Direct conversion of methane to value-added hydrocarbons using alkali metal-promoted cobalt catalysts†
Abstract
The oxidative coupling of methane (OCM) is a promising pathway for directly converting methane into higher hydrocarbons (C2+). This research investigated the influence of alkali metal promoters (Li, Na, K, or Rb) on Co/Al2O3 catalysts prepared based on incipient wetness impregnation for the OCM reaction. The catalyst investigations demonstrated that the catalysts promoted with K and Rb had superior performance, with the 4.6K–Co/Al2O3 catalyst achieving a maximum C2+ yield of 8.1%, C2+ selectivity of 24.0%, and CH4 conversion of 32.1% at 640 °C. Catalyst characterization, based on XRD, HR-TEM, BET, XPS, CO2-TPD, and H2-TPR analyses, revealed the structural and physicochemical properties responsible for the enhanced catalytic activity. Specifically, K and Rb promoters increased surface basicity and enhanced the electron density of active sites, thereby promoting selective methane activation. In-situ DRIFTS and mechanistic studies highlighted the role of reactive oxygen species in promoting C2+ hydrocarbon formation. These results should position K–Co/Al2O3 as a promising catalyst for OCM and provide valuable guidance for designing more efficient catalytic systems for methane utilization.