Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66

23 pages, 12 figures

Detalhes bibliográficos
Autores: Kultaeva, Anastasiia, Biktagirov, Timur, Sperlich, Andreas, Dörflinger, Patrick, Calvo, Mauricio E., Otal, Eugenio, Dyakonov, Vladimir
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2025
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/386424
Acesso em linha:http://hdl.handle.net/10261/386424
http://arxiv.org/abs/2404.14911v2
Access Level:Acceso aberto
Palavra-chave:photocatalysis
DFT
EPR
Metal–Organic framework
MOF
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spelling Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66Kultaeva, AnastasiiaBiktagirov, TimurSperlich, AndreasDörflinger, PatrickCalvo, Mauricio E.Otal, EugenioDyakonov, VladimirphotocatalysisDFTEPRMetal–Organic frameworkMOF23 pages, 12 figuresMetal-Organic frameworks (MOFs) are promising candidates for advanced photocatalytically active materials. These porous crystalline compounds have large active surface areas and structural tunability and are thus highly competitive with oxides, the well-established material class for photocatalysis. However, due to their complex organic and coordination chemistry composition, photophysical mechanisms involved in the photocatalytic processes in MOFs are still not well understood. Employing electron paramagnetic resonance (EPR) spectroscopy and time-resolved photoluminescence spectroscopy (trPL), the fundamental processes of electron and hole generation are investigated, as well as capture events that lead to the formation of various radical species in UiO-66, an archetypical MOF photocatalyst. A manifold of photoinduced electron spin centers is detected, which is subsequently analyzed and identified with the help of density-functional theory (DFT) calculations. Under UV illumination, the symmetry, g-tensors and lifetimes of three distinct contributions are revealed: a surface O2-radical, a light-induced electron-hole pair, and a triplet exciton. Notably, the latter was found to emit (delayed) fluorescence. Our findings provide new insights into the photoinduced charge transfer processes, which are the basis of photocatalytic activity in UiO-66. This sets the stage for further studies on photogenerated spin centers in this and similar MOF materials.A.K. and V.D. acknowledge financial support from the Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter ct.qmat (EXC 2147, DFG project ID 390858490). P.D. acknowledges the German Research Foundation (DFG) program SPP2196 under DY18/14-2 (Project number 424101351). The authors thank Paul Konrad for participating in the LED set-up preparation and Philipp Rieder for assisting with the XRD measurements.Peer reviewedJohn Wiley & SonsGerman Research FoundationWürzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum MatterKultaeva, Anastasiia [0000-0003-2040-7193]Biktagirov, Timur [0000-0002-6819-7124]Sperlich, Andreas [0000-0002-0850-6757]Dörflinger, Patrick [0000-0003-0872-3513]Calvo, Mauricio E. [0000-0002-1721-7260]Otal, Eugenio [0000-0003-0801-854X]Dyakonov, Vladimir [0000-0001-8725-9573]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/386424http://arxiv.org/abs/2404.14911v2reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttps://doi.org/10.1002/adfm.202413297Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3864242026-05-22T06:33:51Z
dc.title.none.fl_str_mv Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
title Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
spellingShingle Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
Kultaeva, Anastasiia
photocatalysis
DFT
EPR
Metal–Organic framework
MOF
title_short Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
title_full Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
title_fullStr Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
title_full_unstemmed Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
title_sort Photoinduced Spin Centers in Photocatalytic Metal-Organic Framework UiO-66
dc.creator.none.fl_str_mv Kultaeva, Anastasiia
Biktagirov, Timur
Sperlich, Andreas
Dörflinger, Patrick
Calvo, Mauricio E.
Otal, Eugenio
Dyakonov, Vladimir
author Kultaeva, Anastasiia
author_facet Kultaeva, Anastasiia
Biktagirov, Timur
Sperlich, Andreas
Dörflinger, Patrick
Calvo, Mauricio E.
Otal, Eugenio
Dyakonov, Vladimir
author_role author
author2 Biktagirov, Timur
Sperlich, Andreas
Dörflinger, Patrick
Calvo, Mauricio E.
Otal, Eugenio
Dyakonov, Vladimir
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv German Research Foundation
Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter
Kultaeva, Anastasiia [0000-0003-2040-7193]
Biktagirov, Timur [0000-0002-6819-7124]
Sperlich, Andreas [0000-0002-0850-6757]
Dörflinger, Patrick [0000-0003-0872-3513]
Calvo, Mauricio E. [0000-0002-1721-7260]
Otal, Eugenio [0000-0003-0801-854X]
Dyakonov, Vladimir [0000-0001-8725-9573]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv photocatalysis
DFT
EPR
Metal–Organic framework
MOF
topic photocatalysis
DFT
EPR
Metal–Organic framework
MOF
description 23 pages, 12 figures
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/386424
http://arxiv.org/abs/2404.14911v2
url http://hdl.handle.net/10261/386424
http://arxiv.org/abs/2404.14911v2
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1002/adfm.202413297
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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