Photothermal Catalysis for Selective Oxidation of Light Alkanes

The selective oxidation of light alkanes (C ₁ –C ₃ ) into value‐added oxygenates and olefins is fundamental to sustainable carbon utilization but is severely hindered by the “activity‐selectivity” trade‐off. Traditional thermal processes require high temperatures that trigger over‐oxidation, while pure photocatalysis suffers from sluggish kinetics. Photothermal catalysis has emerged as a transformative “1 + 1 > 2” strategy, synergistically integrating photonic excitation with localized thermal effects to transcend these limitations. This review systematically summarizes recent progress in the photothermal selective oxidation of light alkanes. We first elucidate the fundamental mechanisms, focusing on how hot carriers, localized thermal spots, and reactive oxygen species cooperatively lower C─H bond activation barriers while promoting intermediate desorption. We then highlight cutting‐edge applications in methane‐to‐oxygenates conversion, oxidative coupling of methane, and oxidative dehydrogenation of ethane and propane. Finally, we discuss current challenges in decoupling thermal and non‐thermal contributions, providing a strategic outlook for future solar‐driven chemical manufacturing.