Covalent organic frameworks for direct photosynthesis of hydrogen peroxide from water, air and sunlight

Solar-driven photosynthesis is a sustainable process for the production of hydrogen peroxide, the efficiency of which is plagued by side reactions. Metal-free covalent organic frameworks (COFs) that can form suitable intermediates and inhibit side reactions show great promise to photo-synthesize H₂O₂. However, the insufficient formation and separation/transfer of photogenerated charges in such materials restricts the efficiency of H₂O₂ production. Herein, we provide a strategy for the design of donor-acceptor COFs to greatly boost H₂O₂ photosynthesis. We demonstrate that the optimal intramolecular polarity of COFs, achieved by using suitable amounts of phenyl groups as electron donors, can maximize the free charge generation, which leads to high H₂O₂ yield rates (605 μmol g⁻¹ h⁻¹) from water, oxygen and visible light without sacrificial agents. Combining in-situ characterization with computational calculations, we describe how the triazine N-sites with optimal N 2p states play a crucial role in H₂O activation and selective oxidation into H₂O₂. We further experimentally demonstrate that H₂O₂ can be efficiently produced in tap, river or sea water with natural sunlight and air for water decontamination.