Nanoarchitecture Manipulation by Polycondensation on KCl Crystals toward Crystalline Lamellar Carbon Nitride for Efficient H₂O₂ Photoproduction

A lamellar carbon nitride (CN) framework is one of the most promising materials for solar-driven hydrogen peroxide production. The low dielectric constant of the organic CN framework leads to severe recombination of the excitons, and the photon-to-chemical conversion efficiency is thus unsatisfactory. In this work, by polycondensation of the small molecules on the KCl crystal surface, K+-incorporated crystalline CN (CNK) frameworks show significantly extended periodicity of the stacking layers and in-plane orderly organized heptazine/triazine units. The crystalline CNK frameworks exhibit a series of favorable photophysical properties, such as enhanced photon absorption, negatively shifted LUMO potentials, and attenuated emissive decay of the excitons. The CNK frameworks thus present remarkable performance in the photocatalytic selective oxygen reduction reaction for hydrogen peroxide production, e.g., CNK framework from the polycondensation of NH4SCN on the KCl surface could produce hydrogen peroxide at a remarkable reaction rate of 26.7 mmol h-1 g-1 with a high apparent quantum yield of 25.0%, which is 23.5 times that on its counterpart synthesized in the absence of KCl. This method is generally applicable to all of the precursors for CN synthesis.