Accelerated Synthesis and Discovery of Covalent Organic Framework Photocatalysts for Hydrogen Peroxide Production

A high-throughput sonochemical synthesis and testing strategy was developed to discover covalent organic frameworks (COFs) for photocatalysis. In total, 76 conjugated polymers were synthesized, including 60 crystalline COFs of which 18 were previously unreported. These COFs were then screened for photocatalytic hydrogen peroxide (H₂O₂) production using water and oxygen. One of these COFs, sonoCOF-F2, was found to be an excellent photocatalyst for photocatalytic H₂O₂ production even in the absence of sacrificial donors. However, after long-term photocatalytic tests (96 h), the imine sonoCOF-F2 transformed into an amide-linked COF with reduced crystallinity and loss of electronic conjugation, decreasing the photocatalytic activity. When benzyl alcohol was introduced to form a two-phase catalytic system, the photostability of sonoCOF-F2 was greatly enhanced, leading to stable H₂O₂ production for at least 1 week.