The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF

The photocatalytic hydrogen evolution activity of a model 2D covalent organic framework (TpDTz) containing a thiazolo[5,4-d]thiazole (DTz) electron acceptor and triformylphloroglucinol (Tp) electron donor groups is enhanced by combining it with well-defined catalytic centers and suitable sacrificial...

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Autores: Reyes-Mesa, David, Sarró, Pau, Gusta, Muriel F., Jiménez-Solano, Alberto, Das, Saunak, Biswal, Bishnu P., Vignolo-González, Hugo A., Velasco-Garcia, Laura, Llobet, Antoni, Bastús, Neus G., Puntes, Víctor, Vallribera, Adelina, Pleixats, Roser, Granados, Albert, Lotsch, Bettina V., Gimbert-Suriñach, Carolina
Tipo de documento: artigo
Data de publicação:2025
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositório:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/489067
Acesso em linha:http://hdl.handle.net/2072/489067
https://doi.org/10.1021/jacs.5c17806
Access Level:Acceso aberto
Palavra-chave:Química
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spelling The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COFReyes-Mesa, DavidSarró, PauGusta, Muriel F.Jiménez-Solano, AlbertoDas, SaunakBiswal, Bishnu P.Vignolo-González, Hugo A.Velasco-Garcia, LauraLlobet, AntoniBastús, Neus G.Puntes, VíctorVallribera, AdelinaPleixats, RoserGranados, AlbertLotsch, Bettina V.Gimbert-Suriñach, CarolinaQuímica54The photocatalytic hydrogen evolution activity of a model 2D covalent organic framework (TpDTz) containing a thiazolo[5,4-d]thiazole (DTz) electron acceptor and triformylphloroglucinol (Tp) electron donor groups is enhanced by combining it with well-defined catalytic centers and suitable sacrificial electron donors. Platinum nanoparticles (PtNPs) with an average diameter of 2.7 ± 0.4 nm achieve rates up to 106 000 μmol H2 g–1 h–1 (5% Pt w/w). The best system requires the use of ascorbic acid/ascorbate buffer, which has been demonstrated to enhance the photoluminescence of TpDTz by forming aggregates while efficiently extracting charges from the excited TpDTz (TpDTz*). The productive charge extraction by the PtNPs from TpDTz* is also supported by steady state and time-resolved photoluminescence studies. All these factors combined with the high catalytic activity of PtNPs catalytic centers lead to the high performance of the overall system. In addition, a noble metal-free molecular catalyst based on a tetraazamacrocyclic cobalt complex has been identified as a good alternative catalyst candidate, efficiently quenching TpDTz photoluminescence. Under optimal conditions, the cobalt-based system achieves catalytic rates of 10 400 μmol H2 g–1 h–1 (1% Co w/w), which is only three times slower than the noble metal-based PtNPs system (1% Pt w/w, 28 300 μmol H2 g–1 h–1). By using controlled catalytic centers, it was possible to identify the factors limiting the hydrogen evolution photocatalytic activity of TpDTz allowing one to minimize undesired pathways and enhancing its performance by 2 orders of magnitude.info:eu-repo/semantics/publishedVersionACS Publications2025info:eu-repo/semantics/article13 p.application/pdfhttp://hdl.handle.net/2072/489067https://doi.org/10.1021/jacs.5c17806RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésPID2021-128496OB-I00, PID2021-124916NB-I00, PID2023-148967OB-C21 and RED2022-134287-T funded by MICIU/AEI/10.13039/501100011033AGAUR-Generalitat de Catalunya (2021SGR00064, 2021SGR-00878 and 2023CLIMA00036)DAAD (91713637)M.F.G. acknowledges funding from the SAPHNA project under Woman Talent Programme grant ICN2A. J.-S. gratefully acknowledges Spanish Ministry of Universities for funding through a Beatriz Galindo Fellowship (BG20/00015)Max Planck Society and the Cluster of Excellene e-conversion, funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy – EXC 2089/2 – 390776260CERCA Program/Generalitat de CatalunyaSevero Ochoa Excellence Accreditation CEX2024-001469-S funded by MICIU / AEI / 10.13039/501100011033, and MICINN for PID2022-140143OB-I00.Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2072/4890672026-05-29T05:05:01Z
dc.title.none.fl_str_mv The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
title The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
spellingShingle The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
Reyes-Mesa, David
Química
54
title_short The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
title_full The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
title_fullStr The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
title_full_unstemmed The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
title_sort The Power of Catalytic Centers and Ascorbate in Boosting the Photocatalytic Hydrogen Evolution Performance of TpDTz 2D-COF
dc.creator.none.fl_str_mv Reyes-Mesa, David
Sarró, Pau
Gusta, Muriel F.
