Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF

Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under m...

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Autores: Martínez, Jordan, Mazarío, Jaime, Lopes, Christian W., Trasobares, Susana, Calvino Gamez, Jose Juan, Agostini, Giovanni, Oña-Burgos, Pascual
Tipo de recurso: artículo
Estado:Versión publicada
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:10261/389138
Acceso en línea:http://hdl.handle.net/10261/389138
Access Level:acceso abierto
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spelling Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOFMartínez, JordanMazarío, JaimeLopes, Christian W.Trasobares, SusanaCalvino Gamez, Jose JuanAgostini, GiovanniOña-Burgos, PascualRecently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under mild conditions before pyrolysis (resulting in PdIn-QT). The resulting material (PdIn-QT) underwent comprehensive characterization via state-of-the-art aberration-corrected electron microscopy, N physisorption, X-ray absorption spectroscopy, Raman, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses have proven the existence of PdIn bimetallic nanoparticles supported on N-doped carbon. In situ DRIFT spectroscopy reveals the advantageous role of indium (In) in regulating Pd activity in alkyne semihydrogenation. Notably, incorporating a soft nucleation step before pyrolysis enhances surface area, porosity, and nitrogen content compared to direct MOF pyrolysis. The optimized material exhibits outstanding catalytic performance with 96% phenylacetylene conversion and 96% selectivity to phenylethylene in the fifth cycle under mild conditions (5 mmol phenylacetylene, 7 mg cat, 5 mL EtOH, R.T., 1 H bar).The authors thank the financial support from the Spanish Government (RTI2018-096399-A-I00, PID2022-140111OB-I00, PID2020-113006-RB-I00, TED2021-130191B-C41, and TED2021-130191B-C44) funded by MCIN/AEI/10.13039/501100011033. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 101022507 and NextGenerationEU/PRTR). HR-STEM studies were performed at the DME-UCA node of the ELECMI Spanish Unique Infrastructure (ICTS) for Electron Microscopy of Materials. Some of these experiments were performed at CLAESS and NOTOS beamlines at ALBA Synchrotron with the collaboration of ALBA staff (Carlos Escudero, Carlo Marini). J.M. Salas is acknowledged for experimental contributions to FTIR measurements.ACS PublicationsMinisterio de Ciencia e Innovación (España)European CommissionConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2025202520242025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/389138reponame: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##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-096399-A-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-140111OB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113006RB-I00info:eu-repo/grantAgreement/EC/Horizon 2020. The Framework Programme for Research and Innovation (2014-2020)/101022507http://dx.doi.org/10.1021/acscatal.4c00310Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3891382026-05-22T06:33:51Z
dc.title.none.fl_str_mv Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
title Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
spellingShingle Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
Martínez, Jordan
title_short Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
title_full Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
title_fullStr Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
title_full_unstemmed Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
title_sort Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF
dc.creator.none.fl_str_mv Martínez, Jordan
Mazarío, Jaime
Lopes, Christian W.
Trasobares, Susana
Calvino Gamez, Jose Juan
Agostini, Giovanni
Oña-Burgos, Pascual
author Martínez, Jordan
author_facet Martínez, Jordan
Mazarío, Jaime
Lopes, Christian W.
Trasobares, Susana
Calvino Gamez, Jose Juan
Agostini, Giovanni
Oña-Burgos, Pascual
author_role author
author2 Mazarío, Jaime
Lopes, Christian W.
Trasobares, Susana
Calvino Gamez, Jose Juan
Agostini, Giovanni
Oña-Burgos, Pascual
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
European Commission
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under mild conditions before pyrolysis (resulting in PdIn-QT). The resulting material (PdIn-QT) underwent comprehensive characterization via state-of-the-art aberration-corrected electron microscopy, N physisorption, X-ray absorption spectroscopy, Raman, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses have proven the existence of PdIn bimetallic nanoparticles supported on N-doped carbon. In situ DRIFT spectroscopy reveals the advantageous role of indium (In) in regulating Pd activity in alkyne semihydrogenation. Notably, incorporating a soft nucleation step before pyrolysis enhances surface area, porosity, and nitrogen content compared to direct MOF pyrolysis. The optimized material exhibits outstanding catalytic performance with 96% phenylacetylene conversion and 96% selectivity to phenylethylene in the fifth cycle under mild conditions (5 mmol phenylacetylene, 7 mg cat, 5 mL EtOH, R.T., 1 H bar).
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
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/389138
url http://hdl.handle.net/10261/389138
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/RTI2018-096399-A-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-140111OB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113006RB-I00
info:eu-repo/grantAgreement/EC/Horizon 2020. The Framework Programme for Research and Innovation (2014-2020)/101022507
http://dx.doi.org/10.1021/acscatal.4c00310
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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