063-18073
1932-7447
url http://hdl.handle.net/11336/2080
identifier_str_mv Garcia Pintos, Delfina; Juan, Alfredo; Irigoyen, Beatriz; Mn-Doped CeO2: DFT+U Study of a Catalyst for Oxidation Reactions; American Chemical Society; Journal Of Physical Chemistry C; 117; 35; 7-8-2013; 18063-18073
1932-7447
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp403911b
info:eu-repo/semantics/altIdentifier/doi/DOI:10.1021/jp403911b
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 Chemical Society
publisher.none.fl_str_mv American Chemical 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 13.13397

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