In₂O₃-ZrO₂ catalysts for CO₂ hydrogenation to methanol: from binary nanostructure and oxygen vacancies to ternary...

CO₂ hydrogenation to methanol (CHM) represents a promising route for carbon recycling and sustainable chemical production. Among the various catalyst systems investigated, In₂O₃-ZrO₂-based catalysts have emerged as one of the most effective platforms owing to their high methanol selectivity, excellent CO₂ activation, and tunable interfacial structures. This review summarizes recent advances in the development of In₂O₃-ZrO₂ catalysts for CHM, with particular emphasis on the structure-activity relationships governing catalytic performance. First, progress in binary In₂O₃-ZrO₂ catalysts is discussed, focusing on nanostructural engineering and O_v regulation strategies for enhancing CO₂ adsorption, activation and methanol selectivity. Subsequently, transition-metal modified In₂O₃-ZrO₂ systems are reviewed, highlighting how promoter metals regulate reactant activation, hydrogen spillover, electronic structure, crystal-phase synergy, and reaction-induced catalyst reconstruction. The dynamic evolution of catalyst structures under reaction conditions and its impact on catalytic performance are critically examined. Furthermore, recent mechanistic insights derived from in situ and/or operando characterization and theoretical calculations are summarized, leading to a unified understanding of the dynamic interfacial mechanism governing methanol synthesis over In₂O₃-ZrO₂ catalysts. Finally, the remaining challenges associated with catalyst stability, scalable synthesis and industrial implementation are discussed, together with future opportunities in atomic-scale interface engineering, multi-component catalyst design and in situ and/or operando-guided catalyst development.