Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles

Autores
Celorrio, Verónica; Quaino, Paola Monica; Santos, Elizabeth del Carmen; Flórez Montaño, Jonathan; Humphrey, Jo J. L.; Guillén Villafuerte, Olmedo; Plana, Daniela; Lázaro, María J.; Pastor, Elena; Fermín, David J.
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The mechanism of CO and HCOOH electrooxidation in an acidic solution on carbon-supported Au-Pd core-shell nanoparticles was investigated by differential electrochemical mass spectrometry and in situ Fourier transform infrared (FTIR) spectroscopy. Analysis performed in nanostructures with 1.3 ± 0.1 nm (CS1) and 9.9 ± 1.1 nm (CS10) Pd shells provides compelling evidence that the mechanism of adsorbed CO (COads) oxidation is affected by structural and electronic effects introduced by the Au cores. In the case of CS10, a band associated with adsorbed OH species (OHads) is observed in the potential range of CO oxidation. This feature is not detected in the case of CS1, suggesting that the reaction follows an alternative mechanism involving COOHads species. The faradaic charge associated with COads oxidation as well as the Stark slope measured from FTIR indicates that the overall affinity and orbital coupling of CO to Pd are weaker for CS1 shells. FTIR spectroscopy also revealed the presence of HCOOads intermediate species only in the case of CS1. This observation allowed us to conclude that the higher activity of CS10 toward this reaction is due to a fast HCOOads oxidation step, probably involving OHads, to generate CO2. Density functional theory calculations are used to estimate the contributions of the so-called ligand and strain effects on the local density of states of the Pd d-band. The calculations strongly suggest that the key parameter contributing to the change in mechanism is the effective lattice strain.
Fil: Celorrio, Verónica. University of Bristol; Reino Unido
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
Fil: Santos, Elizabeth del Carmen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universitat Ulm; Alemania
Fil: Flórez Montaño, Jonathan. Universidad de La Laguna; España
Fil: Humphrey, Jo J. L.. University of Bristol; Reino Unido
Fil: Guillén Villafuerte, Olmedo. Universidad de La Laguna; España
Fil: Plana, Daniela. University of Bristol; Reino Unido
Fil: Lázaro, María J.. Consejo Superior de Investigaciones Científicas; España
Fil: Pastor, Elena. Universidad de La Laguna; España
Fil: Fermín, David J.. University of Bristol; Reino Unido
Materia
AU-PD CORE-SHELLS
DEMS
FORMIC ACID
IN SITU FTIR
STRAIN EFFECT
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:11336/66730
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/66730
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell NanoparticlesCelorrio, VerónicaQuaino, Paola MonicaSantos, Elizabeth del CarmenFlórez Montaño, JonathanHumphrey, Jo J. L.Guillén Villafuerte, OlmedoPlana, DanielaLázaro, María J.Pastor, ElenaFermín, David J.AU-PD CORE-SHELLSDEMSFORMIC ACIDIN SITU FTIRSTRAIN EFFECThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The mechanism of CO and HCOOH electrooxidation in an acidic solution on carbon-supported Au-Pd core-shell nanoparticles was investigated by differential electrochemical mass spectrometry and in situ Fourier transform infrared (FTIR) spectroscopy. Analysis performed in nanostructures with 1.3 ± 0.1 nm (CS1) and 9.9 ± 1.1 nm (CS10) Pd shells provides compelling evidence that the mechanism of adsorbed CO (COads) oxidation is affected by structural and electronic effects introduced by the Au cores. In the case of CS10, a band associated with adsorbed OH species (OHads) is observed in the potential range of CO oxidation. This feature is not detected in the case of CS1, suggesting that the reaction follows an alternative mechanism involving COOHads species. The faradaic charge associated with COads oxidation as well as the Stark slope measured from FTIR indicates that the overall affinity and orbital coupling of CO to Pd are weaker for CS1 shells. FTIR spectroscopy also revealed the presence of HCOOads intermediate species only in the case of CS1. This observation allowed us to conclude that the higher activity of CS10 toward this reaction is due to a fast HCOOads oxidation step, probably involving OHads, to generate CO2. Density functional theory calculations are used to estimate the contributions of the so-called ligand and strain effects on the local density of states of the Pd d-band. The calculations strongly suggest that the key parameter contributing to the change in mechanism is the effective lattice strain.Fil: Celorrio, Verónica. University of Bristol; Reino UnidoFil: 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.; ArgentinaFil: Santos, Elizabeth del Carmen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universitat Ulm; AlemaniaFil: Flórez Montaño, Jonathan. Universidad de La Laguna; EspañaFil: Humphrey, Jo J. L.. University of Bristol; Reino UnidoFil: Guillén Villafuerte, Olmedo. Universidad de La Laguna; EspañaFil: Plana, Daniela. University of Bristol; Reino UnidoFil: Lázaro, María J.. Consejo Superior de Investigaciones Científicas; EspañaFil: Pastor, Elena. Universidad de La Laguna; EspañaFil: Fermín, David J.. University of Bristol; Reino UnidoAmerican Chemical Society2017-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/66730Celorrio, Verónica; Quaino, Paola Monica; Santos, Elizabeth del Carmen; Flórez Montaño, Jonathan; Humphrey, Jo J. L.; et al.; Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles; American Chemical Society; ACS Catalysis; 7; 3; 3-2017; 1673-16802155-5435CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.6b03237info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acscatal.6b03237info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:07:52Zoai:ri.conicet.gov.ar:11336/66730instacron: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 10:07:52.366CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
title Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
spellingShingle Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
Celorrio, Verónica
AU-PD CORE-SHELLS
DEMS
FORMIC ACID
IN SITU FTIR
STRAIN EFFECT
title_short Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
title_full Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
title_fullStr Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
title_full_unstemmed Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
title_sort Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles
dc.creator.none.fl_str_mv Celorrio, Verónica
Quaino, Paola Monica
Santos, Elizabeth del Carmen
Flórez Montaño, Jonathan
Humphrey, Jo J. L.
