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Heterogeneous dimerization of ethylene by coordinatively unsaturated metal sites in two forms of Ni-MIL-77

Cong Wang,Gang Li,Hongchen Guo

Compared with the mainstream approaches of doping the active metal in the MOFs structure and post-synthetic modification, it is more convenient to directly use the coordinatively unsaturated metal sites of MOFs for catalytic reactions. Herein, two forms of Ni-MIL-77 (1D Ni-MIL-77 and 3D MIL-77) were prepared using one-pot method and characterized by ICP-AES, XRD, FT-IR, XPS and SEM. Among them, 1D Ni-MIL-77 without high temperature heat treatment exhibited a better heterogeneous catalytic ethylene dimerization activity that was up to 989.6 g pro. /(g cat. ·h) (TOF=5544 h −1 ) and the selectivity of 1-butene could reach 93.3% at the optimal conditions. In addition, a probable Cossee-Arlman-like mechanism was proposed. By studying the catalyst structure after reaction, it was found that the reason for limited reuse was the hydrolysis products of the co-catalyst covered the catalysts.