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

[EN] 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 byproducts 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 (approximate to 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.