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dc.contributor.author | Rojas-Buzo, Sergio | es_ES |
dc.contributor.author | Concepción Heydorn, Patricia | es_ES |
dc.contributor.author | Olloqui-Sariego, José Luis | es_ES |
dc.contributor.author | Moliner Marin, Manuel | es_ES |
dc.contributor.author | Corma Canós, Avelino | es_ES |
dc.date.accessioned | 2022-06-10T18:06:45Z | |
dc.date.available | 2022-06-10T18:06:45Z | |
dc.date.issued | 2021-07-07 | es_ES |
dc.identifier.issn | 1944-8244 | es_ES |
dc.identifier.uri | http://hdl.handle.net/10251/183195 | |
dc.description.abstract | [EN] The structure of UiO-66(Ce) is formed by CeO2-x defective nanoclusters connected by terephthalate ligands. The initial presence of accessible Ce3+ sites in the as-synthesized UiO-66(Ce) has been determined by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR)-CO analyses. Moreover, linear scan voltammetric measurements reveal a reversible Ce4+/Ce3+ interconversion within the UiO-66(Ce) material, while nanocrystalline ceria shows an irreversible voltammetric response. This suggests that terephthalic acid ligands facilitate charge transfer between subnanometric metallic nodes, explaining the higher oxidase-like activity of UiO-66(Ce) compared to nanoceria for the mild oxidation of organic dyes under aerobic conditions. Based on these results, we propose the use of Ce-based metal-organic frameworks (MOFs) as efficient catalysts for the halogenation of activated arenes, as 1,3,5-trimethoxybenzene (TMB), using oxygen as a green oxidant. Kinetic studies demonstrate that UiO-66(Ce) is at least three times more active than nanoceria under the same reaction conditions. In addition, the UiO-66(Ce) catalyst shows an excellent stability and can be reused after proper washing treatments. Finally, a general mechanism for the oxidative halogenation reaction is proposed when using Ce-MOF as a catalyst, which mimics the mechanistic pathway described for metalloenzymes. The superb control in the generation of subnanometric CeO2-x defective clusters connected by adequate organic ligands in MOFs offers exciting opportunities in the design of Ce-based redox catalysts. | es_ES |
dc.description.sponsorship | This work has been supported by the Spanish Government through the "Severo Ochoa" (SEV-2016-0683, MINECO) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE). J. M. Salas is acknowledged for his contribution to CO-IR experiments. The Electron Microscopy Service of the UPV is also acknowledged for their help in sample characterization. | es_ES |
dc.language | Inglés | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.relation.ispartof | ACS Applied Materials & Interfaces | es_ES |
dc.rights | Reconocimiento (by) | es_ES |
dc.subject | Ce-MOF | es_ES |
dc.subject | Subnanometric CeO2-x clusters | es_ES |
dc.subject | Oxidase activity | es_ES |
dc.subject | Ligand-to-metal charge transfer | es_ES |
dc.subject | Oxidative halogenation | es_ES |
dc.subject.classification | QUIMICA ORGANICA | es_ES |
dc.title | Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions | es_ES |
dc.type | Artículo | es_ES |
dc.identifier.doi | 10.1021/acsami.1c07496 | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-101033-B-I00/ES/DISEÑO DE CATALIZADORES MULTIFUNCIONALES PARA LA CONVERSION EFICIENTE DE BIOGAS Y GAS NATURAL A HIDROCARBUROS DE INTERES INDUSTRIAL/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MINISTERIO DE ECONOMÍA, INDUSTRIA Y COMPETITIVIDAD//SEV-2016-0683//Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelencia/ | es_ES |
dc.rights.accessRights | Abierto | 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 | Rojas-Buzo, S.; Concepción Heydorn, P.; Olloqui-Sariego, JL.; Moliner Marin, M.; Corma Canós, A. (2021). Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions. ACS Applied Materials & Interfaces. 13(26):31021-31030. https://doi.org/10.1021/acsami.1c07496 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | https://doi.org/10.1021/acsami.1c07496 | es_ES |
dc.description.upvformatpinicio | 31021 | es_ES |
dc.description.upvformatpfin | 31030 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 13 | es_ES |
dc.description.issue | 26 | es_ES |
dc.identifier.pmid | 34176269 | es_ES |
dc.identifier.pmcid | PMC9131423 | es_ES |
dc.relation.pasarela | S\446646 | es_ES |
dc.contributor.funder | European Regional Development Fund | es_ES |
dc.contributor.funder | Ministerio de Ciencia e Innovación | es_ES |
dc.contributor.funder | MINISTERIO DE ECONOMÍA, INDUSTRIA Y COMPETITIVIDAD | es_ES |