Theoretical investigation on the CO2 hydrogenation to methanol mechanism at electron-rich active interface over Cu/Ga-Ti-Al-O catalyst

Density functional theory investigations on CO2 hydrogenation to methanol mechanisms over Cu13 cluster loaded catalyst were performed. The results indicate that introducing TiO2 into Al2O3 promoted the residual electrons from Al2O3 surface directionally transmitted to the interface formed by the loaded Cu13 cluster and the support surface, thus created the electron-rich active interface. Incorporating single atom Ga promoter further gathered the residual electrons and stabilized the loaded Cu13 clusters. The electron-rich property of the active interface promoted the chemical adsorption and activation of both CO2 and the generated carbonyl species. Further favors the hydrogenating of carbonyl intermediates to methanol and effectively enhances the methanol selectivity. Moreover, CO2 priors to hydrogenated to methanol via reverse water gas shift pathway over Cu13/Ga-AT computational model with changed reaction rate controlling step with reduced activation energy. This work offers a simple approach for efficient copper-based methanol synthesis catalysts through control of interface electron structure.