Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41

Autores
Alegre, Clara Iris Aymará; Zalazar, Maria Fernanda; Bulhões Cazula, Bárbara; Alves, Helton José; Peruchena, Nelida Maria
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, a theoretical study in conjunction with a spectroscopic analysis by FTIR were carried out in order to obtain molecular insights on the role of (CTA+)(≡SiO−) ion pair into the catalytic activity of [CTA+]–Si–MCM-41, the non-calcined form of Si–MCM-41. The reaction of transesterification of ethyl acetate with methanol was used as a model of transesterification of vegetal oils using the mesoporous heterogeneous catalyst. The theoretical study was performed in the framework of density functional theory (DFT) in order to provide new insights that could be helpful in the understanding of these chemical reactions on solid surfaces. It is found that the most favorable reaction mechanism is the dual site mechanism and that the presence of the (CTA+)(≡SiO−) ionic pair is fundamental for the catalytic activity. The basic center of [CTA+]–Si–MCM-41 catalyst polarizes the adsorbed methanol and the acid center polarizes the carbonyl of adsorbed ethyl acetate. Thus, this bifunctional catalytic site makes possible the concerted adsorption of both reactants at the pore mouth and generates a concerted transition state that gives rise to the beginning of the transesterification reaction and the formation of the unstable tetrahedral intermediate which will give rise to the products.
Fil: Alegre, Clara Iris Aymará. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Zalazar, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina
Fil: Bulhões Cazula, Bárbara. Universidade Federal do Paraná; Brasil
Fil: Alves, Helton José. Universidade Federal do Paraná; Brasil
Fil: Peruchena, Nelida Maria. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Materia
BIFUNCTIONAL CATALYTIC SITE
CONCERTED ADSORPTION
DFT
HETEROGENEOUS BASIC CATALYSIS
TRANSESTERIFICATION REACTION
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:11336/130768
Acceder
id CONICETDig_522ecc6f0625a9fef964b46397f41bf5
oai_identifier_str oai:ri.conicet.gov.ar:11336/130768
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41Alegre, Clara Iris AymaráZalazar, Maria FernandaBulhões Cazula, BárbaraAlves, Helton JoséPeruchena, Nelida MariaBIFUNCTIONAL CATALYTIC SITECONCERTED ADSORPTIONDFTHETEROGENEOUS BASIC CATALYSISTRANSESTERIFICATION REACTIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this work, a theoretical study in conjunction with a spectroscopic analysis by FTIR were carried out in order to obtain molecular insights on the role of (CTA+)(≡SiO−) ion pair into the catalytic activity of [CTA+]–Si–MCM-41, the non-calcined form of Si–MCM-41. The reaction of transesterification of ethyl acetate with methanol was used as a model of transesterification of vegetal oils using the mesoporous heterogeneous catalyst. The theoretical study was performed in the framework of density functional theory (DFT) in order to provide new insights that could be helpful in the understanding of these chemical reactions on solid surfaces. It is found that the most favorable reaction mechanism is the dual site mechanism and that the presence of the (CTA+)(≡SiO−) ionic pair is fundamental for the catalytic activity. The basic center of [CTA+]–Si–MCM-41 catalyst polarizes the adsorbed methanol and the acid center polarizes the carbonyl of adsorbed ethyl acetate. Thus, this bifunctional catalytic site makes possible the concerted adsorption of both reactants at the pore mouth and generates a concerted transition state that gives rise to the beginning of the transesterification reaction and the formation of the unstable tetrahedral intermediate which will give rise to the products.Fil: Alegre, Clara Iris Aymará. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Zalazar, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; ArgentinaFil: Bulhões Cazula, Bárbara. Universidade Federal do Paraná; BrasilFil: Alves, Helton José. Universidade Federal do Paraná; BrasilFil: Peruchena, Nelida Maria. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaSpringer/Plenum Publishers2019-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/130768Alegre, Clara Iris Aymará; Zalazar, Maria Fernanda; Bulhões Cazula, Bárbara; Alves, Helton José; Peruchena, Nelida Maria; Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41; Springer/Plenum Publishers; Topics In Catalysis; 62; 12-16; 5-2019; 941-9551022-5528CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://link.springer.com/10.1007/s11244-019-01181-2info:eu-repo/semantics/altIdentifier/doi/10.1007/s11244-019-01181-2info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:51:11Zoai:ri.conicet.gov.ar:11336/130768instacron: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 09:51:12.025CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
title Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
spellingShingle Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
Alegre, Clara Iris Aymará
BIFUNCTIONAL CATALYTIC SITE
CONCERTED ADSORPTION
DFT
HETEROGENEOUS BASIC CATALYSIS
TRANSESTERIFICATION REACTION
title_short Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
