Stability of formate species on beta-Ga2O3

Autores
Calatayud, M.; Collins, Sebastián Enrique; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Gallia (gallium oxide) has been proved to enhance the performance of metal catalysts in a variety of catalytic reactions involving methanol, CO and H2. The presence of formate species as key intermediates in some of these reactions has been reported, although their role is still a matter of debate. In this work, a combined theoretical and experimental approach has been carried out in order to characterize the formation of such formate species over the gallium oxide surface. Infrared spectroscopy experiments of CO adsorption over H2 (or D2) pretreated b-Ga2O3 revealed the formation of several formate species. The b-Ga2O3 (100) surface was modelled by means of periodic DFT calculations. The stability of said species and their vibrational mode assignments are discussed together with the formate interconversion barriers. A possible mechanism is proposed based on the experimental and theoretical results: first CO inserts into surface (monocoordinate) hydroxyl groups leading to monocoordinate formate; this species might evolve to the thermodynamically most stable dicoordinate formate, or might transfer hydrogen to the surface oxidizing to CO2 creating an oxygen vacancy and a hydride group. The barrier for the first step, CO insertion, is calculated to be significantly higher than that of the monocoordinate formate conversion steps. Monocoordinate formates are thus short-lived intermediates playing a key role in the CO oxidation reaction, while bidentate formates are mainly spectators.
Fil: Calatayud, M.. Universite Pierre et Marie Curie; Francia
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
Fil: Baltanas, Miguel Angel. 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: 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
Materia
Infrared
Dft
Formate
Ga2o3
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:11336/21693
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Stability of formate species on beta-Ga2O3Calatayud, M.Collins, Sebastián EnriqueBaltanas, Miguel AngelBonivardi, Adrian LionelInfraredDftFormateGa2o3https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Gallia (gallium oxide) has been proved to enhance the performance of metal catalysts in a variety of catalytic reactions involving methanol, CO and H2. The presence of formate species as key intermediates in some of these reactions has been reported, although their role is still a matter of debate. In this work, a combined theoretical and experimental approach has been carried out in order to characterize the formation of such formate species over the gallium oxide surface. Infrared spectroscopy experiments of CO adsorption over H2 (or D2) pretreated b-Ga2O3 revealed the formation of several formate species. The b-Ga2O3 (100) surface was modelled by means of periodic DFT calculations. The stability of said species and their vibrational mode assignments are discussed together with the formate interconversion barriers. A possible mechanism is proposed based on the experimental and theoretical results: first CO inserts into surface (monocoordinate) hydroxyl groups leading to monocoordinate formate; this species might evolve to the thermodynamically most stable dicoordinate formate, or might transfer hydrogen to the surface oxidizing to CO2 creating an oxygen vacancy and a hydride group. The barrier for the first step, CO insertion, is calculated to be significantly higher than that of the monocoordinate formate conversion steps. Monocoordinate formates are thus short-lived intermediates playing a key role in the CO oxidation reaction, while bidentate formates are mainly spectators.Fil: Calatayud, M.. Universite Pierre et Marie Curie; FranciaFil: 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; ArgentinaFil: Baltanas, Miguel Angel. 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: 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; ArgentinaRoyal Society of Chemistry2009-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/21693Calatayud, M.; Collins, Sebastián Enrique; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel; Stability of formate species on beta-Ga2O3; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 9; 12-2009; 1397-14051463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/b800519binfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2009/CP/b800519b#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:49:22Zoai:ri.conicet.gov.ar:11336/21693instacron: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 09:49:22.316CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Stability of formate species on beta-Ga2O3
title Stability of formate species on beta-Ga2O3
spellingShingle Stability of formate species on beta-Ga2O3
Calatayud, M.
