Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited

Autores
Petelski, Andre Nicolai; Peruchena, Nelida Maria; Zalazar, Maria Fernanda
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Isomorphic substitution of zeolites with B, Al and Ga is a widely used approach in catalysis. The experimentally reported trend of their acidities decreases in the order: Al > Ga > B. However, a consistent explanation is still lacking in the literature. To bring more understanding of this trend, density functional theory computations were conducted on several model systems. First, the acidity of small clusters with two (2T) and five (5T) tetrahedral sites was analyzed. These systems were then projected onto three large void structures: H-[A]-BEA (52T), H-[A]-FAU (84T) and H-[A]-MOR (112T) with A = B, Al, Ga. Our electron density and Interacting Quantum Atom analyses show that the acidity of Al zeolites originates from the much stronger O–Al bond, which is dominated by the electrostatic attraction. The bridging hydroxyl therefore donates more charge density to the metal, the proton becomes more positive and consequently more acidic. Ga zeolites are more acidic than B zeolites due to the greater covalent nature on the O–Ga bond. The resulting acidity, as seen by ammonia, depends on both the acidic oxygen and the charge distribution of the surrounding oxygens exerted by the substituents.
Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Peruchena, Nelida Maria. 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
Materia
ZEOLITES
CHARGE DENSITY
ACIDITY
Nivel de accesibilidad
acceso embargado
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:11336/236273
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/236273
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Acidity of Isomorphic Substituted Zeolites with B, Al and Ga RevisitedPetelski, Andre NicolaiPeruchena, Nelida MariaZalazar, Maria FernandaZEOLITESCHARGE DENSITYACIDITYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Isomorphic substitution of zeolites with B, Al and Ga is a widely used approach in catalysis. The experimentally reported trend of their acidities decreases in the order: Al > Ga > B. However, a consistent explanation is still lacking in the literature. To bring more understanding of this trend, density functional theory computations were conducted on several model systems. First, the acidity of small clusters with two (2T) and five (5T) tetrahedral sites was analyzed. These systems were then projected onto three large void structures: H-[A]-BEA (52T), H-[A]-FAU (84T) and H-[A]-MOR (112T) with A = B, Al, Ga. Our electron density and Interacting Quantum Atom analyses show that the acidity of Al zeolites originates from the much stronger O–Al bond, which is dominated by the electrostatic attraction. The bridging hydroxyl therefore donates more charge density to the metal, the proton becomes more positive and consequently more acidic. Ga zeolites are more acidic than B zeolites due to the greater covalent nature on the O–Ga bond. The resulting acidity, as seen by ammonia, depends on both the acidic oxygen and the charge distribution of the surrounding oxygens exerted by the substituents.Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Peruchena, Nelida Maria. 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; ArgentinaWiley VCH Verlag2024-02info:eu-repo/date/embargoEnd/2024-08-28info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/236273Petelski, Andre Nicolai; Peruchena, Nelida Maria; Zalazar, Maria Fernanda; Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited; Wiley VCH Verlag; Chemphyschem; 25; 9; 2-2024; 1-101439-4235CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cphc.202400080info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.202400080info:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:57:15Zoai:ri.conicet.gov.ar:11336/236273instacron: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:34982025-10-22 11:57:15.965CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
title Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
spellingShingle Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
Petelski, Andre Nicolai
ZEOLITES
CHARGE DENSITY
ACIDITY
title_short Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
title_full Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
title_fullStr Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
title_full_unstemmed Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
title_sort Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited
dc.creator.none.fl_str_mv Petelski, Andre Nicolai
Peruchena, Nelida Maria
Zalazar, Maria Fernanda
author Petelski, Andre Nicolai
author_facet Petelski, Andre Nicolai
Peruchena, Nelida Maria
Zalazar, Maria Fernanda
author_role author
author2 Peruchena, Nelida Maria
Zalazar, Maria Fernanda
author2_role author
author
dc.subject.none.fl_str_mv ZEOLITES
CHARGE DENSITY
ACIDITY
topic ZEOLITES
CHARGE DENSITY
ACIDITY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Isomorphic substitution of zeolites with B, Al and Ga is a widely used approach in catalysis. The experimentally reported trend of their acidities decreases in the order: Al > Ga > B. However, a consistent explanation is still lacking in the literature. To bring more understanding of this trend, density functional theory computations were conducted on several model systems. First, the acidity of small clusters with two (2T) and five (5T) tetrahedral sites was analyzed. These systems were then projected onto three large void structures: H-[A]-BEA (52T), H-[A]-FAU (84T) and H-[A]-MOR (112T) with A = B, Al, Ga. Our electron density and Interacting Quantum Atom analyses show that the acidity of Al zeolites originates from the much stronger O–Al bond, which is dominated by the electrostatic attraction. The bridging hydroxyl therefore donates more charge density to the metal, the proton becomes more positive and consequently more acidic. Ga zeolites are more acidic than B zeolites due to the greater covalent nature on the O–Ga bond. The resulting acidity, as seen by ammonia, depends on both the acidic oxygen and the charge distribution of the surrounding oxygens exerted by the substituents.
Fil: Petelski, Andre Nicolai. Universidad Tecnológica Nacional. Facultad Regional Resistencia. Centro de Investigación en Química Orgánica Biológica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Peruchena, Nelida Maria. 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
description Isomorphic substitution of zeolites with B, Al and Ga is a widely used approach in catalysis. The experimentally reported trend of their acidities decreases in the order: Al > Ga > B. However, a consistent explanation is still lacking in the literature. To bring more understanding of this trend, density functional theory computations were conducted on several model systems. First, the acidity of small clusters with two (2T) and five (5T) tetrahedral sites was analyzed. These systems were then projected onto three large void structures: H-[A]-BEA (52T), H-[A]-FAU (84T) and H-[A]-MOR (112T) with A = B, Al, Ga. Our electron density and Interacting Quantum Atom analyses show that the acidity of Al zeolites originates from the much stronger O–Al bond, which is dominated by the electrostatic attraction. The bridging hydroxyl therefore donates more charge density to the metal, the proton becomes more positive and consequently more acidic. Ga zeolites are more acidic than B zeolites due to the greater covalent nature on the O–Ga bond. The resulting acidity, as seen by ammonia, depends on both the acidic oxygen and the charge distribution of the surrounding oxygens exerted by the substituents.
publishDate 2024
dc.date.none.fl_str_mv 2024-02
info:eu-repo/date/embargoEnd/2024-08-28
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/11336/236273
Petelski, Andre Nicolai; Peruchena, Nelida Maria; Zalazar, Maria Fernanda; Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited; Wiley VCH Verlag; Chemphyschem; 25; 9; 2-2024; 1-10
1439-4235
CONICET Digital
CONICET
url http://hdl.handle.net/11336/236273
identifier_str_mv Petelski, Andre Nicolai; Peruchena, Nelida Maria; Zalazar, Maria Fernanda; Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited; Wiley VCH Verlag; Chemphyschem; 25; 9; 2-2024; 1-10
1439-4235
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://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cphc.202400080
info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.202400080
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv embargoedAccess
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
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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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