Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst

Autores
Vecchietti, María Julia; Belletti, Gustavo Daniel; Quaino, Paola Monica; Bonivardi, Adrian Lionel; Collins, Sebastián Enrique
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
ChemCatChem homepage for more articles in the collection. The mechanism of the low-temperature water gas shift reaction (LTWGS) on an Au/CeO2 catalyst was investigated by means of in situ diffuse reflectance infrared (DRIFT) spectroscopy. Under steady-state LTWGS reaction (373–623 K), the catalyst is partially reduced, and signals from carbonate/formate dominates the infrared spectra. Time-resolved pulse of CO experiment under a constant partial pressure of water at 423 K indicates that Ce4+ can be reduced to Ce3+ and that formate (HCOO) species cannot be directly related to the CO2 production. Further information was obtained by performing modulation excitation spectroscopy (MES) experiments coupled with a phase-sensitive detection (PSD) method. Under periodic modulation of the CO partial pressure while keeping the H2O concentration constant, most of the intense bands of carbonate and formate remained constant, indicating that these species are only spectators. The same is observed for the concentration of Ce3+. Conversely, signals in-phase with the conversion of CO to CO2 are observed and assigned to carboxyl [C(O)OH] and carboxylate (CO2δ−) species, while some monodentate formate (m-HCOO) also changes but at a lower rate. A plausible associative reaction mechanism where carboxyl/carboxylate are key intermediates is postulated.
Fil: Vecchietti, María Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; 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: 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: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Collins, Sebastián Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Materia
CARBOXYL
CARBOXYLATE
CERIUM OXIDE
FORMATE
GOLD CATALYSTS
MODULATION SPECTROSCOPY
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:11336/226241
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/226241
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria CatalystVecchietti, María JuliaBelletti, Gustavo DanielQuaino, Paola MonicaBonivardi, Adrian LionelCollins, Sebastián EnriqueCARBOXYLCARBOXYLATECERIUM OXIDEFORMATEGOLD CATALYSTSMODULATION SPECTROSCOPYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1ChemCatChem homepage for more articles in the collection. The mechanism of the low-temperature water gas shift reaction (LTWGS) on an Au/CeO2 catalyst was investigated by means of in situ diffuse reflectance infrared (DRIFT) spectroscopy. Under steady-state LTWGS reaction (373–623 K), the catalyst is partially reduced, and signals from carbonate/formate dominates the infrared spectra. Time-resolved pulse of CO experiment under a constant partial pressure of water at 423 K indicates that Ce4+ can be reduced to Ce3+ and that formate (HCOO) species cannot be directly related to the CO2 production. Further information was obtained by performing modulation excitation spectroscopy (MES) experiments coupled with a phase-sensitive detection (PSD) method. Under periodic modulation of the CO partial pressure while keeping the H2O concentration constant, most of the intense bands of carbonate and formate remained constant, indicating that these species are only spectators. The same is observed for the concentration of Ce3+. Conversely, signals in-phase with the conversion of CO to CO2 are observed and assigned to carboxyl [C(O)OH] and carboxylate (CO2δ−) species, while some monodentate formate (m-HCOO) also changes but at a lower rate. A plausible associative reaction mechanism where carboxyl/carboxylate are key intermediates is postulated.Fil: Vecchietti, María Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; 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: 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: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Collins, Sebastián Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaWiley VCH Verlag2023-08info: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/11336/226241Vecchietti, María Julia; Belletti, Gustavo Daniel; Quaino, Paola Monica; Bonivardi, Adrian Lionel; Collins, Sebastián Enrique; Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst; Wiley VCH Verlag; Chemcatchem; 15; 19; 8-2023; 1-231867-3880CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202300435info:eu-repo/semantics/altIdentifier/doi/10.1002/cctc.202300435info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:11:42Zoai:ri.conicet.gov.ar:11336/226241instacron: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:34982025-10-22 12:11:42.609CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
title Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
spellingShingle Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
Vecchietti, María Julia
CARBOXYL
CARBOXYLATE
CERIUM OXIDE
FORMATE
GOLD CATALYSTS
MODULATION SPECTROSCOPY
title_short Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
