Efficient Role of Nanosheet-Like Pr₂O₃ Induced Surface-Interface Synergistic Structures over Cu-Based Catalysts for...

In a complex heterogeneous metal-catalyzed reaction process, unique cooperative effects between metal sites and surface-interface active sites, as well as favorable synergy between surface-interface active sites, can play crucial roles in improving their catalytic performances. In this work, a ZnO-modified Cu-based catalyst over defect-rich Pr₂O₃ nanosheets for high-efficiency CO₂ hydrogenation to produce methanol was successfully constructed. It was demonstrated that an as-fabricated nanosheet-like Cu-based catalyst presented several structural advantages including the formation of highly dispersive Cu⁰ sites and the coexistence of abundant defective Pr³⁺-V_o-Pr³⁺ structures (V_o: oxygen vacancy) and interfacial Cu-O-Pr sites. Combining structural characterization and catalytic reaction results with density functional theory calculations, it was clearly unveiled that the synergy between surface defective structures and Cu-Pr₂O₃ interfaces over the catalyst remarkably promoted the adsorption of CO₂ and CO intermediate, thus boosting the CO₂ hydrogenation simultaneously via both the formate intermediate pathway and the intense reverse water-gas shift reaction-derived CO hydrogenation pathway, along with a high space-time yield of methanol of 0.395 g_MeOH·g_cat^-1·h^-1 under mild reaction conditions (260 °C and 3.0 MPa). The study provides a new strategy to construct high-performance Cu-based catalysts for high-efficiency CO₂ hydrogenation to produce methanol and a deep understanding of the promotional roles of synergy between surface-interface active sites in the CO₂ hydrogenation.