Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface
- Autores
- García Pintos, Delfina; Juan, Alfredo; Irigoyen, Beatriz del Luján
- Año de publicación
- 2014
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Spin-polarized density functional theory (DFT + U) periodic calculations have been performed to study water adsorption and dissociation on the 12.5% Mn-doped CeO2(1 1 1) surface. Our results indicated that Mn cation is the surface active site for water adsorption and dissociation reactions. The H2O molecule preferably adsorbs on a Mn cation, causing some relaxation of the surface O-layer and, thus, facilitating the bonding of one of the HH2O with the nearest oxygen atom. After overcoming an energy barrier of 0.46 eV, the water molecule could dissociate into OH and H species. The latter configuration is about 50% more exothermic than the molecular one, suggesting the Ce0.875Mn0.125O1.9375(1 1 1) surface would be easily hydroxylated under reaction conditions. In addition, the calculations showed that water adsorption on the Mn-doped CeO2(1 1 1) surface did not favor the creation of surface oxygen vacancies as it has been reported for pure CeO2(1 1 1). On the other hand, we created a surface oxygen defect in the slab with structural oxygen vacancies and computed water interactions on the reduced surface. Although, the adsorption of OH species in the O-hole caused many surface and subsurface atomic displacements, no changes in the oxidation state of Mn and Ce cations were detected.
Fil: García 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. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Irigoyen, Beatriz del Luján. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Ingeniería Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina - Materia
-
Water Adsorption
Mn-Doped Ceo2(1 1 1) Surface
Dft + u Calculations
Ceria - 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:11336/29878
Ver los metadatos del registro completo
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Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surfaceGarcía Pintos, DelfinaJuan, AlfredoIrigoyen, Beatriz del LujánWater AdsorptionMn-Doped Ceo2(1 1 1) SurfaceDft + u CalculationsCeriahttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2Spin-polarized density functional theory (DFT + U) periodic calculations have been performed to study water adsorption and dissociation on the 12.5% Mn-doped CeO2(1 1 1) surface. Our results indicated that Mn cation is the surface active site for water adsorption and dissociation reactions. The H2O molecule preferably adsorbs on a Mn cation, causing some relaxation of the surface O-layer and, thus, facilitating the bonding of one of the HH2O with the nearest oxygen atom. After overcoming an energy barrier of 0.46 eV, the water molecule could dissociate into OH and H species. The latter configuration is about 50% more exothermic than the molecular one, suggesting the Ce0.875Mn0.125O1.9375(1 1 1) surface would be easily hydroxylated under reaction conditions. In addition, the calculations showed that water adsorption on the Mn-doped CeO2(1 1 1) surface did not favor the creation of surface oxygen vacancies as it has been reported for pure CeO2(1 1 1). On the other hand, we created a surface oxygen defect in the slab with structural oxygen vacancies and computed water interactions on the reduced surface. Although, the adsorption of OH species in the O-hole caused many surface and subsurface atomic displacements, no changes in the oxidation state of Mn and Ce cations were detected.Fil: García Pintos, Delfina. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Ingeniería Química; 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. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Ingeniería Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaElsevier Science2014-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/29878García Pintos, Delfina ; Juan, Alfredo; Irigoyen, Beatriz del Luján; Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface; Elsevier Science; Applied Surface Science; 313; 6-2014; 784-7930169-4332CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2014.06.076info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0169433214013610info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:02:20Zoai:ri.conicet.gov.ar:11336/29878instacron: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 10:02:21.017CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
title |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
spellingShingle |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface García Pintos, Delfina Water Adsorption Mn-Doped Ceo2(1 1 1) Surface Dft + u Calculations Ceria |
title_short |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
title_full |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
title_fullStr |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
title_full_unstemmed |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
title_sort |
Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface |
dc.creator.none.fl_str_mv |
García Pintos, Delfina Juan, Alfredo Irigoyen, Beatriz del Luján |
author |
García Pintos, Delfina |
author_facet |
García Pintos, Delfina 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 |
Water Adsorption Mn-Doped Ceo2(1 1 1) Surface Dft + u Calculations Ceria |
topic |
Water Adsorption Mn-Doped Ceo2(1 1 1) Surface Dft + u Calculations Ceria |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/2.4 https://purl.org/becyt/ford/2 |
dc.description.none.fl_txt_mv |
Spin-polarized density functional theory (DFT + U) periodic calculations have been performed to study water adsorption and dissociation on the 12.5% Mn-doped CeO2(1 1 1) surface. Our results indicated that Mn cation is the surface active site for water adsorption and dissociation reactions. The H2O molecule preferably adsorbs on a Mn cation, causing some relaxation of the surface O-layer and, thus, facilitating the bonding of one of the HH2O with the nearest oxygen atom. After overcoming an energy barrier of 0.46 eV, the water molecule could dissociate into OH and H species. The latter configuration is about 50% more exothermic than the molecular one, suggesting the Ce0.875Mn0.125O1.9375(1 1 1) surface would be easily hydroxylated under reaction conditions. In addition, the calculations showed that water adsorption on the Mn-doped CeO2(1 1 1) surface did not favor the creation of surface oxygen vacancies as it has been reported for pure CeO2(1 1 1). On the other hand, we created a surface oxygen defect in the slab with structural oxygen vacancies and computed water interactions on the reduced surface. Although, the adsorption of OH species in the O-hole caused many surface and subsurface atomic displacements, no changes in the oxidation state of Mn and Ce cations were detected. Fil: García 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. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina Fil: Irigoyen, Beatriz del Luján. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Ingeniería Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina |
description |
Spin-polarized density functional theory (DFT + U) periodic calculations have been performed to study water adsorption and dissociation on the 12.5% Mn-doped CeO2(1 1 1) surface. Our results indicated that Mn cation is the surface active site for water adsorption and dissociation reactions. The H2O molecule preferably adsorbs on a Mn cation, causing some relaxation of the surface O-layer and, thus, facilitating the bonding of one of the HH2O with the nearest oxygen atom. After overcoming an energy barrier of 0.46 eV, the water molecule could dissociate into OH and H species. The latter configuration is about 50% more exothermic than the molecular one, suggesting the Ce0.875Mn0.125O1.9375(1 1 1) surface would be easily hydroxylated under reaction conditions. In addition, the calculations showed that water adsorption on the Mn-doped CeO2(1 1 1) surface did not favor the creation of surface oxygen vacancies as it has been reported for pure CeO2(1 1 1). On the other hand, we created a surface oxygen defect in the slab with structural oxygen vacancies and computed water interactions on the reduced surface. Although, the adsorption of OH species in the O-hole caused many surface and subsurface atomic displacements, no changes in the oxidation state of Mn and Ce cations were detected. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-06 |
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/11336/29878 García Pintos, Delfina ; Juan, Alfredo; Irigoyen, Beatriz del Luján; Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface; Elsevier Science; Applied Surface Science; 313; 6-2014; 784-793 0169-4332 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/29878 |
identifier_str_mv |
García Pintos, Delfina ; Juan, Alfredo; Irigoyen, Beatriz del Luján; Density functional theory study of water interactions on Mn-doped CeO2(1 1 1) surface; Elsevier Science; Applied Surface Science; 313; 6-2014; 784-793 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/doi/10.1016/j.apsusc.2014.06.076 info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0169433214013610 |
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 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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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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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1842269752512217088 |
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13.13397 |