Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955, Saudi Arabia.
College of Pharmacy, Changchun University of Chinese Medicine, Changchun, 130012, China.
Small. 2023 Jun;19(25):e2301235. doi: 10.1002/smll.202301235. Epub 2023 Mar 15.
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 Ni replaces Zn in MOF-5. Unlike Zn with tetrahedral coordination in MOF-5, Ni 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 , 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.
本文报道了一种超高活性的 Ni-MOF-5 催化剂，其镍负载量高，可用于乙烯二聚反应。该 Ni-MOF-5 催化剂通过室温下的简便一锅共沉淀法合成，其中 Ni 取代了 MOF-5 中的 Zn。与 MOF-5 中四面体配位的 Zn 不同，Ni 除了与骨架中的四个氧配位外，还与额外的溶剂分子配位。除去配位的溶剂分子后，Ni-MOF-5 在 35°C 和 50 巴下的乙烯转化频率达到 352000 h-1，对应于每克催化剂每小时每克催化剂生成 9040 克产物，远远超过所有报道的多相催化剂的活性。高镍负载量和完全暴露的结构解释了其优异的催化性能。同位素标记实验表明，催化过程遵循 Cossee-Arlman 机理，合理解释了催化剂的高活性和选择性。这些结果表明，Ni-MOF-5 催化剂在工业催化乙烯二聚反应中具有很大的应用潜力。
