Oxygen vacancy‐induced dynamic evolution of Cu‐based active sites boosts
CO
2
hydrogenation to methanol
Kaixuan Huo, Lei Jiang, Qi Li, Yang Wang, Fanyi Meng, Jiwang Chen, Xiaojie Liu, Xinze Bi, Chao Wang, Jiancai Sui, Qiang Liu, Noritatsu Tsubaki, Mingbo Wu Abstract
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.