Study on the Synergistic Effect of SiO2 and H2O on Oxidative Coupling of Methane over Mn–Na2WO4/SiO2 Catalyst

Mn–Na2WO4-based catalysts with different supports were prepared using the incipient wetness impregnation method and evaluated for their oxidative coupling of methane (OCM) reaction performance. The results demonstrated that the SiO2- supported catalyst exhibited the best catalytic performance, and the introduction of H2O further enhanced its activity. Under the conditions of a feed gas mixture of CH4/O2/H2O = 6:1:24 at 800 °C and atmospheric pressure, the CH4 conversion and C2+ selectivity over the Mn–Na2WO4/SiO2 catalyst increased from 28.4% and 77.4% (without H2O) to 33.2% and 84.9%, respectively. In contrast, the catalytic activity using TiO2 and MgO supports drastically declined. Characterizations using X-ray diffraction (XRD), in situ infrared spectroscopy (In-situ IR), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), and oxygen temperature-programmed desorption (O2-TPD) revealed that the introduction of steam not only served as a diluent to decrease the partial pressures of the reactants CH4 and O2, thereby reducing deep oxidation reactions in the gas phase, but also interacted with surface oxygen species (O22–) and silica to form adjacent surface-bonded disilanol free radicals Si–OIH. This interaction facilitated the dehydrogenation and coupling of two methane molecules on the catalyst surface, resulting in the generation of C2+ products, significantly enhancing the catalytic activity and selectivity of OCM.