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Nature of active sites on UiO-66 and beneficial influence of water in the catalysis of Fischer esterification

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Nature of active sites on UiO-66 and beneficial influence of water in the catalysis of Fischer esterification

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dc.contributor.author Caratelli, Chiara es_ES
dc.contributor.author Hajek, J. es_ES
dc.contributor.author García Cirujano, Francisco es_ES
dc.contributor.author Warroquier, M. es_ES
dc.contributor.author Llabrés i Xamena, Francesc Xavier es_ES
dc.contributor.author Van Speybroeck, Veronique es_ES
dc.date.accessioned 2018-10-01T04:29:28Z
dc.date.available 2018-10-01T04:29:28Z
dc.date.issued 2017 es_ES
dc.identifier.issn 0021-9517 es_ES
dc.identifier.uri http://hdl.handle.net/10251/108665
dc.description.abstract [EN] Zirconium terephthalate UiO-66 type metal organic frameworks (MOFs) are known to be highly active, stable and reusable catalysts for the esterification of carboxylic acids with alcohols. Moreover, when defects are present in the structure of these MOFs, coordinatively unsaturated Zr ions with Lewis acid properties are created, which increase the catalytic activity of the resulting defective solids. In the present work, molecular modeling techniques combined with new experimental data on various defective hydrated and dehydrated materials allow to unravel the nature and role of defective active sites in the Fischer esterification and the role of coordinated water molecules to provide additional Bronsted sites. Periodic models of UiO-66 and UiO-66-NH2 catalysts have been used to unravel the reaction mechanism on hydrated and dehydrated materials. Various adsorption modes of water and methanol are investigated. The proposed mechanisms are in line with experimental observations that amino groups yield a reduction in the reaction barriers, although they have a passive role in modulating the electronic structure of the material. Water has a beneficial role on the reaction cycle by providing extra Bronsted sites and by providing stabilization for various intermediates through hydrogen bonds. (C) 2017 The Authors. Published by Elsevier Inc. es_ES
dc.description.sponsorship This work is supported by the Fund for Scientific Research Flanders (FWO) (project number 3G048612), the Research Board of Ghent University (BOF) and BELSPO in the frame of IAP/7/05. This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET). Funding was also received from the European Union's Horizon 2020 research and innovation programme [consolidator ERC grant agreement no. 647755-DYNPOR (2015-2020)]. Computational resources (Stevin Supercomputer Infrastructure) and services were provided by Ghent University. Financial support from the Generalitat Valenciana (project AICO/2015/065), the Spanish Ministry of Economy and Competitiveness (program Severo Ochoa SEV20120267), and the Spanish Ministry of Science and Innovation (project MAT2014-52085-C2-1-P) is gratefully acknowledged. en_EN
dc.language Inglés es_ES
dc.publisher Elsevier es_ES
dc.relation.ispartof Journal of Catalysis es_ES
dc.rights Reconocimiento - No comercial - Sin obra derivada (by-nc-nd) es_ES
dc.subject UiO-66 es_ES
dc.subject UiO-66-NH2 es_ES
dc.subject Heterogeneous catalysis es_ES
dc.subject Fischer esterification es_ES
dc.subject First-principle kinetics es_ES
dc.subject DFT es_ES
dc.title Nature of active sites on UiO-66 and beneficial influence of water in the catalysis of Fischer esterification es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1016/j.jcat.2017.06.014 es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//MAT2014-52085-C2-1-P/ES/NUEVOS MATERIALES CON DIFERENTES CENTROS ACTIVOS INCORPORADOS EN POSICIONES ESPECIFICAS DE LA RED Y SU APLICACION PARA PROCESOS CATALITICOS MULTI-ETAPA Y NANOTECNOLOGICOS/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/EC/H2020/641887/EU/DEFect NETwork materials science and engineering/ es_ES
dc.rights.accessRights Abierto es_ES
dc.date.embargoEndDate 2019-08-01 es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Caratelli, C.; Hajek, J.; García Cirujano, F.; Warroquier, M.; Llabrés I Xamena, FX.; Van Speybroeck, V. (2017). Nature of active sites on UiO-66 and beneficial influence of water in the catalysis of Fischer esterification. Journal of Catalysis. 352:401-414. https://doi.org/10.1016/j.jcat.2017.06.014 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://doi.org/10.1016/j.jcat.2017.06.014 es_ES
dc.description.upvformatpinicio 401 es_ES
dc.description.upvformatpfin 414 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 352 es_ES
dc.relation.pasarela S\342175 es_ES
dc.contributor.funder Ministerio de Economía y Competitividad es_ES


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