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.
As novel metal-free photocatalysts, covalent organic frameworks (COFs) have great potential to decontaminate pollutants in water. Fast charge recombination in COFs yet inhibits their photocatalytic performance. We found that the intramolecular charge transfer within COFs could be modulated via constructing a donor−acceptor (D−A) structure, leading to the improved photocatalytic performance of COFs toward pollutant degradation. By integrating electron donor units (1,3,4-thiadiazole or 1,2,4-thiadiazole ring) and electron acceptor units (quinone), two COFs (COF-TD1 and COF-TD2) with robust D−A characteristics were fabricated as visible-light-driven photocatalysts to decontaminate paracetamol. With the readily excited electrons in 1,3,4-thiadiazole rings, COF-TD1 exhibited efficient electron−hole separation through a push−pull electronic effect, resulting in superior paracetamol photodegradation performance (>98% degradation in 60 min) than COF-TD2 (∼60% degradation within 120 min). COF-TD1 could efficiently photodegrade paracetamol in complicated water matrices even in river water, lake water, and sewage wastewater. Diclofenac, bisphenol A, naproxen, and tetracycline hydrochloride were also effectively degraded by COF-TD1. Efficient photodegradation of paracetamol in a scaled-up reactor could be achieved either by COF-TD1 in a powder form or that immobilized onto a glass slide (to further ease recovery and reuse) under natural sunlight irradiation. Overall, this study provided an effective strategy for designing excellent COF-based photocatalysts to degrade emerging contaminants.
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