Abstract
Metal???organic frameworks (MOFs) hold great potential in heteroge-neous catalysis due to their unique properties and tunable structures. Zeolitic imidazolate frameworks (ZIFs) are series of classical MOFs that have been widely studied, where Zn2+ is coordinated with four imidazoles to form a tetrahedral structure. ZIF-L, one type of ZIF, is known for its unique two-dimensional (2D) leaf-like morphology and large external specific surface area. In this work, we reported a facile and green synthesis of the Ni-loaded ZIF-L (Ni-ZIF-L) catalysts, where water as solvent and product collection by filtration make the preparation easy for large-scale industrial production. Considering the incompatibility of the d8 electron configuration of Ni with the three-dimensional (3D) framework of ZIF-L, Ni can only be selectively anchored to the surface of ZIF-L. The Ni-ZIF-L has shown high crystallinity and 2D leaf-like microflakes similar to those of pure ZIF-L. After systematic analysis, we speculate that the Ni sites in Ni-ZIF-L samples have a square planar configuration, which should be coordinated by two imidazole groups from the framework, one NO3??? group, and one free imidazole group. Ni-ZIF-L possesses fully exposed Ni active sites and a large specific surface area, accounting for the good performance for ethylene dimerization. In addition, the large particle size of the Ni-ZIF-L catalyst is beneficial for separation. With the assistance of cocatalyst, Ni-ZIF-L achieves an average ethylene turnover frequency of 330 320 moles of ethylene per mole of Ni per hour (1-butene selectivity >90%)) under 40 ??C and 30 bar, comparable to the activity of the benchmark heterogeneous catalyst. The isotope experiments are used to illustrate that the ethylene dimerization catalyzed by Ni-ZIF-L follows the Cossee-Arlman mechanism, which also rationalizes the high catalytic activity and the small amount of isomerization and trimerization product formation.