A quadruple-strategy of modification on carbon nitride boosts oxygen reduction for high performance photocatalytic hydrogen peroxide production.

This paper reports a quadruple-strategy for material design, simultaneously applying morphology control, group modification, defect engineering and alkali metal doping to the design of catalysts, and successfully constructing irregular clusters of carbon nitride (pMNK-CN) with excellent photogenerated carrier separation performance and structural stability. The pMNK-CN is an irregular flower cluster-like morphology with a nanosheet structure on the surface, and the repolymerization process of the prepolymer in the microvoid of the metal salt gives it an open pore structure. With the help of essential characterization, it was confirmed that the heptazine unit in the backbone underwent partial decomposition due to the etching of metal salts at high temperatures, reducing the overall polymerization and introducing cyano and nitrogen vacancies. Meanwhile, the potassium ion embedded in the lattice can induce the growth of ordered structures and thus improve the short-range order. The pMNK-CN possesses a hydrogen peroxide production efficiency of 240.0 μmol·g·h in pure water, which is 31 times higher than that of bulk carbon nitride. And the apparent quantum efficiencies of pMNK-CN in the 380 and 420 nm bands are 17.5 % and 14.8 % in the presence of isopropanol. The effects of each modification strategies on the electronic structure of carbon nitride were investigated using First-Principles, and it was demonstrated that the multiple modification strategies synergistically enhanced the optical absorption, photogenerated charge separation efficiency, and lowered the reaction energy barrier, thus greatly contributing to the oxygen reduction to hydrogen peroxide performance.