Ultra-Highly Active Ni-Doped MOF-5 Heterogeneous Catalysts for Ethylene Dimerization

Here, an ultra-highly active Ni-MOF-5 catalyst with high Ni loading for ethylene dimerization is reported. The Ni-MOF-5 catalysts are synthesized by a facile one-pot co-precipitation method at room temperature, where Ni²⁺ replaces Zn²⁺ in MOF-5. Unlike Zn²⁺ with tetrahedral coordination in MOF-5, Ni²⁺ is coordinated with extra solvent molecules except for four-oxygen from the framework. After removing coordinated solvent molecules, Ni-MOF-5 achieves an ethylene turnover frequency of 352 000 h⁻¹, corresponding to 9040 g of product per gram of catalyst per hour, at 35 °C and 50 bar, far exceeding the activities of all reported heterogeneous catalysts. The high Ni loading and full exposure structure account for the excellent catalytic performance. Isotope labeling experiments reveal that the catalytic process follows the Cossee–Arlman mechanism, rationalizing the high activity and selectivity of the catalyst. These results demonstrate that Ni-MOF-5 catalysts are very promising for industrial catalytic ethylene dimerization.