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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/52675
Ver los metadatos del registro completo
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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 Técnicas2025-09-03T09:44:51Zoai: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:34982025-09-03 09:44:51.678CONICET 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 |
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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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13.13397 |