Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design

The RWGS reaction is gathering momentum as an effective route for CO2 valorisation and given its endothermic nature the challenge lies in the design of active low-temperature catalysts. Herein we have designed two catalysts based on subnanometric Pt clusters providing effective CO2 conversion and, m...

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Autores: Torres-Sempere, Guillermo, Blay-Roger, Rubén, Luque-Álvarez, Ligia A., Santos, José L., Bobadilla, Luis F., Pastor-Pérez, Laura, Centeno, Miguel Ángel, Hernández, Willinton Y., Yousef, Ibraheem, Odriozola, José Antonio, Ramírez-Reina, Tomás
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:10261/355356
Acceso en línea:http://hdl.handle.net/10261/355356
https://api.elsevier.com/content/abstract/scopus_id/85180579344
Access Level:acceso abierto
Palabra clave:http://vocabularies.unesco.org/thesaurus/concept640
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spelling Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst designTorres-Sempere, GuillermoBlay-Roger, RubénLuque-Álvarez, Ligia A.Santos, José L.Bobadilla, Luis F.Pastor-Pérez, LauraCenteno, Miguel ÁngelHernández, Willinton Y.Yousef, IbraheemOdriozola, José AntonioRamírez-Reina, Tomáshttp://vocabularies.unesco.org/thesaurus/concept640The RWGS reaction is gathering momentum as an effective route for CO2 valorisation and given its endothermic nature the challenge lies in the design of active low-temperature catalysts. Herein we have designed two catalysts based on subnanometric Pt clusters providing effective CO2 conversion and, more importantly, high CO selectivity in the low-temperature range. The impact of Cs as a dopant in the catalyst's formulation is crucial leading to full selectivity at 300 °C. The reaction mechanisms for the studied systems namely Pt/TiO2 and PtCs/TiO2 are significantly different due to the presence of the alkali promoter. The presence of Cs neutralises the hydroxide groups of the TiO2 surface, changing the reaction pathway. The Pt/TiO2 catalyst follows a redox mechanism where CO2 dissociates to CO in the oxygen vacancies, and then these vacancies are recovered by the migration of H2 by spill over phenomena. On the other hand, the Cs doped catalyst has two possible mechanism pathways: the (ii) formyl/acyl pathway, where -CHO species are formed and, depending on the reaction conditions, evolve to CO gas or oxygenated compounds, and (ii) frustrated Lewis pair (FLP) assisted CO2 reduction route, in which the FLP induces the heterolytic dissociation of H2 and the subsequent hydrogenation of CO2 to CO. The latter route enabled by Cs-doping combined with the subnanometric Pt domains seems to be responsible for the excellent catalytic behaviour leading to fully selective low-temperature RWGS systems and thus unlocking new possibilities for less energy demanding CO2 valorisation units based on RWGS.The team at the University of Seville acknowledges financial support from the Spanish Ministry of Science through the projects NICER-BIOFUELS (ref: PLEC2021-008086), sponsored by MCIN/AEI/10.13039/501100011033 Next Generation Europe and SMART-FTS (ref: PID2021-126876OB-I00). Authors also acknowledge access to ALBA's facilities and support provided by ALBA's staff.Peer reviewedRoyal Society of Chemistry (UK)Agencia Estatal de Investigación (España)European CommissionMinisterio de Ciencia e Innovación (España)Bobadilla, Luis F.[0000-0003-0085-9811]Pastor-Pérez, Laura[0000-0003-4943-0282]Centeno, Miguel Ángel[0000-0002-8349-3044]Odriozola, José Antonio[0000-0002-8283-0459]Ramírez-Reina, Tomás[0000-0001-9693-5107]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://hdl.handle.net/10261/355356https://api.elsevier.com/content/abstract/scopus_id/85180579344reponame: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/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PLEC2021-008086info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-126876OB-I00Info:eu-repo/grantAgreement/MCIN/AEI//10.13039/501100011033Journal of Materials Chemistry Ahttps://doi.org/10.1039/D3TA05482ASíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3553562026-05-22T06:33:51Z
dc.title.none.fl_str_mv Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
title Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
spellingShingle Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
Torres-Sempere, Guillermo
http://vocabularies.unesco.org/thesaurus/concept640
title_short Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
title_full Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
title_fullStr Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
title_full_unstemmed Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
title_sort Subnanometric Pt clusters dispersed over Cs-doped TiO2 for CO2 upgrading via low-temperature RWGS: operando mechanistic insights to guide an optimal catalyst design
dc.creator.none.fl_str_mv Torres-Sempere, Guillermo
Blay-Roger, Rubén
Luque-Álvarez, Ligia A.
