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 Li₂CO₃-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 C₂₊ 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 Li₂CO₃ shell, as well as the interplay between the Pr oxidation state and active peroxide formation upon Li₂CO₃ coating. Furthermore, we establish a generalized correlation between Pr⁴⁺ content in the mixed lanthanide oxide and hydrocarbons yield, offering a valuable optimization strategy for this class of oxidative coupling of methane redox catalysts.