A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst

Autores
Gómez, Guillermina; Belelli, Patricia Gabriela; Cabeza, Gabriela Fernanda; Castellani, Norberto Jorge
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The production of cis-2-butene (cis-2B) on Pd/Ni(1 1 1) bimetallic model was evaluated considering two possible reactions: through the hydrogenation of 1,3-butadiene (13BD) adsorbed on a cis-geometry site and through the isomerization of trans-2-butene (trans-2B). For that purpose, density functional theory (DFT) calculations were performed following the corresponding Horiuti–Polanyi mechanisms. In the hydrogenation, two competitive pathways produce cis-2B and trans-2B from 13BD species adsorbed on di-π-cis and 1,2,3,4-tetra-σ sites, respectively. The cis-2B is obtained with smaller energy requirements than the trans-2B isomer in spite of the adsorption of 13BD on the di-π-cis site is 0.10 eV less stable than on the 1,2,3,4-tetra-σ site. On the other hand, the trans-2B previously formed could be isomerized to cis-2B, and vice versa, trough the 2-butyl intermediates, but the elevated energetic barriers to hydrogenate/dehydrogenate both 2B isomers would avoid these processes. In fact, the dehydrogenation reaction is the limiting step of the isomerization reaction. From these results, we infer that on the Pd/Ni(1 1 1) surface the cis-2B isomer is easier to be formed via the 13BD hydrogenation on the di-π-cis site than via the trans/cis isomerization of 2B
Fil: Gómez, Guillermina. 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: Belelli, Patricia Gabriela. 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: Cabeza, Gabriela Fernanda. 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: Castellani, Norberto Jorge. 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
1,3 Butadiene
Isomerization
Pd-Ni Surface
Periodic Dft
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:11336/47633
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/47633
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalystGómez, GuillerminaBelelli, Patricia GabrielaCabeza, Gabriela FernandaCastellani, Norberto Jorge1,3 ButadieneIsomerizationPd-Ni SurfacePeriodic Dfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The production of cis-2-butene (cis-2B) on Pd/Ni(1 1 1) bimetallic model was evaluated considering two possible reactions: through the hydrogenation of 1,3-butadiene (13BD) adsorbed on a cis-geometry site and through the isomerization of trans-2-butene (trans-2B). For that purpose, density functional theory (DFT) calculations were performed following the corresponding Horiuti–Polanyi mechanisms. In the hydrogenation, two competitive pathways produce cis-2B and trans-2B from 13BD species adsorbed on di-π-cis and 1,2,3,4-tetra-σ sites, respectively. The cis-2B is obtained with smaller energy requirements than the trans-2B isomer in spite of the adsorption of 13BD on the di-π-cis site is 0.10 eV less stable than on the 1,2,3,4-tetra-σ site. On the other hand, the trans-2B previously formed could be isomerized to cis-2B, and vice versa, trough the 2-butyl intermediates, but the elevated energetic barriers to hydrogenate/dehydrogenate both 2B isomers would avoid these processes. In fact, the dehydrogenation reaction is the limiting step of the isomerization reaction. From these results, we infer that on the Pd/Ni(1 1 1) surface the cis-2B isomer is easier to be formed via the 13BD hydrogenation on the di-π-cis site than via the trans/cis isomerization of 2BFil: Gómez, Guillermina. 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: Belelli, Patricia Gabriela. 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: Cabeza, Gabriela Fernanda. 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: Castellani, Norberto Jorge. 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 Science2015-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/47633Gómez, Guillermina; Belelli, Patricia Gabriela; Cabeza, Gabriela Fernanda; Castellani, Norberto Jorge; A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst; Elsevier Science; Applied Surface Science; 353; 10-2015; 820-8280169-4332CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.apsusc.2015.06.127info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0169433215014749info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:50:15Zoai:ri.conicet.gov.ar:11336/47633instacron: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:34982025-10-15 14:50:15.537CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
title A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
spellingShingle A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
Gómez, Guillermina
1,3 Butadiene
Isomerization
Pd-Ni Surface
Periodic Dft
title_short A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
