Dual Ce@g-C 3 N 4 -Photoredox/Chlorine Catalysis: Cross-Dehydrogenative Coupling of N -Heteroarenes and Alkanes/Ethers with H 2 Evolution.

With Ce@g-C ₃ N ₄ as a heterogeneous semiconductor photocatalyst, ⁿ Bu ₄ NCl as both a redox catalyst and a hydrogen atom transfer catalyst, the first example of semiheterogeneous photocatalytic cross-dehydrogenative coupling of N -heteroarenes and alkanes/ethers with H ₂ evolution was developed. Both a diverse array of high-value alkylated N -heteroarenes and clean H ₂ can be efficiently coproduced under sacrificial reagent- and chemical oxidant/reductant-free conditions. Combining both the reversible Ce ⁴⁺ /Ce ³⁺ redox pair and the reversible Cl̅/Cl ̇ redox pair can considerably improve the photocatalytic efficiency.