Adsorption and decomposition of methanol on gallium oxide polymorphs

Autores
Collins, Sebastián Enrique; Briand, Laura Estefania; Gambaro, Luis Alberto; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The adsorption of methanol was studied on three gallia polymorphs (alpha, beta, and gamma), pretreated under oxygen or hydrogen at 723 K. Their Brunauer-Emmett-Teller surface areas were in the range 12-105 m2 g-1. Methanol (or methanol-d3) chemisorbs on the gallium oxides both molecularly, as CH3OHS (or CD3OHS,) and dissociatively, as methoxy (CH3O or CD3O) species, at 373 K. The quantification of the total amount of chemisorbed methanol at this temperature allowed us to determine the number of available surface active sites per unit area (NS), which is in the range 1-2 µmol m-2 for the oxygen pretreated oxides at 723 K. The density of active sites was moderately smaller (~25%) after pretreating the oxides under hydrogen at 723 K. The temperature-programmed surface reaction of adsorbed methanol and methoxy was followed by mass spectrometry and infrared spectroscopy under He flow, up to 723 K. It was found that, upon heating above 473 K, methoxy oxidized to methylenbisoxi (H2COO) and, then, to formate (HCOO) species, and traces of dimethyl ether were also detected. Surface formate species further decompose to give CO(g) and CO2(g) at temperatures higher than 573 K, with the concurrent generation of OH and H species over the surface, which react toward H2(g). It is suggested that the CO2 production implies the removal of lattice oxygen, generating a surface oxygen vacancy, which can be restored by water molecules from the gas phase. Thus, gallia can be envisaged as a promising support for the steam reforming of methanol, as long as a (noble) metal officiates/ acts as a rapid H2 releaser from the surface.
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: Briand, Laura Estefania. Universidad Nacional de La Plata; Argentina
Fil: Gambaro, Luis Alberto. Universidad Nacional de La Plata; 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
Methanol
Adsorption
Gallia
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:11336/19781
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/19781
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Adsorption and decomposition of methanol on gallium oxide polymorphsCollins, Sebastián EnriqueBriand, Laura EstefaniaGambaro, Luis AlbertoBaltanas, Miguel AngelBonivardi, Adrian LionelMethanolAdsorptionGalliahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The adsorption of methanol was studied on three gallia polymorphs (alpha, beta, and gamma), pretreated under oxygen or hydrogen at 723 K. Their Brunauer-Emmett-Teller surface areas were in the range 12-105 m2 g-1. Methanol (or methanol-d3) chemisorbs on the gallium oxides both molecularly, as CH3OHS (or CD3OHS,) and dissociatively, as methoxy (CH3O or CD3O) species, at 373 K. The quantification of the total amount of chemisorbed methanol at this temperature allowed us to determine the number of available surface active sites per unit area (NS), which is in the range 1-2 µmol m-2 for the oxygen pretreated oxides at 723 K. The density of active sites was moderately smaller (~25%) after pretreating the oxides under hydrogen at 723 K. The temperature-programmed surface reaction of adsorbed methanol and methoxy was followed by mass spectrometry and infrared spectroscopy under He flow, up to 723 K. It was found that, upon heating above 473 K, methoxy oxidized to methylenbisoxi (H2COO) and, then, to formate (HCOO) species, and traces of dimethyl ether were also detected. Surface formate species further decompose to give CO(g) and CO2(g) at temperatures higher than 573 K, with the concurrent generation of OH and H species over the surface, which react toward H2(g). It is suggested that the CO2 production implies the removal of lattice oxygen, generating a surface oxygen vacancy, which can be restored by water molecules from the gas phase. Thus, gallia can be envisaged as a promising support for the steam reforming of methanol, as long as a (noble) metal officiates/ acts as a rapid H2 releaser from the surface.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; ArgentinaFil: Briand, Laura Estefania. Universidad Nacional de La Plata; ArgentinaFil: Gambaro, Luis Alberto. Universidad Nacional de La Plata; 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; ArgentinaAmerican Chemical Society2008-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/19781Collins, Sebastián Enrique; Briand, Laura Estefania; Gambaro, Luis Alberto; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel; Adsorption and decomposition of methanol on gallium oxide polymorphs; American Chemical Society; Journal of Physical Chemistry C; 112; 38; 12-2008; 14988-150001932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp801252dinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp801252dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:52:10Zoai:ri.conicet.gov.ar:11336/19781instacron: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 09:52:11.245CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Adsorption and decomposition of methanol on gallium oxide polymorphs
title Adsorption and decomposition of methanol on gallium oxide polymorphs
spellingShingle Adsorption and decomposition of methanol on gallium oxide polymorphs
Collins, Sebastián Enrique
Methanol
Adsorption
Gallia
title_short Adsorption and decomposition of methanol on gallium oxide polymorphs
