Nanoarchitectonics in the Ionothermal Synthesis for Nucleation of Crystalline Potassium Poly (heptazine imide) Towards an Enhanced Solar‐Driven H2O2 Production

Solar-driven selective oxygen reduction reaction on polymeric carbon nitride framework is one of the most promising approaches toward sustainable H2 O2 production. Potassium poly(heptazine imide) (PHI), with regular metal sites in the framework and favorable crystalline structure, is highly active for photocatalytic selective 2e oxygen reduction to produce H2 O2 . By introducing NH4 Cl into the eutectic KCl-LiCl salt mixture, the PHI framework exhibits a remarkable performance for photocatalytic production of H2 O2 , for example, a record high H2 O2 photo-production rate of 29.5 μmol h-1 mg-1 . The efficient photocatalytic performance is attributed to the favorable properties of the new PHI framework, such as improved porosity, negatively shifted LUMO position, enhanced exciton dissociation and charges migration properties. A mechanistic investigation by quenching and electron spin resonance technique reveals the critical role of superoxide radicals for the formation singlet oxygen, and the singlet oxygen is one of the critical intermediates towards the formation of the H2 O2 by proton extraction from the ethanol.