Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U

Autores
Reimers, Walter Guillermo; Branda, Maria Marta
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
GGA + U calculations have been carried out to study the complete methanol decomposition on the more stable Ceria surfaces, i.e. (111), (221), (331) and (110). These results have shown that the methanol adsorption is exothermic on oxidized as well as on the partially reduced surfaces though the adsorption energy is greater for the latest. The first dehydrogenation step of methanol is highly probable for all the studied sites with activation barriers smaller than 0.2 eV. The first dehydrogenation reaction could also occur by breaking the C[sbnd]H methyl bond, but we found that this reaction is very unlikely. Reaction and activation energies for the second dehydrogenation – from methoxy to formaldehyde, are very similar for perfect (111) and stepped surfaces but these activation barriers are not negligible, almost ten times as many the first step barriers. Next, the formaldehyde decomposition to formyl and CO species on perfect CeO2(111) have an important energetic cost, therefore these reactions could occur only on stepped surfaces.
Fil: Reimers, Walter Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Branda, Maria Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Materia
Catalysis
Dft
Methanol Decomposition
Oxide
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/63312
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/63312
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network_name_str CONICET Digital (CONICET)
spelling Methanol decomposition on low index and stepped CeO2 surfaces from GGA+UReimers, Walter GuillermoBranda, Maria MartaCatalysisDftMethanol DecompositionOxidehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1GGA + U calculations have been carried out to study the complete methanol decomposition on the more stable Ceria surfaces, i.e. (111), (221), (331) and (110). These results have shown that the methanol adsorption is exothermic on oxidized as well as on the partially reduced surfaces though the adsorption energy is greater for the latest. The first dehydrogenation step of methanol is highly probable for all the studied sites with activation barriers smaller than 0.2 eV. The first dehydrogenation reaction could also occur by breaking the C[sbnd]H methyl bond, but we found that this reaction is very unlikely. Reaction and activation energies for the second dehydrogenation – from methoxy to formaldehyde, are very similar for perfect (111) and stepped surfaces but these activation barriers are not negligible, almost ten times as many the first step barriers. Next, the formaldehyde decomposition to formyl and CO species on perfect CeO2(111) have an important energetic cost, therefore these reactions could occur only on stepped surfaces.Fil: Reimers, Walter Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Branda, Maria Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaElsevier Science2017-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/63312Reimers, Walter Guillermo; Branda, Maria Marta; Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U; Elsevier Science; Applied Surface Science; 394; 2-2017; 509-5180169-4332CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0169433216322784info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2016.10.154info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:07:57Zoai:ri.conicet.gov.ar:11336/63312instacron: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:34982025-09-03 10:07:57.417CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
title Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
spellingShingle Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
Reimers, Walter Guillermo
Catalysis
Dft
Methanol Decomposition
Oxide
title_short Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
title_full Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
title_fullStr Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
title_full_unstemmed Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
title_sort Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U
dc.creator.none.fl_str_mv Reimers, Walter Guillermo
Branda, Maria Marta
author Reimers, Walter Guillermo
author_facet Reimers, Walter Guillermo
Branda, Maria Marta
author_role author
author2 Branda, Maria Marta
author2_role author
dc.subject.none.fl_str_mv Catalysis
Dft
Methanol Decomposition
Oxide
topic Catalysis
Dft
Methanol Decomposition
Oxide
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv GGA + U calculations have been carried out to study the complete methanol decomposition on the more stable Ceria surfaces, i.e. (111), (221), (331) and (110). These results have shown that the methanol adsorption is exothermic on oxidized as well as on the partially reduced surfaces though the adsorption energy is greater for the latest. The first dehydrogenation step of methanol is highly probable for all the studied sites with activation barriers smaller than 0.2 eV. The first dehydrogenation reaction could also occur by breaking the C[sbnd]H methyl bond, but we found that this reaction is very unlikely. Reaction and activation energies for the second dehydrogenation – from methoxy to formaldehyde, are very similar for perfect (111) and stepped surfaces but these activation barriers are not negligible, almost ten times as many the first step barriers. Next, the formaldehyde decomposition to formyl and CO species on perfect CeO2(111) have an important energetic cost, therefore these reactions could occur only on stepped surfaces.
Fil: Reimers, Walter Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Branda, Maria Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
description GGA + U calculations have been carried out to study the complete methanol decomposition on the more stable Ceria surfaces, i.e. (111), (221), (331) and (110). These results have shown that the methanol adsorption is exothermic on oxidized as well as on the partially reduced surfaces though the adsorption energy is greater for the latest. The first dehydrogenation step of methanol is highly probable for all the studied sites with activation barriers smaller than 0.2 eV. The first dehydrogenation reaction could also occur by breaking the C[sbnd]H methyl bond, but we found that this reaction is very unlikely. Reaction and activation energies for the second dehydrogenation – from methoxy to formaldehyde, are very similar for perfect (111) and stepped surfaces but these activation barriers are not negligible, almost ten times as many the first step barriers. Next, the formaldehyde decomposition to formyl and CO species on perfect CeO2(111) have an important energetic cost, therefore these reactions could occur only on stepped surfaces.
publishDate 2017
dc.date.none.fl_str_mv 2017-02
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/11336/63312
Reimers, Walter Guillermo; Branda, Maria Marta; Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U; Elsevier Science; Applied Surface Science; 394; 2-2017; 509-518
0169-4332
CONICET Digital
CONICET
url http://hdl.handle.net/11336/63312
identifier_str_mv Reimers, Walter Guillermo; Branda, Maria Marta; Methanol decomposition on low index and stepped CeO2 surfaces from GGA+U; Elsevier Science; Applied Surface Science; 394; 2-2017; 509-518
0169-4332
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://www.sciencedirect.com/science/article/pii/S0169433216322784
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2016.10.154
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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 13.13397

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