O–O Bond Homolysis Inhibition Strategy on B-<i>g</i>-C₃N₄ Boosts Selectivity for the Photosynthesis of H₂O₂

Photocatalytic oxygen reduction offers a green and sustainable route for hydrogen peroxide production. Among various photocatalysts, graphitic carbon nitride (g-C3N4) stands out owing to its low cost and tunable electronic structure. However, the competing four-electron O2 reduction reaction (ORR) to H2O significantly compromises the selectivity, posing a major challenge for practical applications. In this study, we propose a boron atom decoration strategy on carbon nitride tubes (BCN) to enhance H2O2 production. Combined experimental and theoretical analyses reveal that the incorporation of B atoms facilitates O2 adsorption and inhibits O–O bond homolysis, improving the selectivity of the two-electron ORR pathway to H2O2. Moreover, B atoms, acting as Lewis acid sites, stabilize the •O2– intermediate through acid–base interactions. As a result, the optimized BCN catalyst (BCN400) achieves a remarkable H2O2 yield of 30 μmol·h–1, representing a 4-fold increase in H2O2 production. This study provides a novel strategy for the design of photocatalysts with optimized active sites, offering significant potential for a wide range of applications in sustainable chemical production.

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