Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory...

Autores
Lustemberg, Pablo German; Bosco, Marta Verónica; Bonivardi, Adrian Lionel; Busnengo, Heriberto Fabio; Ganduglia Pirovano, M. V.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Formation of formate species on oxide surfaces plays a role in reactions for hydrogenproduction such as the water-gas shift, and the steam reforming of alcohols. It has beensuggested that bridge formates are the most common and stable configuration on metaloxides. Ceria-based catalysts are important for these reactions where ceria is a ?noninnocent?support. In this work, the nature of the formate species that are formedduring decomposition and reaction of methanol on ceria surfaces have been studiedusing a combination of infrared temperature programmed surface reaction (TPSR-IR)on a real powder catalyst support, and density functional theory (DFT) together withstatistical thermodynamics for model CeO2(111) surfaces. The influence of surfaceoxygen vacancies, hydroxyl groups, and water has been considered. Three differentformate species have been identified (450−550 K). Initially, formates are adsorbed onthe oxidized surface that is gradually hydroxylated by the release of hydrogen frommethoxy groups (> 500 K), which leads to a partially reduced surface. On the formerone kind of species is observed, whereas on the latter the other two kinds appeared. Weprovide computational evidence that the bonding is only initially of the bridge type, butbecomes of the monodentate type, as the surface concentration of hydroxyl groups rises.The calculated frequencies of the O−C−O symmetric and asymmetric stretching modesfor the three structures are in good agreement with those experimentally observed. Theexistence of monodentate species is discussed in terms of a stabilizing effect of hydrogenbonds. The combined experimental and theoretical results on real and model systems,respectively, thus provide important insights on the reaction of methanol on ceriasurfaces.
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Bosco, Marta Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química (i); Argentina
Fil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química (i); Argentina
Fil: Busnengo, Heriberto Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Ganduglia Pirovano, M. V.. Consejo Superior de Investigaciones Cientificas. Instituto de Catalisis y Petroleoquimica; España
Materia
Formate Species
Co-Adsorbed Hydroxyl
Ir Spectroscopy
Density Functional Theory
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:11336/9734
Acceder
id CONICETDig_3f4e1079455a0a6e857324c5190d5887
oai_identifier_str oai:ri.conicet.gov.ar:11336/9734
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory StudyLustemberg, Pablo GermanBosco, Marta VerónicaBonivardi, Adrian LionelBusnengo, Heriberto FabioGanduglia Pirovano, M. V.Formate SpeciesCo-Adsorbed HydroxylIr SpectroscopyDensity Functional Theoryhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Formation of formate species on oxide surfaces plays a role in reactions for hydrogenproduction such as the water-gas shift, and the steam reforming of alcohols. It has beensuggested that bridge formates are the most common and stable configuration on metaloxides. Ceria-based catalysts are important for these reactions where ceria is a ?noninnocent?support. In this work, the nature of the formate species that are formedduring decomposition and reaction of methanol on ceria surfaces have been studiedusing a combination of infrared temperature programmed surface reaction (TPSR-IR)on a real powder catalyst support, and density functional theory (DFT) together withstatistical thermodynamics for model CeO2(111) surfaces. The influence of surfaceoxygen vacancies, hydroxyl groups, and water has been considered. Three differentformate species have been identified (450−550 K). Initially, formates are adsorbed onthe oxidized surface that is gradually hydroxylated by the release of hydrogen frommethoxy groups (> 500 K), which leads to a partially reduced surface. On the formerone kind of species is observed, whereas on the latter the other two kinds appeared. Weprovide computational evidence that the bonding is only initially of the bridge type, butbecomes of the monodentate type, as the surface concentration of hydroxyl groups rises.The calculated frequencies of the O−C−O symmetric and asymmetric stretching modesfor the three structures are in good agreement with those experimentally observed. Theexistence of monodentate species is discussed in terms of a stabilizing effect of hydrogenbonds. The combined experimental and theoretical results on real and model systems,respectively, thus provide important insights on the reaction of methanol on ceriasurfaces.Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); ArgentinaFil: Bosco, Marta Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química (i); ArgentinaFil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química (i); ArgentinaFil: Busnengo, Heriberto Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); ArgentinaFil: Ganduglia Pirovano, M. V.. Consejo Superior de Investigaciones Cientificas. Instituto de Catalisis y Petroleoquimica; EspañaAmerican Chemical Society2015-08info: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/11336/9734Lustemberg, Pablo German; Bosco, Marta Verónica; Bonivardi, Adrian Lionel; Busnengo, Heriberto Fabio; Ganduglia Pirovano, M. V.; Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study; American Chemical Society; Journal Of Physical Chemistry C; 119; 37; 8-2015; 21452-214641932-7447enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b05070info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.5b05070info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:20:36Zoai:ri.conicet.gov.ar:11336/9734instacron: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 12:20:36.977CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
title Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
spellingShingle Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
Lustemberg, Pablo German
Formate Species
Co-Adsorbed Hydroxyl
Ir Spectroscopy
Density Functional Theory
title_short Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
title_full Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
title_fullStr Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
title_full_unstemmed Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
title_sort Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study
dc.creator.none.fl_str_mv Lustemberg, Pablo German
Bosco, Marta Verónica
Bonivardi, Adrian Lionel
Busnengo, Heriberto Fabio
Ganduglia Pirovano, M. V.
