Heterogeneous Photocatalytic Recycling of FeX2/FeX3 for Efficient Halogenation of C−H Bonds Using NaX

Environmental‐friendly halogenation of C−H bonds using abundant, non‐toxic halogen salts is in high demand in various chemical industries, yet the efficiency and selectivity of laboratory available protocols are far behind the conventional photolytic halogenation process which uses hazardous halogen sources. Here we report an FeX2 (X=Br, Cl) coupled semiconductor system for efficient, selective, and continuous photocatalytic halogenation using NaX as halogen source under mild conditions. Herein, FeX2 catalyzes the reduction of molecular oxygen and the consumption of generated oxygen radicals, thus boosting the generation of halogen radicals and elemental halogen for direct halogenation and indirect halogenation via the formation of FeX3. Recycling of FeX2 and FeX3 during the photocatalytic process enables the halogenation of a wide range of hydrocarbons in a continuous flow, rendering it a promising method for applications. An FeX2 coupled semiconductor system accelerates oxygen reduction and halogen radical generation, resulting in efficient, selective, and continuous photocatalytic halogenation using NaX as the halogen source under mild conditions.