Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water

[EN] The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of...

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Autores: Fernández-Villanueva, Estefanía, Ramírez, Pedro J., Lustemberg, Pablo G., Pérez, Rubén, Ganduglia-Pirovano, Maria Veronica, Rodríguez, José A.
Formato: artículo
Fecha de publicación:2025
País:España
Recursos:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/228466
Acesso em linha:https://riunet.upv.es/handle/10251/228466
Access Level:acceso abierto
Palavra-chave:Alloy oxide interface
DFT calculations
Methane-to-methanol conversion
PdAu/CeO2 catalyst
XPS characterization
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dc.title.none.fl_str_mv Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
title Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
spellingShingle Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
Fernández-Villanueva, Estefanía
Alloy oxide interface
DFT calculations
Methane-to-methanol conversion
PdAu/CeO2 catalyst
XPS characterization
title_short Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
title_full Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
title_fullStr Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
title_full_unstemmed Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
title_sort Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with Water
dc.creator.none.fl_str_mv Fernández-Villanueva, Estefanía
Ramírez, Pedro J.
Lustemberg, Pablo G.
Pérez, Rubén
Ganduglia-Pirovano, Maria Veronica
Rodríguez, José A.
author Fernández-Villanueva, Estefanía
author_facet Fernández-Villanueva, Estefanía
Ramírez, Pedro J.
Lustemberg, Pablo G.
Pérez, Rubén
Ganduglia-Pirovano, Maria Veronica
Rodríguez, José A.
author_role author
author2 Ramírez, Pedro J.
Lustemberg, Pablo G.
Pérez, Rubén
Ganduglia-Pirovano, Maria Veronica
Rodríguez, José A.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Xunta de Galicia
European Commission
U.S. Department of Energy
Universidad Autónoma de Madrid
Agencia Estatal de Investigación
European Regional Development Fund
Red Española de Supercomputación
Ministerio de Ciencia e Innovación
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Alloy oxide interface
DFT calculations
Methane-to-methanol conversion
PdAu/CeO2 catalyst
XPS characterization
topic Alloy oxide interface
DFT calculations
Methane-to-methanol conversion
PdAu/CeO2 catalyst
XPS characterization
description [EN] The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of experimental techniques, including XPS and catalytic testing, alongside density functional theory (DFT) calculations, we demonstrate that a Pd0.3Au0.7/CeO2 catalyst, which predominantly exposes isolated Pd atoms, achieves remarkable methanol selectivity (similar to 80%) at 500 K with a 1:1 methane-to-water ratio. While Pd/CeO2 efficiently activates methane, its tendency for overreaction leads to complete methanol decomposition, thereby limiting selectivity. Alloying Pd with Au on ceria mitigates this over-reactivity, preventing methanol degradation while maintaining sufficient catalytic activity. The PdAu/CeO2 composite exhibits a synergistic effect: Pd in contact with the ceria support facilitates methane activation and water dissociation, while Au fine-tunes reactivity to promote methanol formation. DFT calculations confirm that isolated Pd sites at the PdAu/CeO2 interface play a key role in balancing activity and selectivity. This work underscores the importance of alloy/oxide interfaces in controlling selective methane conversion with water and offers valuable insights for designing highly efficient catalysts for methanol synthesis.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-07-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/228466
url https://riunet.upv.es/handle/10251/228466
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2021-128915NB-I00 CATALIZADORES NANOESTRUCTURADOS BASADOS EN OXIDO DE CERIO PARA VALORIZACION DE GASES DE EFECTO INVERNADERO
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2023-149150OB-I00 HERRAMIENTAS DE SIMULACION Y APRENDIZAJE AUTOMATICO PARA LA CARACTERIZACION DE LA ESTRUCTURA Y LA RESPUESTA MECANICA DE MATERIALES AVANZADOS Y BIOMOLECULAS
U.S. Department of Energy https://doi.org/10.13039/100000015 DE-SC0012704
Ministerio de Ciencia e Innovación http://dx.doi.org/10.13039/501100004837 CEX2023-001316-M
