Optimized Active Structure Configuration of the MOF Derived Cu-based Catalysts via Different Atmospheres for Selective CO2 Hydrogenation

Significant progress has been evidenced in the development of the synergistic effect of the various active sites for selective catalyzing CO 2 hydrogenation toward the target product. Unveiling the roles of different active sites is conducive to understanding the structure–activity relationship in complex reactions. In this study, the pretreatment atmosphere plays a pivotal role in modulating active site properties. The optimized Ar-pretreated Cu-UiO-66-Ar catalyst shows a high methanol space–time yield of 733 μmol g cat. −1 h −1 at 200 °C, 3.0 MPa, which is 2.7 times than that of H 2 -pretreated Cu-UiO-66-H 2 catalyst (274 μmol g cat. −1 h −1 ). We revealed the interface (Cu–O–Zr sites) and Cu nanoparticles (Cu–Cu sites) co-play a pivotal role in promoting CO 2 conversion and H 2 dissociation via Cu–Cu sites feeds H* to Cu–O–Zr-anchored CO*/HCO* species. Rational contrast experiments of the in-situ DRIFTS highlight the accelerated elementary steps in the CO 2 conversion process contact with the enhanced catalytic activity. Thus, this work is helpful to advance the understanding of the potential mechanism in a composite cross-reaction network.