Constructing Abundant Cu–ZnO Interfaces via an MOF-on-MOF Precursor for Efficient CO2 Hydrogenation to Methanol

In this study, a series of CuaZnbOx catalysts with tunable Cu/Zn molar ratios were fabricated via a MOF-on-MOF precursor strategy for CO2 hydrogenation to methanol. The optimal catalyst, Cu6Zn4Ox, achieved a CO2 conversion of 14.4%, a methanol selectivity of 81.1%, and a space-time yield of 902.1 gMeOH·kgcat−1·h−1 at 280 °C and 3 MPa with a GHSV of 24,000 mL·gcat−1·h−1. Characterization results revealed that this strategy successfully constructed small-sized Cu and ZnO particles as well as abundant Cu–ZnO interfaces, reaching the optimal structural and compositional state when the Cu/Zn molar ratio is tuned to 6:4. The effective Cu–ZnO interface on Cu6Zn4Ox promotes the CO2 adsorption and H2 dissociation, triggering the formation of carbonate species and resulting in the generation of methanol via a carbonate–formate pathway. This work provides a new insight for the rational design of high-performance CO2 hydrogenation catalysts through precursor interface engineering.