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.

Highly Active Heterogeneous Catalyst for Ethylene Dimerization Prepared by Selectively Doping Ni on the Surface of a Zeolitic Imidazolate Framework.

The production of 1-butene by ethylene dimerization is an important chemical industrial process currently implemented using homogeneous catalysts. Here, we describe a highly active heterogeneous catalyst (Ni-ZIF-8) for ethylene dimerization, which consists of isolating Ni-active sites selectively located on the crystal surface of a zeolitic imidazolate framework. Ni-ZIF-8 can be easily prepared by a simple one-pot synthesis method in which site-specific anchoring of Ni is achieved spontaneously because of the incompatibility between the d8 electronic configuration of Ni2+ and the three-dimensional framework of ZIF-8. The full exposure and square-planar coordination of the Ni sites accounts for the high catalytic activity of Ni-ZIF-8. It exhibits an average ethylene turnover frequency greater than 1 000 000 h-1 (1-butene selectivity >85%) at 35 °C and 50 bar, far exceeding the activities of previously reported heterogeneous catalysts and many homogeneous catalysts under similar conditions. Moreover, compared to molecular Ni complexes used as homogeneous catalysts for ethylene dimerization, Ni-ZIF-8 has significantly higher stability and shows constant activity during 4 h of continuous reaction. Isotopic labeling experiments indicate that ethylene dimerization over Ni-ZIF-8 follows the Cossee-Arlman mechanism, and detailed characterizations combined with density functional theory calculations rationalize this observed high activity.

Correction: Facile preparation of a Ni-imidazole compound with high activity for ethylene dimerization.

Correction for 'Facile preparation of a Ni-imidazole compound with high activity for ethylene dimerization' by Zhaohui Liu et al., Chem. Commun., 2024, 60, 188-191, https://doi.org/10.1039/D3CC04794F.

Facile preparation of a Ni-imidazole compound with high activity for ethylene dimerization.

A compound consisting of Ni and imidazole (Ni-imidazole) was synthesized in large quantities by a one-step co-precipitation method. The structure and stability of this Ni-imidazole were well studied by a series of characterization methods. The Ni-imidazole compound exhibited excellent catalytic properties for the dimerization of ethylene to 1-butene.