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
Institución: Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador: oai:ri.conicet.gov.ar:11336/9734

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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 Técnicas2025-09-29T10:47:11Zoai: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:34982025-09-29 10:47:12.08CONICET 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)
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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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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...

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