Efficient methanol synthesis is considered a promising approach for carbon resource recycling. Hydrogenation of carbon dioxide (CO₂) to methanol is thermodynamically favored at low temperatures, but the sluggish activation kinetics of CO₂ under such conditions lead to low catalytic activity.

Higher temperatures can enhance reaction rates but also promote the reverse water-gas shift side reaction, which reduces methanol selectivity. This "seesaw" effect between activity and selectivity has limited the increasing of methanol yield.

In a study published in Chem on March 13, a team led by Prof. SUN Jian and Prof. YU Jiafeng from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences proposed a novel design strategy that spatially decouples active sites through a strong metal-support interaction (SMSI)-driven overlayer structure, enabling efficient methanol synthesis from CO₂.

By reconstructing the structure of catalyst surface and modifying the adsorption and dissociation modes of reactants as well as the reaction pathway, researchers achieved a space-time yield of 1.2 g·gcat^-1·h^-1 under reaction conditions of 300 ℃ and 3 MPa, which was about three times higher than that of commercial Cu/Zn/Al catalysts.

Researchers found that this strategy could direct CO₂ to preferentially adsorb and activate on zirconia (ZrO₂), guiding the reaction toward methanol synthesis via the formate pathway. Unlike the conventional activation mode on Cu sites involving breaking the C=O bond before hydrogenation, this strategy allowed hydrogenation to occur first on ZrO₂ sites, followed by C=O bond cleavage, which effectively suppressed the formation of CO by-product while retaining the high efficiency of Cu sites for H₂ dissociation.

"Our study provides a new way to address the long-standing trade-off between activity and selectivity in methanol synthesis from CO₂," said Prof. SUN, one of the corresponding authors of this study.