Synergistic role of Cu0-Cu+ sites and oxygen vacancies on MOF-derived Cu supported CeO2 for enhancing hydrogenation of cyclohexyl acetate to cyclohexanol

Unraveling the synergistic interplay between Cu 0 /Cu + and support sites in Cu-based catalysts, coupled with oxygen vacancy-mediated active site modulation and their impact on hydrogenation performance metrics, remains a critical challenge in heterogeneous catalysis. Herein, we engineered a family of MOF-derived Cu/CeO 2 catalysts with tunable Cu loadings and oxygen vacancy(O V ) concentrations, featuring Cu 0 -Cu + -O V interfacial sites, through a MOF-mediated pyrolysis strategy. Operando DRIFTS, XPS, and Raman analyses revealed dynamic restructuring of active sites during hydrogenation of cyclohexyl acetate. The optimized catalyst achieved 98.0 % substrate conversion and 97.3 % cyclohexanol selectivity at 250 ℃ under 3 MPa H 2 , exhibiting a TOF 2.8-fold higher than conventional Cu/CeO 2 . The results indicate that the superior catalytic performance of Cu/CeO 2 -MOF should be attributed to the synergistic effects of Cu + , Cu 0 , and O V . This synergy enhances the ability of catalysts to adsorb and activate cyclohexanone, as well as its hydrogen dissociation capability. Further analysis indicates that O V exerts a direct influence on product selectivity. Moreover, the concentration of O V modulates the ratio of Cu + /(Cu + +Cu 0 ), which significantly affects conversion efficiency of the reaction. This work introduces an innovative approach to designing the electronic structure of copper-based catalysts, thereby optimizing the hydrogenation reactions of carbonyl compounds.