Oxygen vacancy‐induced dynamic evolution of Cu‐based active sites boosts CO 2 hydrogenation to methanol

Cu/ZrO 2 catalysts have attracted interest for thermal‐catalytic CO 2 hydrogenation to methanol. The oxygen vacancies (O v ) in the reducible ZrO 2 support have been widely recognized as essential sites for CO 2 adsorption and activation, but their roles in tailoring Cu site geometry/electronic properties and the structure–function relationship for methanol synthesis remain underexplored. Herein, we report a sequential carbonization‐oxidation strategy to synthesize an O v ‐rich ZrO 2 ‐supported Cu cluster catalyst (SCO‐Cu/ZrO 2 ). Multiple in‐situ characterization and theoretical simulations reveal that dynamic evolution of O v density during the reduction and reaction processes can optimize the valence state of Cu species, especially the Cu + /Cu 0 ratio, via a localized electron redistribution mechanism. Benefiting from this effect, SCO‐Cu/ZrO 2 achieves a methanol space–time yield of 384 g kg cat. −1 h −1 under mild reaction conditions (≤260°C and 3 MPa), ranking among the leading analogous catalysts. Our work offers new perspectives for the rational design of highly efficient methanol synthesis catalysts.