Structural and electronic modulation by Ce-doping in MOF-derived In2O3@CeO2-ZrO2 catalysts for CO2 hydrogenation

Indium oxide (In2O3) has emerged as a promising catalyst for CO2 hydrogenation to methanol due to its exceptional selectivity compared with conventional Cu-based systems, which typically yield undesired by-products despite higher conversion rates. However, the reduction of In2O3 under reaction condi...

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Detalles Bibliográficos
Autores: Bracciotti, Edoardo, Salusso, Davide, López-Luque, Iván, Bertinetti, Stefano, Luque-Álvarez, Ligia A., Bobadilla Baladrón, Luis Francisco, Prieto, Gonzalo, Moliner, Manuel, Bordiga, Silvia, Rojas-Buzo, Sergio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/183290
Acceso en línea:https://hdl.handle.net/11441/183290
https://doi.org/10.1016/j.cej.2025.171706
Access Level:acceso abierto
Palabra clave:MOF-derived
Ce-doping
CO2 hydrogenation
Formate pathway
Descripción
Sumario:Indium oxide (In2O3) has emerged as a promising catalyst for CO2 hydrogenation to methanol due to its exceptional selectivity compared with conventional Cu-based systems, which typically yield undesired by-products despite higher conversion rates. However, the reduction of In2O3 under reaction conditions limits its long-term stability, motivating the development of robust oxide supports. In this work, we present a systematic study on the influence of cerium concentration in CeO2–ZrO2 supports on the performance of In2O3-based catalysts. A series of In2O3@Ce(100−x)Zrx materials were synthesized via a scalable and reproducible MOF-templated approach using UiO-66(Ce/Zr) precursors and subsequent calcination. Comprehensive characterization by in situ PXRD, XAS and H2-TPR revealed that low cerium incorporation (≈5 %) promotes unique Ce-Zr-In interfacial interactions, enhancing indium oxide dispersion and suppressing its reduction to metallic indium. Catalytic tests under CO2 hydrogenation conditions (25 bar, 513–573 K) demonstrated unprecedented methanol selectivity and stability for the low-Ce composition. These findings highlight the critical role of controlled Ce doping in tuning the structural and electronic properties of CeO2–ZrO2 supports and demonstrate the scalability of MOF-derived synthesis routes for designing next-generation catalysts for sustainable methanol production