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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Detalles Bibliográficos
Autores: Fernández-Villanueva, Estefanía, Ramírez, Pedro J., Lustemberg, Pablo G., Pérez, Rubén, Ganduglia-Pirovano, Maria Veronica, Rodríguez, José A.
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución: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
Acceso en línea:https://riunet.upv.es/handle/10251/228466
Access Level:acceso abierto
Palabra clave:Alloy oxide interface
DFT calculations
Methane-to-methanol conversion
PdAu/CeO2 catalyst
XPS characterization
Descripción
Sumario:[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.