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

Abstract

Synergistic interactions between active sites have been widely explored to enhance the catalytic performance of hydrogenation of CO 2 to methanol, yet the fundamental mechanisms, especially at the atomic level, remain unclear. Herein, we demonstrate that atomically dispersed Ga species incorporated into the ZrO 2 lattice significantly enhanced the catalytic performance of Cu/ZrO 2 for CO 2 hydrogenation to methanol. The optimized Cu/3GaZrO x catalyst exhibited a high methanol selectivity of 87% with a CO 2 conversion of 7.6% and a methanol space-time yield of up to 424 mg g cat –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 H 2 dissociation, created additional CO 2 adsorption sites, and promoted the transformation of formate to methoxy species via the formate pathway over Cu/GaZrO x . This work provides a promising strategy for rationalizing an efficient catalyst for the hydrogenation of CO 2 to methanol.