Synergistic Effects of CeO2 Modification and 3D Ordered Macroporous Architecture on CO2 Hydrogenation to Methanol over Cu-ZnO-ZrO2 Catalysts

Rare earth CeO2 was introduced into the Cu-ZnO-ZrO2 catalyst system through coprecipitation and three-dimensionally ordered macroporous (3DOM) preparation methods for material modification. Activity tests revealed that CeO2 modification significantly enhanced the catalytic performance of catalysts prepared by both methods in CO2 hydrogenation to methanol, with the most pronounced improvement observed in the 3DOM-structured CeO2-modified catalyst. Under reaction conditions of 200°C and 4 MPa, the CZZC-3DOM/Cu-ZnO-ZrO2 catalyst loaded with 3 wt% CeO2 exhibited increased CO2 conversion (from 8.24% to 11.1%), improved methanol selectivity (from 79.5% to 88.3%), and enhanced methanol space-time yield (from 195 to 292 gMeOHkgcata-1h-1), representing an overall 50% performance enhancement. Characterization results (XRD, SEM, TEM) demonstrated that compared to coprecipitation-derived catalysts, the 3DOM-structured catalyst achieved more uniform spatial distribution of active sites after CeO2 modification. The 3DOM architecture facilitated Ce element dispersion on the catalyst surface and promoted oxygen vacancy formation, thereby improving CO2 adsorption. This study demonstrates that the combination of CeO2 modification and 3DOM structure creates synergistic effects for catalytic enhancement, providing valuable insights for designing novel catalysts for CO2-to-methanol conversion.