Cerium(IV) Enhances the Catalytic Oxidation Activity of Single-Site Cu Active Sites in MOFs

The rates of catalytic oxidation of cyclohexane and CO are 4 and 20 times higher, respectively, with Cu supported on a cerium-based metal–organic framework (MOF) than on the structurally analogous zirconium material. Both Ce- and Zr-based copper catalysts feature uncommon three-coordinate CuII sites bearing different nuclearities, as determined by Cu K-edge extended X-ray absorption fine structure analysis. These results offer molecular-level understanding of the metal–support interface in MOF catalysts and establish correlations with the more established literature on zirconia- and ceria-supported heterogeneous catalysis.