Defect-Promoted Catalytic Conversion of Carbon Monoxide to Methanol on ThO₂ Surfaces

The conversion of carbon monoxide (CO) to methanol (CH 3 OH) is an attractive process as it converts a toxic and environmentally harmful gas into a widely used industrial chemical via hydrogenation. Traditionally, this process is catalyzed by Cu-based multicomponent materials, which require high pressures and temperatures, making the process costly and environmentally unfriendly. In this article, we show that thorium dioxide (ThO 2 ) is an attractive alternative catalyst that is earth abundant and chemically and thermally stable. Using quantum chemistry calculations based on density functional theory (DFT), we investigated the feasibility and reaction mechanism of the CO-to-CH 3 OH conversion catalyzed by the ThO 2 (111) surface. Particular focus is given to the role of O vacancies. It is found that that the O vacancies act as catalytic centers, promoting the chemical activation of CO and H 2 simultaneously and facilitating the reaction steps to form CH 3 OH. Based on these observations, we propose a dual-site catalytic mechanism wherein oxygen vacancies activate CO and H 2 in parallel. This work demonstrates that the presence of O vacancies on the ThO 2 surface improves its catalytic performance, paving the way for broader application of ThO 2 catalysis to sustainable chemistry.