Rational design of halogen-bond-assisted organic polymers (XOPs) with [N···I⁺···N] orthogonal structures for enhanced hydrogen peroxide production under visible light

Photocatalytic hydrogen peroxide (H2O2) production under visible light holds significant promise for sustainable chemistry. Although materials incorporating fused aromatic rings or S-, O-, and N-rich heterocycles exhibited good photocatalytic efficiency, the photocatalytic efficiency of simple aromatic materials is still pretty poor. Herein, we propose a novel strategy using o-phenyl-modified halogen-bonded-assisted organic polymers (XOPs) utilizing the unique [N···I+···N] halogen bonds to tune the electronic properties and enhance photocatalytic efficiency. XOPs offer a streamlined design, maintaining high photocatalytic performance with simple synthesis. The incorporation of o-phenyl groups and [N···I+···N] halogen bonds enhances structural stability and facilitates charge separation, key for improved photocatalytic activity. Experimental results show that XOP-TppPh achieves a H2O2 production rate of 3507 μmol g−1 h−1, surpassing most currently reported simple aromatic materials. This work introduces a sustainable, cost-effective approach to improving photocatalytic efficiency without relying on fused rings or heterocycles.