Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)

Meso-tetrakis(4-carboxyphenyl)porphyrin (HTCPP) has been loaded on a partially exchanged Zn poly(heptazine imide) (PHI), changing the light harvesting properties of the system, without altering the PHI structure. At the optimal loading (20 wt %), the photosensitized (Zn/K)-PHI is able to produce 1.0...

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Autores: Szalad, Horatiu, Uscategui, Andres, García-Muelas, Rodrigo, Galushchinskiy, Alexey, Savateev, Oleksandr, Antonietti, Markus, Albero, J., García Gómez, Hermenegildo
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2024
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/384912
Acceso en línea:http://hdl.handle.net/10261/384912
Access Level:acceso abierto
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spelling Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)Szalad, HoratiuUscategui, AndresGarcía-Muelas, RodrigoGalushchinskiy, AlexeySavateev, OleksandrAntonietti, MarkusAlbero, J.García Gómez, HermenegildoMeso-tetrakis(4-carboxyphenyl)porphyrin (HTCPP) has been loaded on a partially exchanged Zn poly(heptazine imide) (PHI), changing the light harvesting properties of the system, without altering the PHI structure. At the optimal loading (20 wt %), the photosensitized (Zn/K)-PHI is able to produce 1.06 mmol/g and 0.46 mmol/g after 12 h of reaction irradiation of Milli-Q water under visible light by a 100 mW/cm white LED. The apparent quantum yield for the overall water splitting reaction was 5.5% at 400 nm and 2% at 700 nm. Outdoor water splitting irradiation with natural sunlight shows the feasibility of the process. The photocatalytic performance of TCPP20%@(Zn/K)-PHI is considerably higher than that of analyzed reference samples such as graphitic carbon nitride, poly(triazine imide), and potassium PHI with HTCPP photosensitization. These relative photocatalytic activities point out the relevance of the PHI structure and the presence of Zn. It is proposed that Zn simultaneously binds PHI and HTCPP. Transient absorption spectroscopy supports the occurrence of photoinduced electron transfer in which electrons are located at the HTCPP and holes at the PHI moiety. Transient photocurrent measurements show a higher charge separation efficiency on TCPP20%@-(Zn/K)-PHI compared to (Zn/K)-PHI, and measurement of the frontier orbitals indicates an adequate energy alignment of the HOMO/LUMO levels of TCPP with respect to (Zn/K)-PHI. The results show the possibility of developing efficient noble metal-free photocatalytic systems based on PHI dye sensitization.Financial support by the Spanish Ministry of Science and Innovation (CEX-2021-001230-S and PDI2021-0126071-OB-CO21 funded by MCIN/AEI/10.13039/501100011033) and Generalitat Valenciana (Prometeo 2021/038 and Advanced Materials program Graphica MFA/2022/023 with funding from European Union NextGenerationEU PRTR-C17.I1) is acknowledged. J.A. thanks the Spanish Ministry of Science and Innovation for a Ramon y Cajal research associate contract (RYC2021-031006-I funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGenerationEU/PRTR) and for the financial support (PID2022-141099OA-I00 funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGenerationEU/PRTR). R.G.M. gratefully acknowledges the generous high-performance computing time provided by CETA-CIEMAT in their Turgalium cluster. H.S. thanks the European ITN Solar2Chem for a postgraduate fellowship. The authors gratefully acknowledge The Max Planck Society for financial support.Peer reviewedACS PublicationsMinisterio de Ciencia e Innovación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2025202520242025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/384912reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgraament/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021-001230-info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-126071OB-C21info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141099OA-I00http://dx.doi.org/10.1021/acsami.4c12548Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3849122026-05-22T06:33:51Z
dc.title.none.fl_str_mv Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
title Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
spellingShingle Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
Szalad, Horatiu
title_short Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
title_full Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
title_fullStr Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
title_full_unstemmed Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
title_sort Natural Sunlight-Driven Photocatalytic Overall Water Splitting with 5.5% Quantum Yield Promoted by Porphyrin-Sensitized Zn Poly(heptazine imide)
dc.creator.none.fl_str_mv Szalad, Horatiu
Uscategui, Andres
García-Muelas, Rodrigo
Galushchinskiy, Alexey
Savateev, Oleksandr
Antonietti, Markus
Albero, J.
García Gómez, Hermenegildo
author Szalad, Horatiu
author_facet Szalad, Horatiu
Uscategui, Andres
García-Muelas, Rodrigo
Galushchinskiy, Alexey
Savateev, Oleksandr
Antonietti, Markus
Albero, J.
García Gómez, Hermenegildo
author_role author
author2 Uscategui, Andres
García-Muelas, Rodrigo
Galushchinskiy, Alexey
Savateev, Oleksandr
Antonietti, Markus
Albero, J.
García Gómez, Hermenegildo
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Meso-tetrakis(4-carboxyphenyl)porphyrin (HTCPP) has been loaded on a partially exchanged Zn poly(heptazine imide) (PHI), changing the light harvesting properties of the system, without altering the PHI structure. At the optimal loading (20 wt %), the photosensitized (Zn/K)-PHI is able to produce 1.06 mmol/g and 0.46 mmol/g after 12 h of reaction irradiation of Milli-Q water under visible light by a 100 mW/cm white LED. The apparent quantum yield for the overall water splitting reaction was 5.5% at 400 nm and 2% at 700 nm. Outdoor water splitting irradiation with natural sunlight shows the feasibility of the process. The photocatalytic performance of TCPP20%@(Zn/K)-PHI is considerably higher than that of analyzed reference samples such as graphitic carbon nitride, poly(triazine imide), and potassium PHI with HTCPP photosensitization. These relative photocatalytic activities point out the relevance of the PHI structure and the presence of Zn. It is proposed that Zn simultaneously binds PHI and HTCPP. Transient absorption spectroscopy supports the occurrence of photoinduced electron transfer in which electrons are located at the HTCPP and holes at the PHI moiety. Transient photocurrent measurements show a higher charge separation efficiency on TCPP20%@-(Zn/K)-PHI compared to (Zn/K)-PHI, and measurement of the frontier orbitals indicates an adequate energy alignment of the HOMO/LUMO levels of TCPP with respect to (Zn/K)-PHI. The results show the possibility of developing efficient noble metal-free photocatalytic systems based on PHI dye sensitization.
publishDate 2024
dc.date.none.fl_str_mv 2024
2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/384912
url http://hdl.handle.net/10261/384912
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgraament/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021-001230-
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-126071OB-C21
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141099OA-I00
http://dx.doi.org/10.1021/acsami.4c12548
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
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)
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