Sci Rep. 2023 Aug 9;13(1):12928. doi: 10.1038/s41598-023-38436-8.
Biogas has been widely regarded as a promising source of renewable energy. Recently, the direct conversion of biogas over heterogeneous catalysts for the simultaneous production of syngas and carbon nanotubes exhibits a high potential for full utilization of biogas with great benefits. Involving the combined dry reforming of methane and catalytic decomposition of methane, the efficiency of process is strongly depended on the catalyst activity/stability, mainly caused by carbon deposition. In this study, Ni-Mo catalyst is engineered to provide a life-long performance and perform high activity in the combined process. The surface modification of catalysts by a controlled carburization pretreatment is proposed for the first time to produce a carbide catalyst along with improving the catalyst stability as well as the reactivity for direct conversion of biogas. The performance of as-prepared carbide catalysts is investigated with comparison to the oxide and metallic ones. As a result, the Ni-Mo2C catalyst exhibited superior activity and stability over its counterparts, even though the condensed nanocarbon was largely grown and covered on the surface. In addition, up to 82% of CH4 conversion and 93% of CO2 conversion could remain almost constant at 800 °C throughout the entire test period of 3 h under a high flowrate inlet stream of pure biogas at 48,000 cm3 g-1 h-1. The XPS spectra of catalysts confirmed that the presence of Mo2C species on the catalyst surface could promote the stability and reactivity of the catalyst, resulting in higher productivity of carbon nanotubes over a longer time.