Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways

By combining kinetics and theoretical calculations, we show here the benefits of going beyond the concept of static localized and defined active sites on solid catalysts, into a system that globally and dynamically considers the active site located in an environment that involves a scaffold structur...

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Autores: Li, Chengeng, Ferri, Pau, Paris Carrizo, Cecilia Gertrudis, Moliner Marín, Manuel, Boronat, Mercedes, Corma, Avelino
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/268300
Acceso en línea:http://hdl.handle.net/10261/268300
Access Level:acceso abierto
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spelling Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic PathwaysLi, ChengengFerri, PauParis Carrizo, Cecilia GertrudisMoliner Marín, ManuelBoronat, MercedesCorma, AvelinoBy combining kinetics and theoretical calculations, we show here the benefits of going beyond the concept of static localized and defined active sites on solid catalysts, into a system that globally and dynamically considers the active site located in an environment that involves a scaffold structure particularly suited for a target reaction. We demonstrate that such a system is able to direct the reaction through a preferred mechanism when two of them are competing. This is illustrated here for an industrially relevant reaction, the diethylbenzene-benzene transalkylation. The zeolite catalyst (ITQ-27) optimizes location, density, and environment of acid sites to drive the reaction through the preselected and preferred diaryl-mediated mechanism, instead of the alkyl transfer pathway. This is achieved by minimizing the activation energy of the selected pathway through weak interactions, much in the way that it occurs in enzymatic catalysts. We show that ITQ-27 outperforms previously reported zeolites for the DEB-Bz transalkylation and, more specifically, industrially relevant zeolites such as faujasite, beta, and mordenite.This work was supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch), Spanish Government through “Severo Ochoa” (SEV-2016-0683, MINECO), MAT2017-82288-C2-1-P (AEI/FEDER, UE) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE), and by Generalitat Valenciana through AICO/2019/060. TACS PublicationsEuropean CommissionMinisterio de Economía y Competitividad (España)Generalitat ValencianaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2022202220212022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/268300reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/EC/Horizon 2020/671093info:eu-repo/grantAgraament/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-82288-C2-1-Pinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-101033-B-I00http://dx.doi.org/10.1021/jacs.1c04818Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2683002026-05-22T06:33:51Z
dc.title.none.fl_str_mv Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
title Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
spellingShingle Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
Li, Chengeng
title_short Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
title_full Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
title_fullStr Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
title_full_unstemmed Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
title_sort Design and Synthesis of the Active Site Environment in Zeolite Catalysts for Selectively Manipulating Mechanistic Pathways
dc.creator.none.fl_str_mv Li, Chengeng
Ferri, Pau
Paris Carrizo, Cecilia Gertrudis
Moliner Marín, Manuel
Boronat, Mercedes
Corma, Avelino
author Li, Chengeng
author_facet Li, Chengeng
Ferri, Pau
Paris Carrizo, Cecilia Gertrudis
Moliner Marín, Manuel
Boronat, Mercedes
Corma, Avelino
author_role author
author2 Ferri, Pau
Paris Carrizo, Cecilia Gertrudis
Moliner Marín, Manuel
Boronat, Mercedes
Corma, Avelino
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
Ministerio de Economía y Competitividad (España)
Generalitat Valenciana
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description By combining kinetics and theoretical calculations, we show here the benefits of going beyond the concept of static localized and defined active sites on solid catalysts, into a system that globally and dynamically considers the active site located in an environment that involves a scaffold structure particularly suited for a target reaction. We demonstrate that such a system is able to direct the reaction through a preferred mechanism when two of them are competing. This is illustrated here for an industrially relevant reaction, the diethylbenzene-benzene transalkylation. The zeolite catalyst (ITQ-27) optimizes location, density, and environment of acid sites to drive the reaction through the preselected and preferred diaryl-mediated mechanism, instead of the alkyl transfer pathway. This is achieved by minimizing the activation energy of the selected pathway through weak interactions, much in the way that it occurs in enzymatic catalysts. We show that ITQ-27 outperforms previously reported zeolites for the DEB-Bz transalkylation and, more specifically, industrially relevant zeolites such as faujasite, beta, and mordenite.
publishDate 2021
dc.date.none.fl_str_mv 2021
2022
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/268300
url http://hdl.handle.net/10261/268300
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/EC/Horizon 2020/671093
info:eu-repo/grantAgraament/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2016-0683
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-82288-C2-1-P
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-101033-B-I00
http://dx.doi.org/10.1021/jacs.1c04818
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
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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