Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)

Autores
Lustemberg, Pablo German; Pan, Y.; Shaw, B. J.; Grinter, D.; Pang, Chi; Thornton, G.; Pérez, Rubén; Ganduglia Pirovano, Maria Veronica; Nilius, N.
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO2-x(111). Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina
Fil: Pan, Y.. Chinese Academy of Sciences; República de China
Fil: Shaw, B. J.. University College London; Estados Unidos
Fil: Grinter, D.. University College London; Estados Unidos
Fil: Pang, Chi. University College London; Estados Unidos
Fil: Thornton, G.. University College London; Estados Unidos
Fil: Pérez, Rubén. Universidad Autónoma de Madrid; España
Fil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas; España
Fil: Nilius, N.. Carl von Ossietzky University; Alemania
Materia
Ceria
Surface Oxygen defects
Au adsorption
DFT
STM
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:11336/52675
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)Lustemberg, Pablo GermanPan, Y.Shaw, B. J.Grinter, D.Pang, ChiThornton, G.Pérez, RubénGanduglia Pirovano, Maria VeronicaNilius, N.CeriaSurface Oxygen defectsAu adsorptionDFTSTMhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO2-x(111). Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; ArgentinaFil: Pan, Y.. Chinese Academy of Sciences; República de ChinaFil: Shaw, B. J.. University College London; Estados UnidosFil: Grinter, D.. University College London; Estados UnidosFil: Pang, Chi. University College London; Estados UnidosFil: Thornton, G.. University College London; Estados UnidosFil: Pérez, Rubén. Universidad Autónoma de Madrid; EspañaFil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas; EspañaFil: Nilius, N.. Carl von Ossietzky University; AlemaniaAmerican Physical Society2016-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/52675Lustemberg, Pablo German; Pan, Y.; Shaw, B. J.; Grinter, D.; Pang, Chi; et al.; Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111); American Physical Society; Physical Review Letters; 116; 23; 6-20160031-9007CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevLett.116.236101info:eu-repo/semantics/altIdentifier/url/https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.116.236101info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:35:00Zoai:ri.conicet.gov.ar:11336/52675instacron: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 09:35:00.939CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
title Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
spellingShingle Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
Lustemberg, Pablo German
Ceria
Surface Oxygen defects
Au adsorption
DFT
STM
title_short Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
title_full Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
title_fullStr Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
title_full_unstemmed Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
title_sort Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111)
dc.creator.none.fl_str_mv Lustemberg, Pablo German
Pan, Y.
Shaw, B. J.
Grinter, D.
Pang, Chi
Thornton, G.
Pérez, Rubén
Ganduglia Pirovano, Maria Veronica
Nilius, N.
author Lustemberg, Pablo German
author_facet Lustemberg, Pablo German
Pan, Y.
Shaw, B. J.
Grinter, D.
Pang, Chi
Thornton, G.
Pérez, Rubén
Ganduglia Pirovano, Maria Veronica
Nilius, N.
author_role author
author2 Pan, Y.
Shaw, B. J.
Grinter, D.
Pang, Chi
Thornton, G.
Pérez, Rubén
Ganduglia Pirovano, Maria Veronica
Nilius, N.
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Ceria
Surface Oxygen defects
Au adsorption
DFT
STM
topic Ceria
Surface Oxygen defects
Au adsorption
DFT
STM
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO2-x(111). Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina
Fil: Pan, Y.. Chinese Academy of Sciences; República de China
Fil: Shaw, B. J.. University College London; Estados Unidos
Fil: Grinter, D.. University College London; Estados Unidos
Fil: Pang, Chi. University College London; Estados Unidos
Fil: Thornton, G.. University College London; Estados Unidos
Fil: Pérez, Rubén. Universidad Autónoma de Madrid; España
Fil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas; España
Fil: Nilius, N.. Carl von Ossietzky University; Alemania
description Surface defects are believed to govern the adsorption behavior of reducible oxides. We challenge this perception on the basis of a combined scanning-tunneling-microscopy and density-functional-theory study, addressing the Au adsorption on reduced CeO2-x(111). Despite a clear thermodynamic preference for oxygen vacancies, individual Au atoms were found to bind mostly to regular surface sites. Even at an elevated temperature, aggregation at step edges and not decoration of defects turned out to be the main consequence of adatom diffusion. Our findings are explained with the polaronic nature of the Au-ceria system, which imprints a strong diabatic character onto the diffusive motion of adatoms. Diabatic barriers are generally higher than those in the adiabatic regime, especially if the hopping step couples to an electron transfer into the ad-gold. As the population of O vacancies always requires a charge exchange, defect decoration by Au atoms becomes kinetically hindered. Our study demonstrates that polaronic effects determine not only electron transport in reducible oxides but also the adsorption characteristics and therewith the surface chemistry.
publishDate 2016
dc.date.none.fl_str_mv 2016-06
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/11336/52675
Lustemberg, Pablo German; Pan, Y.; Shaw, B. J.; Grinter, D.; Pang, Chi; et al.; Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111); American Physical Society; Physical Review Letters; 116; 23; 6-2016
0031-9007
CONICET Digital
CONICET
url http://hdl.handle.net/11336/52675
identifier_str_mv Lustemberg, Pablo German; Pan, Y.; Shaw, B. J.; Grinter, D.; Pang, Chi; et al.; Diffusion Barriers Block Defect Occupation on Reduced CeO2 (111); American Physical Society; Physical Review Letters; 116; 23; 6-2016
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/doi/10.1103/PhysRevLett.116.236101
info:eu-repo/semantics/altIdentifier/url/https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.116.236101
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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score 13.070432

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