Jiménez-Solano, Alberto
Das, Saunak
Biswal, Bishnu P.
Vignolo-González, Hugo A.
Velasco-Garcia, Laura
Llobet, Antoni
Bastús, Neus G.
Puntes, Víctor
Vallribera, Adelina
Pleixats, Roser
Granados, Albert
Lotsch, Bettina V.
Gimbert-Suriñach, Carolina
author Reyes-Mesa, David
author_facet Reyes-Mesa, David
Sarró, Pau
Gusta, Muriel F.
Jiménez-Solano, Alberto
Das, Saunak
Biswal, Bishnu P.
Vignolo-González, Hugo A.
Velasco-Garcia, Laura
Llobet, Antoni
Bastús, Neus G.
Puntes, Víctor
Vallribera, Adelina
Pleixats, Roser
Granados, Albert
Lotsch, Bettina V.
Gimbert-Suriñach, Carolina
author_role author
author2 Sarró, Pau
Gusta, Muriel F.
Jiménez-Solano, Alberto
Das, Saunak
Biswal, Bishnu P.
Vignolo-González, Hugo A.
Velasco-Garcia, Laura
Llobet, Antoni
Bastús, Neus G.
Puntes, Víctor
Vallribera, Adelina
Pleixats, Roser
Granados, Albert
Lotsch, Bettina V.
Gimbert-Suriñach, Carolina
author2_role author
author
author
author
author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Química
54
topic Química
54
description The photocatalytic hydrogen evolution activity of a model 2D covalent organic framework (TpDTz) containing a thiazolo[5,4-d]thiazole (DTz) electron acceptor and triformylphloroglucinol (Tp) electron donor groups is enhanced by combining it with well-defined catalytic centers and suitable sacrificial electron donors. Platinum nanoparticles (PtNPs) with an average diameter of 2.7 ± 0.4 nm achieve rates up to 106 000 μmol H2 g–1 h–1 (5% Pt w/w). The best system requires the use of ascorbic acid/ascorbate buffer, which has been demonstrated to enhance the photoluminescence of TpDTz by forming aggregates while efficiently extracting charges from the excited TpDTz (TpDTz*). The productive charge extraction by the PtNPs from TpDTz* is also supported by steady state and time-resolved photoluminescence studies. All these factors combined with the high catalytic activity of PtNPs catalytic centers lead to the high performance of the overall system. In addition, a noble metal-free molecular catalyst based on a tetraazamacrocyclic cobalt complex has been identified as a good alternative catalyst candidate, efficiently quenching TpDTz photoluminescence. Under optimal conditions, the cobalt-based system achieves catalytic rates of 10 400 μmol H2 g–1 h–1 (1% Co w/w), which is only three times slower than the noble metal-based PtNPs system (1% Pt w/w, 28 300 μmol H2 g–1 h–1). By using controlled catalytic centers, it was possible to identify the factors limiting the hydrogen evolution photocatalytic activity of TpDTz allowing one to minimize undesired pathways and enhancing its performance by 2 orders of magnitude.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/489067
https://doi.org/10.1021/jacs.5c17806
url http://hdl.handle.net/2072/489067
https://doi.org/10.1021/jacs.5c17806
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv PID2021-128496OB-I00, PID2021-124916NB-I00, PID2023-148967OB-C21 and RED2022-134287-T funded by MICIU/AEI/10.13039/501100011033
AGAUR-Generalitat de Catalunya (2021SGR00064, 2021SGR-00878 and 2023CLIMA00036)
DAAD (91713637)
M.F.G. acknowledges funding from the SAPHNA project under Woman Talent Programme grant ICN2
A. J.-S. gratefully acknowledges Spanish Ministry of Universities for funding through a Beatriz Galindo Fellowship (BG20/00015)
Max Planck Society and the Cluster of Excellene e-conversion, funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy – EXC 2089/2 – 390776260
CERCA Program/Generalitat de Catalunya
Severo Ochoa Excellence Accreditation CEX2024-001469-S funded by MICIU / AEI / 10.13039/501100011033, and MICINN for PID2022-140143OB-I00.
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 13 p.
application/pdf
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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