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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/236273
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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 Técnicas2025-09-29T10:24:30Zoai: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:34982025-09-29 10:24:30.569CONICET 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 |
reponame_str |
CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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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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1844614241594638336 |
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13.070432 |