Enhancement of Methanol Yield in CO ₂ Hydrogenation by Promoting CO ₂ Activation and Unlocking the RWGS + CO-Hydrogenation Pathway over Cu–La/ZrO _<i>X</i> Catalysts

Cu-based catalysts have been widely recognized as the most representative systems for the hydrogenation of CO2 to methanol, and they also serve as the primary catalysts for the reverse water–gas shift (RWGS) reaction. However, effectively tuning the active sites and reaction pathways of Cu-based catalysts through promoters to overcome the trade-off between CO2 conversion and methanol selectivity remains a significant challenge. In this work, a RWGS + CO-hydrogenation pathway was established on Cu–La/ZrOX (CLZ-X) catalysts by selectively enhancing the interaction between La2O3 and Cu. In situ X-ray absorption spectroscopy (XAS) demonstrated that the coordination environment of Cu was altered upon La2O3 addition, rendering it highly sensitive to the reaction atmosphere and the reaction conditions. Meanwhile, La2O3 enhanced CO2 adsorption and activation on the catalyst surface and optimized its distribution, leading to a 1.5- to 2.4-fold increase in CO2 conversion, accompanied by a simultaneous enhancement in methanol selectivity, with the CLZ-3 catalyst achieving the highest value of methanol selectivity (76.33%). In situ DRIFTS and DFT calculation results indicated that the hydrogenation of CO2 to methanol was more favorable on La2O3/Cu(111), where the resulting *CO species could be efficiently converted into subsequent intermediates with the rate-determining step further optimized, whereas the conventional formate pathway primarily occurred at the Cu–Zr interface. These two pathways cooperatively promoted the hydrogenation of surface oxygenate intermediates. The findings offer clear and practical guidelines for controlling active sites and reaction pathways in CO2 hydrogenation.