title_full A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
title_fullStr A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
title_full_unstemmed A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
title_sort A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst
dc.creator.none.fl_str_mv Gómez, Guillermina
Belelli, Patricia Gabriela
Cabeza, Gabriela Fernanda
Castellani, Norberto Jorge
author Gómez, Guillermina
author_facet Gómez, Guillermina
Belelli, Patricia Gabriela
Cabeza, Gabriela Fernanda
Castellani, Norberto Jorge
author_role author
author2 Belelli, Patricia Gabriela
Cabeza, Gabriela Fernanda
Castellani, Norberto Jorge
author2_role author
author
author
dc.subject.none.fl_str_mv 1,3 Butadiene
Isomerization
Pd-Ni Surface
Periodic Dft
topic 1,3 Butadiene
Isomerization
Pd-Ni Surface
Periodic Dft
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 production of cis-2-butene (cis-2B) on Pd/Ni(1 1 1) bimetallic model was evaluated considering two possible reactions: through the hydrogenation of 1,3-butadiene (13BD) adsorbed on a cis-geometry site and through the isomerization of trans-2-butene (trans-2B). For that purpose, density functional theory (DFT) calculations were performed following the corresponding Horiuti–Polanyi mechanisms. In the hydrogenation, two competitive pathways produce cis-2B and trans-2B from 13BD species adsorbed on di-π-cis and 1,2,3,4-tetra-σ sites, respectively. The cis-2B is obtained with smaller energy requirements than the trans-2B isomer in spite of the adsorption of 13BD on the di-π-cis site is 0.10 eV less stable than on the 1,2,3,4-tetra-σ site. On the other hand, the trans-2B previously formed could be isomerized to cis-2B, and vice versa, trough the 2-butyl intermediates, but the elevated energetic barriers to hydrogenate/dehydrogenate both 2B isomers would avoid these processes. In fact, the dehydrogenation reaction is the limiting step of the isomerization reaction. From these results, we infer that on the Pd/Ni(1 1 1) surface the cis-2B isomer is easier to be formed via the 13BD hydrogenation on the di-π-cis site than via the trans/cis isomerization of 2B
Fil: Gómez, Guillermina. 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: Belelli, Patricia Gabriela. 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: Cabeza, Gabriela Fernanda. 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: Castellani, Norberto Jorge. 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 The production of cis-2-butene (cis-2B) on Pd/Ni(1 1 1) bimetallic model was evaluated considering two possible reactions: through the hydrogenation of 1,3-butadiene (13BD) adsorbed on a cis-geometry site and through the isomerization of trans-2-butene (trans-2B). For that purpose, density functional theory (DFT) calculations were performed following the corresponding Horiuti–Polanyi mechanisms. In the hydrogenation, two competitive pathways produce cis-2B and trans-2B from 13BD species adsorbed on di-π-cis and 1,2,3,4-tetra-σ sites, respectively. The cis-2B is obtained with smaller energy requirements than the trans-2B isomer in spite of the adsorption of 13BD on the di-π-cis site is 0.10 eV less stable than on the 1,2,3,4-tetra-σ site. On the other hand, the trans-2B previously formed could be isomerized to cis-2B, and vice versa, trough the 2-butyl intermediates, but the elevated energetic barriers to hydrogenate/dehydrogenate both 2B isomers would avoid these processes. In fact, the dehydrogenation reaction is the limiting step of the isomerization reaction. From these results, we infer that on the Pd/Ni(1 1 1) surface the cis-2B isomer is easier to be formed via the 13BD hydrogenation on the di-π-cis site than via the trans/cis isomerization of 2B
publishDate 2015
dc.date.none.fl_str_mv 2015-10
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/11336/47633
Gómez, Guillermina; Belelli, Patricia Gabriela; Cabeza, Gabriela Fernanda; Castellani, Norberto Jorge; A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst; Elsevier Science; Applied Surface Science; 353; 10-2015; 820-828
0169-4332
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47633
identifier_str_mv Gómez, Guillermina; Belelli, Patricia Gabriela; Cabeza, Gabriela Fernanda; Castellani, Norberto Jorge; A theoretical view of 1,3-butadiene selective hydrogenation toward cis-2-butene on PdNi layered catalyst; Elsevier Science; Applied Surface Science; 353; 10-2015; 820-828
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/doi/10.1016/j.apsusc.2015.06.127
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0169433215014749
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 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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