title_full Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
title_fullStr Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
title_full_unstemmed Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
title_sort Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41
dc.creator.none.fl_str_mv Alegre, Clara Iris Aymará
Zalazar, Maria Fernanda
Bulhões Cazula, Bárbara
Alves, Helton José
Peruchena, Nelida Maria
author Alegre, Clara Iris Aymará
author_facet Alegre, Clara Iris Aymará
Zalazar, Maria Fernanda
Bulhões Cazula, Bárbara
Alves, Helton José
Peruchena, Nelida Maria
author_role author
author2 Zalazar, Maria Fernanda
Bulhões Cazula, Bárbara
Alves, Helton José
Peruchena, Nelida Maria
author2_role author
author
author
author
dc.subject.none.fl_str_mv BIFUNCTIONAL CATALYTIC SITE
CONCERTED ADSORPTION
DFT
HETEROGENEOUS BASIC CATALYSIS
TRANSESTERIFICATION REACTION
topic BIFUNCTIONAL CATALYTIC SITE
CONCERTED ADSORPTION
DFT
HETEROGENEOUS BASIC CATALYSIS
TRANSESTERIFICATION REACTION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work, a theoretical study in conjunction with a spectroscopic analysis by FTIR were carried out in order to obtain molecular insights on the role of (CTA+)(≡SiO−) ion pair into the catalytic activity of [CTA+]–Si–MCM-41, the non-calcined form of Si–MCM-41. The reaction of transesterification of ethyl acetate with methanol was used as a model of transesterification of vegetal oils using the mesoporous heterogeneous catalyst. The theoretical study was performed in the framework of density functional theory (DFT) in order to provide new insights that could be helpful in the understanding of these chemical reactions on solid surfaces. It is found that the most favorable reaction mechanism is the dual site mechanism and that the presence of the (CTA+)(≡SiO−) ionic pair is fundamental for the catalytic activity. The basic center of [CTA+]–Si–MCM-41 catalyst polarizes the adsorbed methanol and the acid center polarizes the carbonyl of adsorbed ethyl acetate. Thus, this bifunctional catalytic site makes possible the concerted adsorption of both reactants at the pore mouth and generates a concerted transition state that gives rise to the beginning of the transesterification reaction and the formation of the unstable tetrahedral intermediate which will give rise to the products.
Fil: Alegre, Clara Iris Aymará. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Zalazar, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina
Fil: Bulhões Cazula, Bárbara. Universidade Federal do Paraná; Brasil
Fil: Alves, Helton José. Universidade Federal do Paraná; Brasil
Fil: Peruchena, Nelida Maria. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
description In this work, a theoretical study in conjunction with a spectroscopic analysis by FTIR were carried out in order to obtain molecular insights on the role of (CTA+)(≡SiO−) ion pair into the catalytic activity of [CTA+]–Si–MCM-41, the non-calcined form of Si–MCM-41. The reaction of transesterification of ethyl acetate with methanol was used as a model of transesterification of vegetal oils using the mesoporous heterogeneous catalyst. The theoretical study was performed in the framework of density functional theory (DFT) in order to provide new insights that could be helpful in the understanding of these chemical reactions on solid surfaces. It is found that the most favorable reaction mechanism is the dual site mechanism and that the presence of the (CTA+)(≡SiO−) ionic pair is fundamental for the catalytic activity. The basic center of [CTA+]–Si–MCM-41 catalyst polarizes the adsorbed methanol and the acid center polarizes the carbonyl of adsorbed ethyl acetate. Thus, this bifunctional catalytic site makes possible the concerted adsorption of both reactants at the pore mouth and generates a concerted transition state that gives rise to the beginning of the transesterification reaction and the formation of the unstable tetrahedral intermediate which will give rise to the products.
publishDate 2019
dc.date.none.fl_str_mv 2019-05
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/11336/130768
Alegre, Clara Iris Aymará; Zalazar, Maria Fernanda; Bulhões Cazula, Bárbara; Alves, Helton José; Peruchena, Nelida Maria; Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41; Springer/Plenum Publishers; Topics In Catalysis; 62; 12-16; 5-2019; 941-955
1022-5528
CONICET Digital
CONICET
url http://hdl.handle.net/11336/130768
identifier_str_mv Alegre, Clara Iris Aymará; Zalazar, Maria Fernanda; Bulhões Cazula, Bárbara; Alves, Helton José; Peruchena, Nelida Maria; Molecular Insights on the Role of (CTA+)(SiO−) Ion Pair into the Catalytic Activity of [CTA+]–Si–MCM-41; Springer/Plenum Publishers; Topics In Catalysis; 62; 12-16; 5-2019; 941-955
1022-5528
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://link.springer.com/10.1007/s11244-019-01181-2
info:eu-repo/semantics/altIdentifier/doi/10.1007/s11244-019-01181-2
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
dc.publisher.none.fl_str_mv Springer/Plenum Publishers
publisher.none.fl_str_mv Springer/Plenum Publishers
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
_version_ 1844613575047380992
score 13.070432

Publicaciones similares