title_full Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
title_fullStr Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
title_full_unstemmed Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
title_sort Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst
dc.creator.none.fl_str_mv Vecchietti, María Julia
Belletti, Gustavo Daniel
Quaino, Paola Monica
Bonivardi, Adrian Lionel
Collins, Sebastián Enrique
author Vecchietti, María Julia
author_facet Vecchietti, María Julia
Belletti, Gustavo Daniel
Quaino, Paola Monica
Bonivardi, Adrian Lionel
Collins, Sebastián Enrique
author_role author
author2 Belletti, Gustavo Daniel
Quaino, Paola Monica
Bonivardi, Adrian Lionel
Collins, Sebastián Enrique
author2_role author
author
author
author
dc.subject.none.fl_str_mv CARBOXYL
CARBOXYLATE
CERIUM OXIDE
FORMATE
GOLD CATALYSTS
MODULATION SPECTROSCOPY
topic CARBOXYL
CARBOXYLATE
CERIUM OXIDE
FORMATE
GOLD CATALYSTS
MODULATION SPECTROSCOPY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv ChemCatChem homepage for more articles in the collection. The mechanism of the low-temperature water gas shift reaction (LTWGS) on an Au/CeO2 catalyst was investigated by means of in situ diffuse reflectance infrared (DRIFT) spectroscopy. Under steady-state LTWGS reaction (373–623 K), the catalyst is partially reduced, and signals from carbonate/formate dominates the infrared spectra. Time-resolved pulse of CO experiment under a constant partial pressure of water at 423 K indicates that Ce4+ can be reduced to Ce3+ and that formate (HCOO) species cannot be directly related to the CO2 production. Further information was obtained by performing modulation excitation spectroscopy (MES) experiments coupled with a phase-sensitive detection (PSD) method. Under periodic modulation of the CO partial pressure while keeping the H2O concentration constant, most of the intense bands of carbonate and formate remained constant, indicating that these species are only spectators. The same is observed for the concentration of Ce3+. Conversely, signals in-phase with the conversion of CO to CO2 are observed and assigned to carboxyl [C(O)OH] and carboxylate (CO2δ−) species, while some monodentate formate (m-HCOO) also changes but at a lower rate. A plausible associative reaction mechanism where carboxyl/carboxylate are key intermediates is postulated.
Fil: Vecchietti, María Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; 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: 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: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Collins, Sebastián Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
description ChemCatChem homepage for more articles in the collection. The mechanism of the low-temperature water gas shift reaction (LTWGS) on an Au/CeO2 catalyst was investigated by means of in situ diffuse reflectance infrared (DRIFT) spectroscopy. Under steady-state LTWGS reaction (373–623 K), the catalyst is partially reduced, and signals from carbonate/formate dominates the infrared spectra. Time-resolved pulse of CO experiment under a constant partial pressure of water at 423 K indicates that Ce4+ can be reduced to Ce3+ and that formate (HCOO) species cannot be directly related to the CO2 production. Further information was obtained by performing modulation excitation spectroscopy (MES) experiments coupled with a phase-sensitive detection (PSD) method. Under periodic modulation of the CO partial pressure while keeping the H2O concentration constant, most of the intense bands of carbonate and formate remained constant, indicating that these species are only spectators. The same is observed for the concentration of Ce3+. Conversely, signals in-phase with the conversion of CO to CO2 are observed and assigned to carboxyl [C(O)OH] and carboxylate (CO2δ−) species, while some monodentate formate (m-HCOO) also changes but at a lower rate. A plausible associative reaction mechanism where carboxyl/carboxylate are key intermediates is postulated.
publishDate 2023
dc.date.none.fl_str_mv 2023-08
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/11336/226241
Vecchietti, María Julia; Belletti, Gustavo Daniel; Quaino, Paola Monica; Bonivardi, Adrian Lionel; Collins, Sebastián Enrique; Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst; Wiley VCH Verlag; Chemcatchem; 15; 19; 8-2023; 1-23
1867-3880
CONICET Digital
CONICET
url http://hdl.handle.net/11336/226241
identifier_str_mv Vecchietti, María Julia; Belletti, Gustavo Daniel; Quaino, Paola Monica; Bonivardi, Adrian Lionel; Collins, Sebastián Enrique; Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au/Ceria Catalyst; Wiley VCH Verlag; Chemcatchem; 15; 19; 8-2023; 1-23
1867-3880
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://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202300435
info:eu-repo/semantics/altIdentifier/doi/10.1002/cctc.202300435
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
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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 12.982451

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