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Catalytic Conversion of Carbon Monoxide and Methane over Metal and Metal Oxide Catalysts: Synthesis, In-Situ X-Ray Spectroscopy Study, and Catalytic Performance


Catalysis is of vital importance in a wide range of areas including energy processing and chemical production. Catalytic conversion of C1 sources such as carbon monoxide and methane to make hydrocarbon fuels and oxygenated products has far reaching implications especially in the context of the gradual depletion of crude oil resource and the potential surge in the natural gas production in the coming decades. The control over reaction activity and selectivity for the conversion CO and CH4 in the Fischer–Tropsch synthesis and oxidative coupling of methane (OCM) have received tremendous attention and have been proved challenging. This dissertation focuses on the catalytic conversion of CO (Fischer–Tropsch synthesis) using supported cobalt based bimetallic nanoparticle model catalysts and the oxidative coupling of methane with noble metal promoted metal oxide catalysts.

Using colloidal synthesis, a series of cobalt based bimetallic nanoparticles Co–M (M = Mn, Ru, Rh, and Re) with well-defined sizes, shapes, and compositions were obtained. Detailed synthesis procedures were presented and key synthetic parameters were discussed. The as-synthesized nanoparticles were subjected to extensive in-situ X-ray spectroscopy studies using ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and X-ray absorption spectroscopy (XAS) under catalytic relevant conditions. Composition wise, the results indicate the surface concentration of Co on the as-synthesized Co–M bimetallic particles is slightly less than the bulk atomic Co %. While oxidation treatment led to a slight increase of the surface Co, major effect was seen after the reduction treatment where surface segregation of the second metal resulted in a drastic decrease of the surface Co content. The effect is more pronounced at elevated reduction temperatures. Under reaction conditions, the surface compositions remained similar to those after the reduction treatment at high temperatures. Among the bimetallics tested, the Co–Mn system is relatively less susceptible to surface reconstructions induced by oxidation and reduction treatments. In addition, the reducibility of Co was also shown to be modified depending on the second metal present and Re was proved to be most efficient in leading to a facile reduction of Co. Catalytic performance of the bimetallic catalysts supported on mesoporous silica MCF–17 indicates a positive effect in the catalytic activity for Co–Rh and Co–Mn systems, while Co–Re and Co–Cu showed decreased activity. Less pronounced promotion effect of the second metal on the product distribution was observed with only a slight increase in the selectivity towards C5+ products. The selectivities for CH4 and C5+ of the various Co–M bimetallic catalysts generally resemble those of pure Co catalysts. Although in extremely low selectivity, alcohols were also formed with Co–Rh and Co–Cu bimetallic catalysts. The appearance of longer chain alcohol such as propanol, which was not present for pure Co catalysts, is an evidence for potential synergistic promotion.

For oxidative coupling of methane (OCM), the promotion effect of noble metals (Pt, Ir, and Rh) on the performance of MnxOy-Na2WO4/MCF–17 catalysts was investigated. The introduction of noble metals had little effect on the surface area and phase composition of the original catalyst but led to a more reduced nature of the surface oxide species. Catalytic study revealed an enhanced selectivity towards both C2 and C3 hydrocarbons as compared to the undoped MnxOy-Na2WO4/MCF–17 catalyst in the order of Rh-doped > Ir-doped > Pt-doped samples together with a lower olefin to paraffin ratio. A more optimized strength of interaction between the carbon intermediates and the catalyst surface was suggested, which in combination with the improved reducibility of Mn and W species are believed to be responsible for the improved performance.

In addition, monodispersed leaf-like manganese–tungsten–oxide (Mn–W–Ox) nanoparticles and hydroxylated hexagonal boron nitride (h-BN) were synthesized and used as novel catalysts in OCM reaction. Preliminary results indicate that the MCF–17 supported Mn–W–Ox nanoparticle catalyst showed a CH4 conversion of 5.4% and C2 selectivity of 42% with good stability over time. On the other hand, hydroxylated h-BN exhibited good activity (~20% CH4 conversion) with moderate selectivity towards C2 hydrocarbons (20%–30%). However, the hydroxylated h-BN catalysts faced serious deactivation, which was not eliminated by lowering the reaction temperature or the oxygen concentration in the reaction gas feed.

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