Recent Advances of Indium Oxide-Based Catalysts for CO₂ Hydrogenation to Methanol: Experimental and Theoretical

Methanol synthesis from the hydrogenation of carbon dioxide (CO₂) with green H₂ has been proven as a promising method for CO₂ utilization. Among the various catalysts, indium oxide (In₂O₃)-based catalysts received tremendous research interest due to the excellent methanol selectivity with appreciable CO₂ conversion. Herein, the recent experimental and theoretical studies on In₂O₃-based catalysts for thermochemical CO₂ hydrogenation to methanol were systematically reviewed. It can be found that a variety of steps, such as the synthesis method and pretreatment conditions, were taken to promote the formation of oxygen vacancies on the In₂O₃ surface, which can inhibit side reactions to ensure the highly selective conversion of CO₂ into methanol. The catalytic mechanism involving the formate pathway or carboxyl pathway over In₂O₃ was comprehensively explored by kinetic studies, in situ and ex situ characterizations, and density functional theory calculations, mostly demonstrating that the formate pathway was extremely significant for methanol production. Additionally, based on the cognition of the In₂O₃ active site and the reaction path of CO₂ hydrogenation over In₂O₃, strategies were adopted to improve the catalytic performance, including (i) metal doping to enhance the adsorption and dissociation of hydrogen, improve the ability of hydrogen spillover, and form a special metal-In₂O₃ interface, and (ii) hybrid with other metal oxides to improve the dispersion of In₂O₃, enhance CO₂ adsorption capacity, and stabilize the key intermediates. Lastly, some suggestions in future research were proposed to enhance the catalytic activity of In₂O₃-based catalysts for methanol production. The present review is helpful for researchers to have an explicit version of the research status of In₂O₃-based catalysts for CO₂ hydrogenation to methanol and the design direction of next-generation catalysts.