Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization

Autores
Vera, Carlos Roman; Pieck, Carlos Luis; Shimizu, Kiyoyuki; Parera, Jose
Año de publicación
2002
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Abstract An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO42−-ZrO2 with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO42−-ZrO2 catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H2 was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work. A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO42−-ZrO2 is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.
Fil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Pieck, Carlos Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Shimizu, Kiyoyuki. National Institute for Resources and Environment (NIRE) (AIST, MITI); Japón
Fil: Parera, Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Materia
Sulfate Zirconia
Crystalline Zirconia
N-Butane Isomerization
Tetragonal Structure
Oxygen Vacancy
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:11336/40208
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/40208
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerizationVera, Carlos RomanPieck, Carlos LuisShimizu, KiyoyukiParera, JoseSulfate ZirconiaCrystalline ZirconiaN-Butane IsomerizationTetragonal StructureOxygen Vacancyhttps://purl.org/becyt/ford/2.7https://purl.org/becyt/ford/2Abstract An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO42−-ZrO2 with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO42−-ZrO2 catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H2 was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work. A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO42−-ZrO2 is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.Fil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Pieck, Carlos Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Shimizu, Kiyoyuki. National Institute for Resources and Environment (NIRE) (AIST, MITI); JapónFil: Parera, Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaElsevier Science2002-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/40208Vera, Carlos Roman; Pieck, Carlos Luis; Shimizu, Kiyoyuki; Parera, Jose; Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization; Elsevier Science; Applied Catalysis A: General; 230; 1-2; 12-2002; 137-1510926-860XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/S0926-860X(01)01002-Xinfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0926860X0101002Xinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:10:50Zoai:ri.conicet.gov.ar:11336/40208instacron: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 10:10:50.296CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
title Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
spellingShingle Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
Vera, Carlos Roman
Sulfate Zirconia
Crystalline Zirconia
N-Butane Isomerization
Tetragonal Structure
Oxygen Vacancy
title_short Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
title_full Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
title_fullStr Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
title_full_unstemmed Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
title_sort Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization
dc.creator.none.fl_str_mv Vera, Carlos Roman
Pieck, Carlos Luis
Shimizu, Kiyoyuki
Parera, Jose
author Vera, Carlos Roman
author_facet Vera, Carlos Roman
Pieck, Carlos Luis
Shimizu, Kiyoyuki
Parera, Jose
author_role author
author2 Pieck, Carlos Luis
Shimizu, Kiyoyuki
Parera, Jose
author2_role author
author
author
dc.subject.none.fl_str_mv Sulfate Zirconia
Crystalline Zirconia
N-Butane Isomerization
Tetragonal Structure
Oxygen Vacancy
topic Sulfate Zirconia
Crystalline Zirconia
N-Butane Isomerization
Tetragonal Structure
Oxygen Vacancy
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.7
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Abstract An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO42−-ZrO2 with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO42−-ZrO2 catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H2 was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work. A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO42−-ZrO2 is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.
Fil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Pieck, Carlos Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
Fil: Shimizu, Kiyoyuki. National Institute for Resources and Environment (NIRE) (AIST, MITI); Japón
Fil: Parera, Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina
description Abstract An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO42−-ZrO2 with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO42−-ZrO2 catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H2 was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work. A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO42−-ZrO2 is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.
publishDate 2002
dc.date.none.fl_str_mv 2002-12
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/11336/40208
Vera, Carlos Roman; Pieck, Carlos Luis; Shimizu, Kiyoyuki; Parera, Jose; Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization; Elsevier Science; Applied Catalysis A: General; 230; 1-2; 12-2002; 137-151
0926-860X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/40208
identifier_str_mv Vera, Carlos Roman; Pieck, Carlos Luis; Shimizu, Kiyoyuki; Parera, Jose; Tetragonal structure, anionic vacancies and catalytic activity of SO42−-ZrO2 catalysts for n-butane isomerization; Elsevier Science; Applied Catalysis A: General; 230; 1-2; 12-2002; 137-151
0926-860X
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/S0926-860X(01)01002-X
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0926860X0101002X
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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score 13.13397

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