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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/63655
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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 Técnicas2025-09-03T09:47:12Zoai: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:34982025-09-03 09:47:12.956CONICET 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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1842268842231857152 |
score |
13.13397 |