Physics

Electron

Organic chemistry

Carbon nitride

Photocatalysis

Homogeneous

Engineering

Catalysis

Atomic orbital

Inorganic chemistry

Chemistry

Materials science

Iodide

Polymerization

Quantum mechanics

Chemical engineering

Polymer

Photochemistry

Thermodynamics

Angewandte Chemie International Edition

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.

Iodide‐Induced Fragmentation of Polymerized Hydrophilic Carbon Nitride for High‐Performance Quasi‐Homogeneous Photocatalytic H<sub>2</sub>O<sub>2</sub> Production

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

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