Light alkene oligomerization on heterogeneous acidic catalysts is widely and successfully used in current commercial processes. However, ethylene oligomerization remains inefficient due to ethylene’s inability to form reaction intermediates to a sufficient extent on acid sites. Adding Ni(II) on solid acids can more efficiently catalyze ethylene oligomerization and selectively produce butenes to fuel range products. The review proposes a complete and detailed mechanism of heterogenous Ni-catalyzed oligomerization, whose structures are supported by combining various studies throughout recent literature, and focuses on the bifunctional effects of the nickel and acid sites on ethylene oligomerization. Using experiments, first-principles calculations, and kinetic modeling, Ni²⁺ has been shown to selectively oligomerize ethylene to light, linear alkenes via the Cossee-Arlman mechanism, while Brønsted H⁺ sites catalyze further alkylation, cracking, and isomerization reactions. The effects of reaction conditions and catalyst properties on selectivity and activity for oligomerization are systematically discussed. Tuning the relative nickel-to-acid site ratio and the framework support can allow for an optimal catalyst design directed towards desirable products.

多相酸性催化剂上的轻烯烃低聚在当前的商业过程中被广泛并成功地使用。然而，由于乙烯不能在酸性位点形成足够程度的反应中间体，因此乙烯低聚反应仍然效率低下。在固体酸上添加 Ni(II) 可以更有效地催化乙烯低聚反应并选择性地生产丁烯以供燃料范围内的产品使用。该综述提出了一个完整而详细的多相镍催化低聚的机制，其结构得到了结合近期文献中各种研究的支持，并侧重于镍和酸位对乙烯低聚的双功能影响。使用实验、第一性原理计算和动力学建模，Ni ²⁺已显示通过 Cossee-Arlman 机制将乙烯选择性低聚为轻质线性烯烃，而 Brønsted H ⁺位点催化进一步的烷基化、裂化和异构化反应。系统地讨论了反应条件和催化剂性质对低聚反应的选择性和活性的影响。调整相对镍酸位点比和骨架载体可以实现针对所需产品的最佳催化剂设计。