Unraveling the Role of Atomically Dispersed Ga Species in the Selective Hydrogenation of CO2 to Methanol over Cu/ZrO2

Synergistic interactions between active sites have been widely explored to enhance the catalytic performance of hydrogenation of CO2 to methanol, yet the fundamental mechanisms, especially at the atomic level, remain unclear. Herein, we demonstrate that atomically dispersed Ga species incorporated into the ZrO2 lattice significantly enhanced the catalytic performance of Cu/ZrO2 for CO2 hydrogenation to methanol. The optimized Cu/3GaZrOx catalyst exhibited a high methanol selectivity of 87% with a CO2 conversion of 7.6% and a methanol space-time yield of up to 424 mg gcat–1 h–1 at 300 °C. In situ experiments combined with computational analyses revealed that the synergistic interaction between atomic Ga species and Cu nanoparticles enhanced H2 dissociation, created additional CO2 adsorption sites, and promoted the transformation of formate to methoxy species via the formate pathway over Cu/GaZrOx. This work provides a promising strategy for rationalizing an efficient catalyst for the hydrogenation of CO2 to methanol.