title_full Adsorption and decomposition of methanol on gallium oxide polymorphs
title_fullStr Adsorption and decomposition of methanol on gallium oxide polymorphs
title_full_unstemmed Adsorption and decomposition of methanol on gallium oxide polymorphs
title_sort Adsorption and decomposition of methanol on gallium oxide polymorphs
dc.creator.none.fl_str_mv Collins, Sebastián Enrique
Briand, Laura Estefania
Gambaro, Luis Alberto
Baltanas, Miguel Angel
Bonivardi, Adrian Lionel
author Collins, Sebastián Enrique
author_facet Collins, Sebastián Enrique
Briand, Laura Estefania
Gambaro, Luis Alberto
Baltanas, Miguel Angel
Bonivardi, Adrian Lionel
author_role author
author2 Briand, Laura Estefania
Gambaro, Luis Alberto
Baltanas, Miguel Angel
Bonivardi, Adrian Lionel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Methanol
Adsorption
Gallia
topic Methanol
Adsorption
Gallia
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 adsorption of methanol was studied on three gallia polymorphs (alpha, beta, and gamma), pretreated under oxygen or hydrogen at 723 K. Their Brunauer-Emmett-Teller surface areas were in the range 12-105 m2 g-1. Methanol (or methanol-d3) chemisorbs on the gallium oxides both molecularly, as CH3OHS (or CD3OHS,) and dissociatively, as methoxy (CH3O or CD3O) species, at 373 K. The quantification of the total amount of chemisorbed methanol at this temperature allowed us to determine the number of available surface active sites per unit area (NS), which is in the range 1-2 µmol m-2 for the oxygen pretreated oxides at 723 K. The density of active sites was moderately smaller (~25%) after pretreating the oxides under hydrogen at 723 K. The temperature-programmed surface reaction of adsorbed methanol and methoxy was followed by mass spectrometry and infrared spectroscopy under He flow, up to 723 K. It was found that, upon heating above 473 K, methoxy oxidized to methylenbisoxi (H2COO) and, then, to formate (HCOO) species, and traces of dimethyl ether were also detected. Surface formate species further decompose to give CO(g) and CO2(g) at temperatures higher than 573 K, with the concurrent generation of OH and H species over the surface, which react toward H2(g). It is suggested that the CO2 production implies the removal of lattice oxygen, generating a surface oxygen vacancy, which can be restored by water molecules from the gas phase. Thus, gallia can be envisaged as a promising support for the steam reforming of methanol, as long as a (noble) metal officiates/ acts as a rapid H2 releaser from the surface.
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: Briand, Laura Estefania. Universidad Nacional de La Plata; Argentina
Fil: Gambaro, Luis Alberto. Universidad Nacional de La Plata; 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 The adsorption of methanol was studied on three gallia polymorphs (alpha, beta, and gamma), pretreated under oxygen or hydrogen at 723 K. Their Brunauer-Emmett-Teller surface areas were in the range 12-105 m2 g-1. Methanol (or methanol-d3) chemisorbs on the gallium oxides both molecularly, as CH3OHS (or CD3OHS,) and dissociatively, as methoxy (CH3O or CD3O) species, at 373 K. The quantification of the total amount of chemisorbed methanol at this temperature allowed us to determine the number of available surface active sites per unit area (NS), which is in the range 1-2 µmol m-2 for the oxygen pretreated oxides at 723 K. The density of active sites was moderately smaller (~25%) after pretreating the oxides under hydrogen at 723 K. The temperature-programmed surface reaction of adsorbed methanol and methoxy was followed by mass spectrometry and infrared spectroscopy under He flow, up to 723 K. It was found that, upon heating above 473 K, methoxy oxidized to methylenbisoxi (H2COO) and, then, to formate (HCOO) species, and traces of dimethyl ether were also detected. Surface formate species further decompose to give CO(g) and CO2(g) at temperatures higher than 573 K, with the concurrent generation of OH and H species over the surface, which react toward H2(g). It is suggested that the CO2 production implies the removal of lattice oxygen, generating a surface oxygen vacancy, which can be restored by water molecules from the gas phase. Thus, gallia can be envisaged as a promising support for the steam reforming of methanol, as long as a (noble) metal officiates/ acts as a rapid H2 releaser from the surface.
publishDate 2008
dc.date.none.fl_str_mv 2008-12
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/11336/19781
Collins, Sebastián Enrique; Briand, Laura Estefania; Gambaro, Luis Alberto; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel; Adsorption and decomposition of methanol on gallium oxide polymorphs; American Chemical Society; Journal of Physical Chemistry C; 112; 38; 12-2008; 14988-15000
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/19781
identifier_str_mv Collins, Sebastián Enrique; Briand, Laura Estefania; Gambaro, Luis Alberto; Baltanas, Miguel Angel; Bonivardi, Adrian Lionel; Adsorption and decomposition of methanol on gallium oxide polymorphs; American Chemical Society; Journal of Physical Chemistry C; 112; 38; 12-2008; 14988-15000
1932-7447
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/jp801252d
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp801252d
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 13.070432

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