Lithium carbonate-promoted mixed rare earth oxides as a generalized strategy for oxidative coupling of methane with exceptional yields

The oxidative coupling of methane to higher hydrocarbons offers a promising autothermal approach for direct methane conversion, but its progress has been hindered by yield limitations, high temperature requirements, and performance penalties at practical methane partial pressures (~1 atm). In this study, we report a class of Li 2 CO 3 -coated mixed rare earth oxides as highly effective redox catalysts for oxidative coupling of methane under a chemical looping scheme. This catalyst achieves a single-pass C 2+ yield up to 30.6%, demonstrating stable performance at 700 °C and methane partial pressures up to 1.4 atm. In-situ characterizations and quantum chemistry calculations provide insights into the distinct roles of the mixed oxide core and Li 2 CO 3 shell, as well as the interplay between the Pr oxidation state and active peroxide formation upon Li 2 CO 3 coating. Furthermore, we establish a generalized correlation between Pr 4+ content in the mixed lanthanide oxide and hydrocarbons yield, offering a valuable optimization strategy for this class of oxidative coupling of methane redox catalysts. Lithium carbonate-promoted mixed rare earth oxides can be used as redox catalysts for OCM at 700 °C and achieve a single-pass C2+ yield up to 30.6%. The high activity is assigned to the peroxide and OH radicals induced by Pr 4+ in the redox catalyst.