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Engineering PdAu/CeO2 Alloy/Oxide Interfaces for Selective Methane-to-Methanol Conversion with WaterFernández-Villanueva, EstefaníaRamírez, Pedro J.Lustemberg, Pablo G.Pérez, RubénGanduglia-Pirovano, Maria VeronicaRodríguez, José A.Alloy oxide interfaceDFT calculationsMethane-to-methanol conversionPdAu/CeO2 catalystXPS characterization[EN] The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of experimental techniques, including XPS and catalytic testing, alongside density functional theory (DFT) calculations, we demonstrate that a Pd0.3Au0.7/CeO2 catalyst, which predominantly exposes isolated Pd atoms, achieves remarkable methanol selectivity (similar to 80%) at 500 K with a 1:1 methane-to-water ratio. While Pd/CeO2 efficiently activates methane, its tendency for overreaction leads to complete methanol decomposition, thereby limiting selectivity. Alloying Pd with Au on ceria mitigates this over-reactivity, preventing methanol degradation while maintaining sufficient catalytic activity. The PdAu/CeO2 composite exhibits a synergistic effect: Pd in contact with the ceria support facilitates methane activation and water dissociation, while Au fine-tunes reactivity to promote methanol formation. DFT calculations confirm that isolated Pd sites at the PdAu/CeO2 interface play a key role in balancing activity and selectivity. This work underscores the importance of alloy/oxide interfaces in controlling selective methane conversion with water and offers valuable insights for designing highly efficient catalysts for methanol synthesis.The authors thank J.M. Chavez and R.A. Soler for their help during the initial characterization of the PdAu alloys and PdAu/CeO2 composites, and B. Hammer, M.-P. V. Christiansen, and A. Bruix for their guidance in applying the GOFEE methodology. The research conducted at the Chemistry Division of Brookhaven National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program (Grant No. DE-SC0012704). P.J.R. is grateful to Zoneca-CENEX for an internal grant that facilitated part of this research. E.F.V. thanks UPV for her Margarita Salas postdoctoral fellowship (Spanish MIU and European Union-Next Generation EU) and the MOMENTUM Program (MMT-24-ICP-01, Plan de Recuperacion, Transformacion y Resiliencia - European Union - NextGenerationEU). M.V.G.P. and P.G.L. thank the Grant PID2021-128915NB-I00 funded by MCIN/AEI/10.13039/501100011033 and by ERDF, UE. R.P. acknowledges support from the Spanish Ministry of Science and Innovation, through project PID2023-149150OB-I00, and the "Maria de Maeztu" Programme for Units of Excellence in R&D (CEX2023-001316-M). The authors also acknowledge computational resources provided by the Red Espanola de Supercomputacion (RES) at MareNostrum 4 and 5 (BSC, Barcelona) node and the Centro de Computacion Cientifica-Universidad Autonoma de Madrid (CCC-UAM). Additionally, this research was supported by access to the Galician Supercomputing Center (CESGA) infrastructure, including its FinisTerrae III supercomputer and its permanent data storage system, funded by the Spanish Ministry of Science and Innovation, the Galician Government, and the ERDF.WileyXunta de GaliciaEuropean CommissionU.S. Department of EnergyUniversidad Autónoma de MadridAgencia Estatal de InvestigaciónEuropean Regional Development FundRed Española de SupercomputaciónMinisterio de Ciencia e InnovaciónRepositorio Institucional de la Universitat Politècnica de València Riunet20252025-07-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/228466reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2021-128915NB-I00 CATALIZADORES NANOESTRUCTURADOS BASADOS EN OXIDO DE CERIO PARA VALORIZACION DE GASES DE EFECTO INVERNADEROAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2023-149150OB-I00 HERRAMIENTAS DE SIMULACION Y APRENDIZAJE AUTOMATICO PARA LA CARACTERIZACION DE LA ESTRUCTURA Y LA RESPUESTA MECANICA DE MATERIALES AVANZADOS Y BIOMOLECULASU.S. Department of Energy https://doi.org/10.13039/100000015 DE-SC0012704Ministerio de Ciencia e Innovación http://dx.doi.org/10.13039/501100004837 CEX2023-001316-Mopen accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento (by)http://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/2284662026-06-13T07:49:27Z
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