Infrared
Dft
Formate
Ga2o3
title_short Stability of formate species on beta-Ga2O3
title_full Stability of formate species on beta-Ga2O3
title_fullStr Stability of formate species on beta-Ga2O3
title_full_unstemmed Stability of formate species on beta-Ga2O3
title_sort Stability of formate species on beta-Ga2O3
dc.creator.none.fl_str_mv Calatayud, M.
Collins, Sebastián Enrique
Baltanas, Miguel Angel
Bonivardi, Adrian Lionel
author Calatayud, M.
author_facet Calatayud, M.
Collins, Sebastián Enrique
Baltanas, Miguel Angel
Bonivardi, Adrian Lionel
author_role author
author2 Collins, Sebastián Enrique
Baltanas, Miguel Angel
Bonivardi, Adrian Lionel
author2_role author
author
author
dc.subject.none.fl_str_mv Infrared
Dft
Formate
Ga2o3
topic Infrared
Dft
Formate
Ga2o3
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Gallia (gallium oxide) has been proved to enhance the performance of metal catalysts in a variety of catalytic reactions involving methanol, CO and H2. The presence of formate species as key intermediates in some of these reactions has been reported, although their role is still a matter of debate. In this work, a combined theoretical and experimental approach has been carried out in order to characterize the formation of such formate species over the gallium oxide surface. Infrared spectroscopy experiments of CO adsorption over H2 (or D2) pretreated b-Ga2O3 revealed the formation of several formate species. The b-Ga2O3 (100) surface was modelled by means of periodic DFT calculations. The stability of said species and their vibrational mode assignments are discussed together with the formate interconversion barriers. A possible mechanism is proposed based on the experimental and theoretical results: first CO inserts into surface (monocoordinate) hydroxyl groups leading to monocoordinate formate; this species might evolve to the thermodynamically most stable dicoordinate formate, or might transfer hydrogen to the surface oxidizing to CO2 creating an oxygen vacancy and a hydride group. The barrier for the first step, CO insertion, is calculated to be significantly higher than that of the monocoordinate formate conversion steps. Monocoordinate formates are thus short-lived intermediates playing a key role in the CO oxidation reaction, while bidentate formates are mainly spectators.
Fil: Calatayud, M.. Universite Pierre et Marie Curie; Francia
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
Fil: Baltanas, Miguel Angel. 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: 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
description Gallia (gallium oxide) has been proved to enhance the performance of metal catalysts in a variety of catalytic reactions involving methanol, CO and H2. The presence of formate species as key intermediates in some of these reactions has been reported, although their role is still a matter of debate. In this work, a combined theoretical and experimental approach has been carried out in order to characterize the formation of such formate species over the gallium oxide surface. Infrared spectroscopy experiments of CO adsorption over H2 (or D2) pretreated b-Ga2O3 revealed the formation of several formate species. The b-Ga2O3 (100) surface was modelled by means of periodic DFT calculations. The stability of said species and their vibrational mode assignments are discussed together with the formate interconversion barriers. A possible mechanism is proposed based on the experimental and theoretical results: first CO inserts into surface (monocoordinate) hydroxyl groups leading to monocoordinate formate; this species might evolve to the thermodynamically most stable dicoordinate formate, or might transfer hydrogen to the surface oxidizing to CO2 creating an oxygen vacancy and a hydride group. The barrier for the first step, CO insertion, is calculated to be significantly higher than that of the monocoordinate formate conversion steps. Monocoordinate formates are thus short-lived intermediates playing a key role in the CO oxidation reaction, while bidentate formates are mainly spectators.
publishDate 2009
dc.date.none.fl_str_mv 2009-12
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/11336/21693
Calatayud, M.; Collins, Sebastián Enrique; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel; Stability of formate species on beta-Ga2O3; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 9; 12-2009; 1397-1405
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/21693
identifier_str_mv Calatayud, M.; Collins, Sebastián Enrique; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel; Stability of formate species on beta-Ga2O3; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 9; 12-2009; 1397-1405
1463-9076
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/b800519b
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2009/CP/b800519b#!divAbstract
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
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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