Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions
[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 analys...
| Autores: | , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:riunet.upv.es:10251/183195 |
| Acceso en línea: | https://riunet.upv.es/handle/10251/183195 |
| Access Level: | acceso abierto |
| Palabra clave: | Ce-MOF Subnanometric CeO2-x clusters Oxidase activity Ligand-to-metal charge transfer Oxidative halogenation QUIMICA ORGANICA |
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Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation ReactionsRojas-Buzo, SergioOlloqui-Sariego, José LuisConcepción Heydorn, Patricia|||0000-0003-2058-3103Moliner Marin, Manuel|||0000-0002-5440-716XCorma Canós, Avelino|||0000-0002-2232-3527Ce-MOFSubnanometric CeO2-x clustersOxidase activityLigand-to-metal charge transferOxidative halogenationQUIMICA ORGANICA[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.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.American Chemical SocietyInstituto Universitario Mixto de Tecnología QuímicaEuropean Regional Development FundMinisterio de Ciencia e InnovaciónMinisterio de Economía, Industria y CompetitividadRepositorio Institucional de la Universitat Politècnica de València Riunet20212021-07-07journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/183195reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 RTI2018-101033-B-I00 DISEÑO DE CATALIZADORES MULTIFUNCIONALES PARA LA CONVERSION EFICIENTE DE BIOGAS Y GAS NATURAL A HIDROCARBUROS DE INTERES INDUSTRIALMINISTERIO DE ECONOMÍA, INDUSTRIA Y COMPETITIVIDAD MINISTERIO DE ECONOMÍA, INDUSTRIA Y COMPETITIVIDAD SEV-2016-0683 Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelenciaopen accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento (by)http://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/1831952026-06-13T07:49:27Z |
| dc.title.none.fl_str_mv |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| title |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| spellingShingle |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions Rojas-Buzo, Sergio Ce-MOF Subnanometric CeO2-x clusters Oxidase activity Ligand-to-metal charge transfer Oxidative halogenation QUIMICA ORGANICA |
| title_short |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| title_full |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| title_fullStr |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| title_full_unstemmed |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| title_sort |
Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions |
| dc.creator.none.fl_str_mv |
Rojas-Buzo, Sergio Olloqui-Sariego, José Luis Concepción Heydorn, Patricia|||0000-0003-2058-3103 Moliner Marin, Manuel|||0000-0002-5440-716X Corma Canós, Avelino|||0000-0002-2232-3527 |
| author |
Rojas-Buzo, Sergio |
| author_facet |
Rojas-Buzo, Sergio Olloqui-Sariego, José Luis Concepción Heydorn, Patricia|||0000-0003-2058-3103 Moliner Marin, Manuel|||0000-0002-5440-716X Corma Canós, Avelino|||0000-0002-2232-3527 |
| author_role |
author |
| author2 |
Olloqui-Sariego, José Luis Concepción Heydorn, Patricia|||0000-0003-2058-3103 Moliner Marin, Manuel|||0000-0002-5440-716X Corma Canós, Avelino|||0000-0002-2232-3527 |
| author2_role |
author author author author |
| dc.contributor.none.fl_str_mv |
Instituto Universitario Mixto de Tecnología Química European Regional Development Fund Ministerio de Ciencia e Innovación Ministerio de Economía, Industria y Competitividad Repositorio Institucional de la Universitat Politècnica de València Riunet |
| dc.subject.none.fl_str_mv |
Ce-MOF Subnanometric CeO2-x clusters Oxidase activity Ligand-to-metal charge transfer Oxidative halogenation QUIMICA ORGANICA |
| topic |
Ce-MOF Subnanometric CeO2-x clusters Oxidase activity Ligand-to-metal charge transfer Oxidative halogenation QUIMICA ORGANICA |
| description |
[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. |
| publishDate |
2021 |
| dc.date.none.fl_str_mv |
2021 2021-07-07 |
| dc.type.none.fl_str_mv |
journal article http://purl.org/coar/resource_type/c_6501 VoR http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
https://riunet.upv.es/handle/10251/183195 |
| url |
https://riunet.upv.es/handle/10251/183195 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.relation.none.fl_str_mv |
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 RTI2018-101033-B-I00 DISEÑO DE CATALIZADORES MULTIFUNCIONALES PARA LA CONVERSION EFICIENTE DE BIOGAS Y GAS NATURAL A HIDROCARBUROS DE INTERES INDUSTRIAL MINISTERIO DE ECONOMÍA, INDUSTRIA Y COMPETITIVIDAD MINISTERIO DE ECONOMÍA, INDUSTRIA Y COMPETITIVIDAD SEV-2016-0683 Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelencia |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 Reconocimiento (by) http://creativecommons.org/licenses/by/4.0/ |
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info:eu-repo/semantics/openAccess |
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open access http://purl.org/coar/access_right/c_abf2 Reconocimiento (by) http://creativecommons.org/licenses/by/4.0/ |
| eu_rights_str_mv |
openAccess |
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application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| publisher.none.fl_str_mv |
American Chemical Society |
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reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia instname:Universitat Politècnica de València (UPV) |
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RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
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