Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study

Autores
Milberg, Brian; Juan, Alfredo; Irigoyen, Beatriz del Luján
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO2(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce0.963Pr0.037O2(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr3+ and Ce3+ ones. Praseodymium doping also favors the activation of O2 molecule on surface O-holes, leading to formation of a superoxide (O2−) radical as well as to reoxidation of the Ce3+ cation to Ce4+ one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO2 molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO2 solids.
Fil: Milberg, Brian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles; Argentina
Fil: Juan, Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Irigoyen, Beatriz del Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles; Argentina
Materia
DFT+U
DIOXYGEN RADICALS
PR-DOPED CEO2
REDOX CAPACITY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/63655
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/63655
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U studyMilberg, BrianJuan, AlfredoIrigoyen, Beatriz del LujánDFT+UDIOXYGEN RADICALSPR-DOPED CEO2REDOX CAPACITYhttps://purl.org/becyt/ford/2.10https://purl.org/becyt/ford/2In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO2(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce0.963Pr0.037O2(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr3+ and Ce3+ ones. Praseodymium doping also favors the activation of O2 molecule on surface O-holes, leading to formation of a superoxide (O2−) radical as well as to reoxidation of the Ce3+ cation to Ce4+ one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO2 molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO2 solids.Fil: Milberg, Brian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles; ArgentinaFil: Juan, Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Irigoyen, Beatriz del Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles; ArgentinaElsevier Science2017-04-15info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/63655Milberg, Brian; Juan, Alfredo; Irigoyen, Beatriz del Luján; Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study ; Elsevier Science; Applied Surface Science; 401; 15-4-2017; 206-2170169-4332CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0169433216329890info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2016.12.245info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:39:02Zoai:ri.conicet.gov.ar:11336/63655instacron: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 09:39:02.511CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
title Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
spellingShingle Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
Milberg, Brian
DFT+U
DIOXYGEN RADICALS
PR-DOPED CEO2
REDOX CAPACITY
title_short Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
title_full Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
title_fullStr Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
title_full_unstemmed Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
title_sort Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study
dc.creator.none.fl_str_mv Milberg, Brian
Juan, Alfredo
Irigoyen, Beatriz del Luján
author Milberg, Brian
author_facet Milberg, Brian
Juan, Alfredo
Irigoyen, Beatriz del Luján
author_role author
author2 Juan, Alfredo
Irigoyen, Beatriz del Luján
author2_role author
author
dc.subject.none.fl_str_mv DFT+U
DIOXYGEN RADICALS
PR-DOPED CEO2
REDOX CAPACITY
topic DFT+U
DIOXYGEN RADICALS
PR-DOPED CEO2
REDOX CAPACITY
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO2(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce0.963Pr0.037O2(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr3+ and Ce3+ ones. Praseodymium doping also favors the activation of O2 molecule on surface O-holes, leading to formation of a superoxide (O2−) radical as well as to reoxidation of the Ce3+ cation to Ce4+ one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO2 molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO2 solids.
Fil: Milberg, Brian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles; Argentina
Fil: Juan, Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Irigoyen, Beatriz del Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías del Hidrogeno y Energias Sostenibles; Argentina
description In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO2(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce0.963Pr0.037O2(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr3+ and Ce3+ ones. Praseodymium doping also favors the activation of O2 molecule on surface O-holes, leading to formation of a superoxide (O2−) radical as well as to reoxidation of the Ce3+ cation to Ce4+ one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO2 molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO2 solids.
publishDate 2017
dc.date.none.fl_str_mv 2017-04-15
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/11336/63655
Milberg, Brian; Juan, Alfredo; Irigoyen, Beatriz del Luján; Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study ; Elsevier Science; Applied Surface Science; 401; 15-4-2017; 206-217
0169-4332
CONICET Digital
CONICET
url http://hdl.handle.net/11336/63655
identifier_str_mv Milberg, Brian; Juan, Alfredo; Irigoyen, Beatriz del Luján; Redox behavior of a low-doped Pr-CeO2(111) surface. A DFT+U study ; Elsevier Science; Applied Surface Science; 401; 15-4-2017; 206-217
0169-4332
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://www.sciencedirect.com/science/article/pii/S0169433216329890
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2016.12.245
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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 13.069144

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