Electricity-driven water splitting reaction achieved by electrochemical method to produce hydrogen and oxygen is utilized as an energy carrier in the form of highly pure hydrogen gas. However, the development of earth-abundant, durable, and highly effective electrocatlyst to overcome the high overpotentials of hydrogen, and oxygen evolution reaction (HER, OER) is extremely challenging. This dissertation presents firstly the catalytic properties of tungsten disulfide (WS2) as highly effective HER catalyst through direct growth of 2H-WS2 layered materials on a conductive substrate. Effect of various gaseous atmosphere and temperatures was studied and it was found that the amorphous structure of WS2 can be strongly affected under H2S environment which leads to the formation of bridging disulfide ligands S2 2- and apical S2- from WS3 phase, which is consequently contribute to the catalytic enhancement toward HER with extremely low overpotential (η10 = 184 mV). On the other hand, OER is the major bottleneck in water splitting reaction due to its poor kinetics originated from the complex four electrons transfer process. Chemical vapor deposition strategy is used here to enable stoichiometric tuning and phase engineering of CoP2 OER electrocatalyst followed by deposition of carbonaceous protection layer to overcome surface oxidation. Electrochemical studies indicate that C@CoP2/CC can achieve a remarkable activity (η10 = 234 mV), with minor decay from its initial current density after continuous operation of 80 hours. Lastly, electrolysis of alkaline water is the most common industrial method to produce H2; however, it is a formidable challenging to compete with Pt catalyst in base at industrial scale. For that, temperature-dependent phase evolution was studied in details and it is found that (Co(OH)2) precursor undergoes phase transition under a unique phosphidation system starting with partially phosphatized phase CoP-CoxOy, followed by phosphorus rich phase CoP2, and ultimately to pure CoP phase under elevated temperatures. Comprehensive analysis revealed that concerted composite CoP-CoxOy is the most active phase to produce H2 electrochemically from alkaline water which is contributed to the unique role of integrated phase and its ability to overcome the sluggish hydrogen kinetics in base.

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.