Towards thermocatalytic methane activation at lower temperatures: Recent advances, mechanistic insights and future perspectives

The catalytic conversion of methane into value-added chemicals and platform molecules is critical for energy decarbonization and methane valorization. This review systematically evaluates four technological routes, namely thermocatalysis, electrocatalysis, photocatalysis, and plasma catalysis, identifying thermocatalysis as the most practical solution due to its industrial maturity and rapid reaction kinetics. However, this approach faces an intrinsic activity-selectivity trade-off: low temperatures suppress C–H bond activation, while elevated temperatures promote side reactions (e.g., cracking and over-oxidation) and carbon deposition, leading to reduced selectivity and catalyst deactivation. Addressing this challenge requires efficient low-temperature C–H activation with precise product control. Methane thermocatalytic systems can be classified into four categories based on target products: olefins, methanol, syngas, and aromatics. Through systematic analysis of reaction conditions, mechanisms, and performance metrics, structure–activity relationships for methane thermocatalysis are established. Several strategies are proposed to resolve this trade-off: soft oxidant, chemical looping, photothermal coupling, catalyst modification design etc. Future research should focus on multiscale catalyst engineering and process intensification, integrating atomic-level active site design, mass transfer optimization, and reactor integration. These advancements will synergistically enable low-temperature activation with high-selectivity conversion, providing theoretical and technical foundations for sustainable methane utilization.