Enhancing methanol selectivity of commercial Cu/ZnO/Al2O3 catalyst in CO2 hydrogenation by surface silylation

Suppressing reverse water-gas-shift (RWGS) reaction is high desirable but challenging and underdeveloped for Cu/ZnO catalysts, particularly for commercial Cu/ZnO/Al2O3 catalysts. Different from the current methodologies to reduce RWGS reaction, we report a simply surface silylation method for efficiently minimizing RWGS reaction over a commercial Cu/ZnO/Al2O3 catalyst. This method suppresses STYCO (Space-time yield) from 97.4 to 0.7 gCO·kgcat−1·h−1, improving STYMeOH from 20.2 to 39.9 gMeOH·kgcat−1·h−1 and methanol selectivity from 15.1 to 92.9 mol%. The combination of characterization methods and density functional theory calculations provide insight into the suppressing mechanism of surface silylation on catalyst. A hydroxyl (on ZnO)-promoted RWGS reaction cycle is discovered, which can be efficiently inhibited by the consuming of hydroxyls via surface silyation. Our results provide a way to regulate RWGS reaction on Cu/ZnO-based catalysts and are expected to the further use of silylation strategy to tune the interconversion of CO and CO2 via RWGS/WGS reaction on hydrogenation catalysts.