Guillén Villafuerte, Olmedo
Plana, Daniela
Lázaro, María J.
Pastor, Elena
Fermín, David J.
author Celorrio, Verónica
author_facet Celorrio, Verónica
Quaino, Paola Monica
Santos, Elizabeth del Carmen
Flórez Montaño, Jonathan
Humphrey, Jo J. L.
Guillén Villafuerte, Olmedo
Plana, Daniela
Lázaro, María J.
Pastor, Elena
Fermín, David J.
author_role author
author2 Quaino, Paola Monica
Santos, Elizabeth del Carmen
Flórez Montaño, Jonathan
Humphrey, Jo J. L.
Guillén Villafuerte, Olmedo
Plana, Daniela
Lázaro, María J.
Pastor, Elena
Fermín, David J.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv AU-PD CORE-SHELLS
DEMS
FORMIC ACID
IN SITU FTIR
STRAIN EFFECT
topic AU-PD CORE-SHELLS
DEMS
FORMIC ACID
IN SITU FTIR
STRAIN EFFECT
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 mechanism of CO and HCOOH electrooxidation in an acidic solution on carbon-supported Au-Pd core-shell nanoparticles was investigated by differential electrochemical mass spectrometry and in situ Fourier transform infrared (FTIR) spectroscopy. Analysis performed in nanostructures with 1.3 ± 0.1 nm (CS1) and 9.9 ± 1.1 nm (CS10) Pd shells provides compelling evidence that the mechanism of adsorbed CO (COads) oxidation is affected by structural and electronic effects introduced by the Au cores. In the case of CS10, a band associated with adsorbed OH species (OHads) is observed in the potential range of CO oxidation. This feature is not detected in the case of CS1, suggesting that the reaction follows an alternative mechanism involving COOHads species. The faradaic charge associated with COads oxidation as well as the Stark slope measured from FTIR indicates that the overall affinity and orbital coupling of CO to Pd are weaker for CS1 shells. FTIR spectroscopy also revealed the presence of HCOOads intermediate species only in the case of CS1. This observation allowed us to conclude that the higher activity of CS10 toward this reaction is due to a fast HCOOads oxidation step, probably involving OHads, to generate CO2. Density functional theory calculations are used to estimate the contributions of the so-called ligand and strain effects on the local density of states of the Pd d-band. The calculations strongly suggest that the key parameter contributing to the change in mechanism is the effective lattice strain.
Fil: Celorrio, Verónica. University of Bristol; Reino Unido
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
Fil: Santos, Elizabeth del Carmen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universitat Ulm; Alemania
Fil: Flórez Montaño, Jonathan. Universidad de La Laguna; España
Fil: Humphrey, Jo J. L.. University of Bristol; Reino Unido
Fil: Guillén Villafuerte, Olmedo. Universidad de La Laguna; España
Fil: Plana, Daniela. University of Bristol; Reino Unido
Fil: Lázaro, María J.. Consejo Superior de Investigaciones Científicas; España
Fil: Pastor, Elena. Universidad de La Laguna; España
Fil: Fermín, David J.. University of Bristol; Reino Unido
description The mechanism of CO and HCOOH electrooxidation in an acidic solution on carbon-supported Au-Pd core-shell nanoparticles was investigated by differential electrochemical mass spectrometry and in situ Fourier transform infrared (FTIR) spectroscopy. Analysis performed in nanostructures with 1.3 ± 0.1 nm (CS1) and 9.9 ± 1.1 nm (CS10) Pd shells provides compelling evidence that the mechanism of adsorbed CO (COads) oxidation is affected by structural and electronic effects introduced by the Au cores. In the case of CS10, a band associated with adsorbed OH species (OHads) is observed in the potential range of CO oxidation. This feature is not detected in the case of CS1, suggesting that the reaction follows an alternative mechanism involving COOHads species. The faradaic charge associated with COads oxidation as well as the Stark slope measured from FTIR indicates that the overall affinity and orbital coupling of CO to Pd are weaker for CS1 shells. FTIR spectroscopy also revealed the presence of HCOOads intermediate species only in the case of CS1. This observation allowed us to conclude that the higher activity of CS10 toward this reaction is due to a fast HCOOads oxidation step, probably involving OHads, to generate CO2. Density functional theory calculations are used to estimate the contributions of the so-called ligand and strain effects on the local density of states of the Pd d-band. The calculations strongly suggest that the key parameter contributing to the change in mechanism is the effective lattice strain.
publishDate 2017
dc.date.none.fl_str_mv 2017-03
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/11336/66730
Celorrio, Verónica; Quaino, Paola Monica; Santos, Elizabeth del Carmen; Flórez Montaño, Jonathan; Humphrey, Jo J. L.; et al.; Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles; American Chemical Society; ACS Catalysis; 7; 3; 3-2017; 1673-1680
2155-5435
CONICET Digital
CONICET
url http://hdl.handle.net/11336/66730
identifier_str_mv Celorrio, Verónica; Quaino, Paola Monica; Santos, Elizabeth del Carmen; Flórez Montaño, Jonathan; Humphrey, Jo J. L.; et al.; Strain Effects on the Oxidation of CO and HCOOH on Au-Pd Core-Shell Nanoparticles; American Chemical Society; ACS Catalysis; 7; 3; 3-2017; 1673-1680
2155-5435
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.6b03237
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acscatal.6b03237
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 Chemical Society
publisher.none.fl_str_mv American Chemical 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 13.13397

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