Production of Linear Alpha Olefins via Heterogeneous Metal-OrganicFramework (MOF) Catalysts

Abstract

Linear Alpha Olefins (LAOs) are one of the most important commodities in the chemical industry, which are currently mainly produced via homogenous catalytic processes. Heterogeneous catalysts have always been desirable from an industrial viewpoint due to their advantages of low operation cost, ease of separation, and catalyst reusability. However, the development of highly active, selective, and stable heterogeneous catalysts for the production of LAOs has been a challenge throughout the last 60 years. In this dissertation, we designed and prepared a series of heterogeneous catalysts by incorporating structural moieties of homogenous benchmark catalysts into metal-organic-frameworks (MOFs), aiming to provide a feasible solution to this long-standing challenge. First, we reviewed the background and state of the art of this field and put forward the main objectives of our research. Then, we thoroughly discussed a novel heterogeneous catalyst (Ni-ZIF-8) that we developed for ethylene dimerization to produce 1-butene, focusing on its designed principle, detailed characterizations, catalytic performance evaluation, and reaction mechanisms. Ni-ZIF-8 exhibits an average ethylene turnover frequency greater than 1,000,000 h$^{-1}$ (1-butene selectivity >85%), far exceeding the activities of previously reported heterogeneous and many homogenous catalysts under similar conditions. Compared with homogenous nickel catalysts, Ni-ZIF-8 has significantly higher stability and showed constant activity during four hours of continuous reaction for at least two reaction cycles. The combination of isotopic labeling studies and Density Functional Theory calculations demonstrated that ethylene dimerization on Ni-ZIF-8 follows the Cossee-Arlman mechanism, and that the full exposure and square-planer coordination of the nickel sites account for the observed high activity. After that, we further optimized the Ni-ZIF-8 catalytic system from the perspective of practical applications. We achieved double productivity of 1-butene by optimizing the synthetic conditions and explored its usability and performances under solvent-free conditions. Then, we extended our catalyst design concept to prepare heterogeneous catalysts comprising other metals and MOFs, which provided a suitable platform for studying the effects of the metallic center and coordination environment on the catalytic production of LAOs. Finally, we gave our perspectives on the further development of heterogeneous catalysts for the production of LAOs.