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dc.creatorRojas Buzo, Sergioes
dc.creatorConcepción, Patriciaes
dc.creatorOlloqui Sariego, José Luises
dc.creatorMoliner, Manueles
dc.creatorCorma, Avelinoes
dc.date.accessioned2022-06-06T09:09:52Z
dc.date.available2022-06-06T09:09:52Z
dc.date.issued2021
dc.identifier.citationRojas Buzo, S., Concepción, P., Olloqui Sariego, J.L., Moliner, M. y Corma, A. (2021). Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions. ACS Applied Materials & Interfaces, 13 (26), 31021-31030.
dc.identifier.issn1944-8252es
dc.identifier.urihttps://hdl.handle.net/11441/134053
dc.description.abstractThe 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
dc.formatapplication/pdfes
dc.format.extent10 p.es
dc.language.isoenges
dc.publisherAmerican Chemical Societyes
dc.relation.ispartofACS Applied Materials & Interfaces, 13 (26), 31021-31030.
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectCe-MOFes
dc.subjectsubnanometric CeO2−x clusterses
dc.subjectoxidase activityes
dc.subjectligand-to-metal charge transferes
dc.subjectoxidative halogenationes
dc.titleMetalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactionses
dc.typeinfo:eu-repo/semantics/articlees
dcterms.identifierhttps://ror.org/03yxnpp24
dc.type.versioninfo:eu-repo/semantics/publishedVersiones
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.contributor.affiliationUniversidad de Sevilla. Departamento de Química Físicaes
dc.relation.publisherversionhttps://dx.doi.org/10.1021/acsami.1c07496es
dc.identifier.doi10.1021/acsami.1c07496es
dc.journaltitleACS Applied Materials & Interfaceses
dc.publication.volumen13es
dc.publication.issue26es
dc.publication.initialPage31021es
dc.publication.endPage31030es

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Except where otherwise noted, this item's license is described as: Attribution-NonCommercial-NoDerivatives 4.0 Internacional