Iodide‐Induced Fragmentation of Polymerized Hydrophilic Carbon Nitride for High‐Performance Quasi‐Homogeneous Photocatalytic H₂O₂ Production

Abstract

Polymeric carbon nitride (PCN) as a class of two-electron oxygen reduction reaction (2 e^- ORR) photocatalyst has attracted much attention for H₂ O₂ production. However, the low activity and inferior selectivity of 2 e^- ORR greatly restrict the H₂ O₂ production efficiency. Herein, we develop a new strategy to synthesize hydrophilic, fragmented PCN photocatalyst by the terminating polymerization (TP-PCN) effect of iodide ions. The obtained TP-PCN with abundant edge active sites (AEASs), which can form quasi-homogeneous photocatalytic system, exhibits superior H₂ O₂ generation rate (3265.4 μM h^-1 ), far surpassing PCN and other PCN-based photocatalysts. DFT calculations further indicate that TP-PCN is more favorable for electron transiting from β spin-orbital to the π* orbitals of O₂ , which optimizes O₂ activation and reduces the energy barrier of H₂ O₂ formation. This work provides a new concept for designing functional photocatalysts and understanding the mechanism of O₂ activation in ORR for H₂ O₂ production.