We show that the activity and selectivity of Cu catalyst can be promoted by a Zr-based metal-organic framework (MOF), ZrO(OH)(BDC) (BDC = 1,4-benzenedicarboxylate), UiO-66, to have a strong interaction with Zr oxide [ZrO(OH)(-CO)] secondary building units (SBUs) of the MOF for CO hydrogenation to methanol. These interesting features are achieved by a catalyst composed of 18 nm single Cu nanocrystal (NC) encapsulated within single crystal UiO-66 (Cu⊂UiO-66). The performance of this catalyst construct exceeds the benchmark Cu/ZnO/AlO catalyst and gives a steady 8-fold enhanced yield and 100% selectivity for methanol. The X-ray photoelectron spectroscopy data obtained on the surface of the catalyst show that Zr 3d binding energy is shifted toward lower oxidation state in the presence of Cu NC, suggesting that there is a strong interaction between Cu NC and Zr oxide SBUs of the MOF to make a highly active Cu catalyst.
Particulate methane monooxygenase (pMMO) is an enzyme that oxidizes methane to methanol with high activity and selectivity. Limited success hasbeenachievedinincorporating biologically relevant ligands for the formation of such active site in a synthetic system. Here, we report the design and synthesis of metal− organic framework (MOF) catalysts inspired by pMMO for selective methane oxidation to methanol. By judicious selection of a framework with appropriate topology and chemical functionality, MOF-808 was used to postsynthetically install ligands bearing imidazole units for subsequent metalation with Cu(I) in the presence of dioxygen. The catalysts show high selectivity for methane oxidation to methanol under isothermal conditions at 150°C. Combined spectroscopies and density functional theory calculations suggest bis(μ-oxo) dicopper species as probable active site of the catalysts.
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