Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity

The Lewis/Brønsted acidity and catalytic properties of UiO-66-type metal-organic frameworks are studied in the context of tunable acid catalysts based on the presence of linker defects that create coordinatively unsaturated Zr4+ centers. Fourier transform infrared spectroscopy of adsorbed CO and dir...

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Autores: Cirujano, F.G., Llabrés i Xamena, Francesc X.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/226568
Acceso en línea:http://hdl.handle.net/10261/226568
Access Level:acceso abierto
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spelling Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted AcidityCirujano, F.G.Llabrés i Xamena, Francesc X.The Lewis/Brønsted acidity and catalytic properties of UiO-66-type metal-organic frameworks are studied in the context of tunable acid catalysts based on the presence of linker defects that create coordinatively unsaturated Zr4+ centers. Fourier transform infrared spectroscopy of adsorbed CO and direct pH measurements are employed to characterize hydrated and dehydrated UiO-66 containing different number of Zr4+ sites associated with defects. These sites can strongly polarize coordinated water molecules, which induces Brønsted acidity in the hydrated material. Upon dehydration of the solid, the coordinated water molecules are removed, and the underlying coordinatively unsaturated Zr4+ cations become exposed and available as Lewis acid sites. Herein we show, for various acid-catalyzed reactions, how it is possible to shift from a Brønsted acid to a Lewis acid catalyst by simply controlling the hydration degree of the solid. This control adds a new dimension to the design and engineering of MOFs for catalytic applications.Financial support by the Spanish Government is acknowledged through projects MAT2017-82288-C2-1-P and the Severo Ochoa program (SEV-2016-0683).ACS PublicationsMinisterio de Economía, Industria y Competitividad (España)Ministerio de Educación, Cultura y Deporte (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2021202120202021info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_dcae04bcPostprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/226568reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/MAT2017-82288-C2-1-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683http://dx.doi.org/10.1021/acs.jpclett.0c00984Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2265682026-05-22T06:33:51Z
dc.title.none.fl_str_mv Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
title Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
spellingShingle Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
Cirujano, F.G.
title_short Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
title_full Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
title_fullStr Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
title_full_unstemmed Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
title_sort Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity
dc.creator.none.fl_str_mv Cirujano, F.G.
Llabrés i Xamena, Francesc X.
author Cirujano, F.G.
author_facet Cirujano, F.G.
Llabrés i Xamena, Francesc X.
author_role author
author2 Llabrés i Xamena, Francesc X.
author2_role author
dc.contributor.none.fl_str_mv Ministerio de Economía, Industria y Competitividad (España)
Ministerio de Educación, Cultura y Deporte (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The Lewis/Brønsted acidity and catalytic properties of UiO-66-type metal-organic frameworks are studied in the context of tunable acid catalysts based on the presence of linker defects that create coordinatively unsaturated Zr4+ centers. Fourier transform infrared spectroscopy of adsorbed CO and direct pH measurements are employed to characterize hydrated and dehydrated UiO-66 containing different number of Zr4+ sites associated with defects. These sites can strongly polarize coordinated water molecules, which induces Brønsted acidity in the hydrated material. Upon dehydration of the solid, the coordinated water molecules are removed, and the underlying coordinatively unsaturated Zr4+ cations become exposed and available as Lewis acid sites. Herein we show, for various acid-catalyzed reactions, how it is possible to shift from a Brønsted acid to a Lewis acid catalyst by simply controlling the hydration degree of the solid. This control adds a new dimension to the design and engineering of MOFs for catalytic applications.
publishDate 2020
dc.date.none.fl_str_mv 2020
2021
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_dcae04bc
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info:eu-repo/semantics/acceptedVersion
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status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/226568
url http://hdl.handle.net/10261/226568
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/MAT2017-82288-C2-1-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683
http://dx.doi.org/10.1021/acs.jpclett.0c00984
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
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