Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths

Autores
Schulte, Erica Daniela; Belletti, Gustavo Daniel; Arce, Mauricio Damián; Quaino, Paola Monica
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O 2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the O–O bond breaking in O 2 ∗ and OOH ∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O 2 ∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The O–O scission of the OOH ∗ was found to be a barrierless process in Au–Pt systems and nearly barrierless in all Au–Pd systems, implying that the reduction ofO 2 in these systems proceeds via the full reduction of O 2 to H 2 O, avoiding H 2 O 2 formation.
Fil: Schulte, Erica Daniela. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina
Fil: Belletti, Gustavo Daniel. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina
Fil: Arce, Mauricio Damián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Quaino, Paola Monica. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina
Materia
BIMETALLIC ELECTROCATALYSTS
CATHODE
DFT
FUEL CELL
OXYGEN REDUCTION REACTION
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:11336/89456
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/89456
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction pathsSchulte, Erica DanielaBelletti, Gustavo DanielArce, Mauricio DamiánQuaino, Paola MonicaBIMETALLIC ELECTROCATALYSTSCATHODEDFTFUEL CELLOXYGEN REDUCTION REACTIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O 2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the O–O bond breaking in O 2 ∗ and OOH ∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O 2 ∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The O–O scission of the OOH ∗ was found to be a barrierless process in Au–Pt systems and nearly barrierless in all Au–Pd systems, implying that the reduction ofO 2 in these systems proceeds via the full reduction of O 2 to H 2 O, avoiding H 2 O 2 formation.Fil: Schulte, Erica Daniela. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaFil: Belletti, Gustavo Daniel. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaFil: Arce, Mauricio Damián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Quaino, Paola Monica. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaElsevier Science2018-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/89456Schulte, Erica Daniela; Belletti, Gustavo Daniel; Arce, Mauricio Damián; Quaino, Paola Monica; Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths; Elsevier Science; Applied Surface Science; 441; 5-2018; 663-6690169-4332CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0169433218302836info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2018.01.265info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:22:25Zoai:ri.conicet.gov.ar:11336/89456instacron: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:34982025-09-10 13:22:25.839CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
title Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
spellingShingle Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
Schulte, Erica Daniela
BIMETALLIC ELECTROCATALYSTS
CATHODE
DFT
FUEL CELL
OXYGEN REDUCTION REACTION
title_short Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
title_full Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
title_fullStr Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
title_full_unstemmed Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
title_sort Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths
dc.creator.none.fl_str_mv Schulte, Erica Daniela
Belletti, Gustavo Daniel
Arce, Mauricio Damián
Quaino, Paola Monica
author Schulte, Erica Daniela
author_facet Schulte, Erica Daniela
Belletti, Gustavo Daniel
Arce, Mauricio Damián
Quaino, Paola Monica
author_role author
author2 Belletti, Gustavo Daniel
Arce, Mauricio Damián
Quaino, Paola Monica
author2_role author
author
author
dc.subject.none.fl_str_mv BIMETALLIC ELECTROCATALYSTS
CATHODE
DFT
FUEL CELL
OXYGEN REDUCTION REACTION
topic BIMETALLIC ELECTROCATALYSTS
CATHODE
DFT
FUEL CELL
OXYGEN REDUCTION REACTION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O 2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the O–O bond breaking in O 2 ∗ and OOH ∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O 2 ∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The O–O scission of the OOH ∗ was found to be a barrierless process in Au–Pt systems and nearly barrierless in all Au–Pd systems, implying that the reduction ofO 2 in these systems proceeds via the full reduction of O 2 to H 2 O, avoiding H 2 O 2 formation.
Fil: Schulte, Erica Daniela. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina
Fil: Belletti, Gustavo Daniel. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina
Fil: Arce, Mauricio Damián. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Quaino, Paola Monica. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina
description The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O 2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the O–O bond breaking in O 2 ∗ and OOH ∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O 2 ∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The O–O scission of the OOH ∗ was found to be a barrierless process in Au–Pt systems and nearly barrierless in all Au–Pd systems, implying that the reduction ofO 2 in these systems proceeds via the full reduction of O 2 to H 2 O, avoiding H 2 O 2 formation.
publishDate 2018
dc.date.none.fl_str_mv 2018-05
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/11336/89456
Schulte, Erica Daniela; Belletti, Gustavo Daniel; Arce, Mauricio Damián; Quaino, Paola Monica; Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths; Elsevier Science; Applied Surface Science; 441; 5-2018; 663-669
0169-4332
CONICET Digital
CONICET
url http://hdl.handle.net/11336/89456
identifier_str_mv Schulte, Erica Daniela; Belletti, Gustavo Daniel; Arce, Mauricio Damián; Quaino, Paola Monica; Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths; Elsevier Science; Applied Surface Science; 441; 5-2018; 663-669
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/S0169433218302836
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2018.01.265
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
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 12.48226

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