author Lustemberg, Pablo German
author_facet Lustemberg, Pablo German
Bosco, Marta Verónica
Bonivardi, Adrian Lionel
Busnengo, Heriberto Fabio
Ganduglia Pirovano, M. V.
author_role author
author2 Bosco, Marta Verónica
Bonivardi, Adrian Lionel
Busnengo, Heriberto Fabio
Ganduglia Pirovano, M. V.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Formate Species
Co-Adsorbed Hydroxyl
Ir Spectroscopy
Density Functional Theory
topic Formate Species
Co-Adsorbed Hydroxyl
Ir Spectroscopy
Density Functional Theory
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Formation of formate species on oxide surfaces plays a role in reactions for hydrogenproduction such as the water-gas shift, and the steam reforming of alcohols. It has beensuggested that bridge formates are the most common and stable configuration on metaloxides. Ceria-based catalysts are important for these reactions where ceria is a ?noninnocent?support. In this work, the nature of the formate species that are formedduring decomposition and reaction of methanol on ceria surfaces have been studiedusing a combination of infrared temperature programmed surface reaction (TPSR-IR)on a real powder catalyst support, and density functional theory (DFT) together withstatistical thermodynamics for model CeO2(111) surfaces. The influence of surfaceoxygen vacancies, hydroxyl groups, and water has been considered. Three differentformate species have been identified (450−550 K). Initially, formates are adsorbed onthe oxidized surface that is gradually hydroxylated by the release of hydrogen frommethoxy groups (> 500 K), which leads to a partially reduced surface. On the formerone kind of species is observed, whereas on the latter the other two kinds appeared. Weprovide computational evidence that the bonding is only initially of the bridge type, butbecomes of the monodentate type, as the surface concentration of hydroxyl groups rises.The calculated frequencies of the O−C−O symmetric and asymmetric stretching modesfor the three structures are in good agreement with those experimentally observed. Theexistence of monodentate species is discussed in terms of a stabilizing effect of hydrogenbonds. The combined experimental and theoretical results on real and model systems,respectively, thus provide important insights on the reaction of methanol on ceriasurfaces.
Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Bosco, Marta Verónica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química (i); Argentina
Fil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química (i); Argentina
Fil: Busnengo, Heriberto Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Física de Rosario (i); Argentina
Fil: Ganduglia Pirovano, M. V.. Consejo Superior de Investigaciones Cientificas. Instituto de Catalisis y Petroleoquimica; España
description Formation of formate species on oxide surfaces plays a role in reactions for hydrogenproduction such as the water-gas shift, and the steam reforming of alcohols. It has beensuggested that bridge formates are the most common and stable configuration on metaloxides. Ceria-based catalysts are important for these reactions where ceria is a ?noninnocent?support. In this work, the nature of the formate species that are formedduring decomposition and reaction of methanol on ceria surfaces have been studiedusing a combination of infrared temperature programmed surface reaction (TPSR-IR)on a real powder catalyst support, and density functional theory (DFT) together withstatistical thermodynamics for model CeO2(111) surfaces. The influence of surfaceoxygen vacancies, hydroxyl groups, and water has been considered. Three differentformate species have been identified (450−550 K). Initially, formates are adsorbed onthe oxidized surface that is gradually hydroxylated by the release of hydrogen frommethoxy groups (> 500 K), which leads to a partially reduced surface. On the formerone kind of species is observed, whereas on the latter the other two kinds appeared. Weprovide computational evidence that the bonding is only initially of the bridge type, butbecomes of the monodentate type, as the surface concentration of hydroxyl groups rises.The calculated frequencies of the O−C−O symmetric and asymmetric stretching modesfor the three structures are in good agreement with those experimentally observed. Theexistence of monodentate species is discussed in terms of a stabilizing effect of hydrogenbonds. The combined experimental and theoretical results on real and model systems,respectively, thus provide important insights on the reaction of methanol on ceriasurfaces.
publishDate 2015
dc.date.none.fl_str_mv 2015-08
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/11336/9734
Lustemberg, Pablo German; Bosco, Marta Verónica; Bonivardi, Adrian Lionel; Busnengo, Heriberto Fabio; Ganduglia Pirovano, M. V.; Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study; American Chemical Society; Journal Of Physical Chemistry C; 119; 37; 8-2015; 21452-21464
1932-7447
url http://hdl.handle.net/11336/9734
identifier_str_mv Lustemberg, Pablo German; Bosco, Marta Verónica; Bonivardi, Adrian Lionel; Busnengo, Heriberto Fabio; Ganduglia Pirovano, M. V.; Insights into the Nature of Formate Species in the Decomposition and Reaction of Methanol over Cerium Oxide Surfaces: A Combined Infrared Spectroscopy and Density Functional Theory Study; American Chemical Society; Journal Of Physical Chemistry C; 119; 37; 8-2015; 21452-21464
1932-7447
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b05070
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.5b05070
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 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
_version_ 1846782654908727296
score 12.982451

Publicaciones similares