Methane Functionalization in Heterogeneous Photocatalysis.

The functionalization of methane is regarded as the "holy grail" reaction in chemistry. Photocatalysis is an emerging approach that activates the inert C-H bond in methane under mild conditions, enabling its functionalization to produce sustainable chemicals. However, achieving selective C-H functionalization remains a significant challenge due to methane's "chameleon-like" behavior under diverse reaction conditions. In this review, we provide a comprehensive overview of recent advances in heterogeneous photocatalytic methane functionalization, covering the fundamental principles of photocatalysis and various synthetic systems, with an emphasis on the mechanisms underlying the structure-activity relationships of the microscopic structure of photocatalysts and the reactions. The potential future applications of artificial intelligence and machine learning in developing efficient methane functionalization systems are also highlighted, aiming to guide future research.