Santos, José L.
Bobadilla, Luis F.
Pastor-Pérez, Laura
Centeno, Miguel Ángel
Hernández, Willinton Y.
Yousef, Ibraheem
Odriozola, José Antonio
Ramírez-Reina, Tomás
author Torres-Sempere, Guillermo
author_facet Torres-Sempere, Guillermo
Blay-Roger, Rubén
Luque-Álvarez, Ligia A.
Santos, José L.
Bobadilla, Luis F.
Pastor-Pérez, Laura
Centeno, Miguel Ángel
Hernández, Willinton Y.
Yousef, Ibraheem
Odriozola, José Antonio
Ramírez-Reina, Tomás
author_role author
author2 Blay-Roger, Rubén
Luque-Álvarez, Ligia A.
Santos, José L.
Bobadilla, Luis F.
Pastor-Pérez, Laura
Centeno, Miguel Ángel
Hernández, Willinton Y.
Yousef, Ibraheem
Odriozola, José Antonio
Ramírez-Reina, Tomás
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación (España)
European Commission
Ministerio de Ciencia e Innovación (España)
Bobadilla, Luis F.[0000-0003-0085-9811]
Pastor-Pérez, Laura[0000-0003-4943-0282]
Centeno, Miguel Ángel[0000-0002-8349-3044]
Odriozola, José Antonio[0000-0002-8283-0459]
Ramírez-Reina, Tomás[0000-0001-9693-5107]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv http://vocabularies.unesco.org/thesaurus/concept640
topic http://vocabularies.unesco.org/thesaurus/concept640
description The RWGS reaction is gathering momentum as an effective route for CO2 valorisation and given its endothermic nature the challenge lies in the design of active low-temperature catalysts. Herein we have designed two catalysts based on subnanometric Pt clusters providing effective CO2 conversion and, more importantly, high CO selectivity in the low-temperature range. The impact of Cs as a dopant in the catalyst's formulation is crucial leading to full selectivity at 300 °C. The reaction mechanisms for the studied systems namely Pt/TiO2 and PtCs/TiO2 are significantly different due to the presence of the alkali promoter. The presence of Cs neutralises the hydroxide groups of the TiO2 surface, changing the reaction pathway. The Pt/TiO2 catalyst follows a redox mechanism where CO2 dissociates to CO in the oxygen vacancies, and then these vacancies are recovered by the migration of H2 by spill over phenomena. On the other hand, the Cs doped catalyst has two possible mechanism pathways: the (ii) formyl/acyl pathway, where -CHO species are formed and, depending on the reaction conditions, evolve to CO gas or oxygenated compounds, and (ii) frustrated Lewis pair (FLP) assisted CO2 reduction route, in which the FLP induces the heterolytic dissociation of H2 and the subsequent hydrogenation of CO2 to CO. The latter route enabled by Cs-doping combined with the subnanometric Pt domains seems to be responsible for the excellent catalytic behaviour leading to fully selective low-temperature RWGS systems and thus unlocking new possibilities for less energy demanding CO2 valorisation units based on RWGS.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
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/10261/355356
https://api.elsevier.com/content/abstract/scopus_id/85180579344
url http://hdl.handle.net/10261/355356
https://api.elsevier.com/content/abstract/scopus_id/85180579344
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PLEC2021-008086
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-126876OB-I00
Info:eu-repo/grantAgreement/MCIN/AEI//10.13039/501100011033
Journal of Materials Chemistry A
https://doi.org/10.1039/D3TA05482A
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
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