Single-Atom Ni Heterogeneous Catalysts Supported UiO-66 Structure: Synthesis and Catalytic Activities

Herein, the single-atom Ni site heterogeneous catalysts supported by the UiO-66 structure (University of Oslo-66 metal organic framework) were successfully synthesized by a postsynthetic metalation method, where Ni ions are covalently attached to the missing-linker defect sites at zirconium oxide clusters (Zr6O4(OH)4) in as-prepared UiO-66 structure, [Zr6O4(OH)4(BDC)(DMF)10(OH)10] (BDC (benzene-1,4-dicarboxylate), DMF (dimethylformamide)). The structure properties of the catalysts were characterized using powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), N2 adsorption-desorption isotherms (BET), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). It was found that single-atom Ni heterogeneous catalysts supported by the UiO-66 structure, UiO-66/Ni1.0 [Zr6O4(OH)4(C8H4O4)(DMF)10(OH)8Ni2(OH)2(Cl)2], showed a sphere-like morphology with a high specific surface area as well as good thermal stability. Specifically, the as-prepared UiO-66/Ni1.0 exhibited the excellent catalytic activity and stability for 4-nitrophenol reduction in terms of low activation energy (Ea=23.15 kJ mol−1), high turnover frequency (76.19 molecules g-1 min-1), and high apparent rate constant (kapp=0.956min−1). In addition, methylene blue (MB) was also chosen as the organic dye model for catalytic reduction reaction. The kapp and TOF for the reduction of MB using UiO-66/Ni1.0 were 0.787 min−1 and 33.89×1020 molecules g−1 min−1, respectively.