Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions

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. M...

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Authors: Rojas Buzo, Sergio, Concepción, Patricia, Olloqui Sariego, José Luis, Moliner, Manuel, Corma, Avelino
Format: article
Status:Published version
Publication Date:2021
Country:España
Institution:Universidad de Sevilla (US)
Repository:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/134053
Online Access:https://hdl.handle.net/11441/134053
https://doi.org/10.1021/acsami.1c07496
Access Level:Open access
Keyword:Ce-MOF
subnanometric CeO2−x clusters
oxidase activity
ligand-to-metal charge transfer
oxidative halogenation
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spelling Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation ReactionsRojas Buzo, SergioConcepción, PatriciaOlloqui Sariego, José LuisMoliner, ManuelCorma, AvelinoCe-MOFsubnanometric CeO2−x clustersoxidase activityligand-to-metal charge transferoxidative halogenationThe 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.American Chemical SocietyQuímica Física2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/134053https://doi.org/10.1021/acsami.1c07496reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésACS Applied Materials & Interfaces, 13 (26), 31021-31030.https://dx.doi.org/10.1021/acsami.1c07496info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1340532026-06-17T12:51:07Z
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
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
Concepción, Patricia
Olloqui Sariego, José Luis
Moliner, Manuel
Corma, Avelino
author Rojas Buzo, Sergio
author_facet Rojas Buzo, Sergio
Concepción, Patricia
Olloqui Sariego, José Luis
Moliner, Manuel
Corma, Avelino
author_role author
author2 Concepción, Patricia
Olloqui Sariego, José Luis
Moliner, Manuel
Corma, Avelino
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Química Física
dc.subject.none.fl_str_mv Ce-MOF
subnanometric CeO2−x clusters
oxidase activity
ligand-to-metal charge transfer
oxidative halogenation
topic Ce-MOF
subnanometric CeO2−x clusters
oxidase activity
ligand-to-metal charge transfer
oxidative halogenation
description 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
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/134053
https://doi.org/10.1021/acsami.1c07496
url https://hdl.handle.net/11441/134053
https://doi.org/10.1021/acsami.1c07496
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv ACS Applied Materials & Interfaces, 13 (26), 31021-31030.
https://dx.doi.org/10.1021/acsami.1c07496
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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