Weakly Hydrophilic Imine-Linked Covalent Benzene–Acetylene Frameworks for Photocatalytic H₂O₂ Production in the Two-Phase System

Conversing oxygen (O 2 ) to hydrogen peroxide (H 2 O 2 ) driven by solar energy is a promising H 2 O 2 onsite production route but often short of efficient and durable photocatalysts. Herein, strong π–π conjugate polycyclic aromatic benzene and acetylene units have been constructed into new covalent organic frameworks (COFs) linked by imine C═N bonding. These COFs demonstrated two-dimensional hexagonal crystalline frameworks with higher crystallinity and larger surface area (>600 m 2 g –1 ). Covalent benzene–acetylene frameworks possessed appropriate visible light-responsive band structure and the suppressed charge recombination rate. The −OH groups on their frameworks enable them to be weakly hydrophilic. As a result, it served as high-performance but durable photocatalysts for H 2 O 2 production in the water–benzyl alcohol (BA) two-phase system. It delivered a H 2 O 2 production rate of 1240 μmol h –1 g cat –1 and durable catalytic efficiency within 60 h, comparable to the best COF-based catalysts. This study provides an efficient two-phase photocatalytic system for H 2 O 2 production based on weakly hydrophilic imine-linked benzene–acetylene organic photocatalysts.