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

Indium oxide (In 2 O 3 ) has emerged as a promising catalyst for CO 2 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 In 2 O 3 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 CeO 2 –ZrO 2 supports on the performance of In 2 O 3 -based catalysts. A series of In 2 O 3 @Ce (100− x ) Zr x 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 H 2 -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 CO 2 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 CeO 2 –ZrO 2 supports and demonstrate the scalability of MOF-derived synthesis routes for designing next-generation catalysts for sustainable methanol production. • In 2 O 3 -based catalysts supported on CeZrO x were prepared via MOFs as sacrificial agents. • Optimal Ce content (~5 mol%) boosts methanol rate and selectivity. • In 2 O 3 @Ce 5 Zr 95 forms highly dispersed In 2 O 3 or InZrO x solid solutions. • In situ measurements confirm enhanced In incorporation into under-coordinated ZrO 2 .