Symmetry-Engineered\nBINOL-Based Porous Aromatic Frameworks\nfor H<sub>2</sub>O<sub>2</sub> Production via Artificial Photosynthesis\nand In Situ Degradation of Pharmaceutical Pollutants

Accomplishing visible light-driven H<sub>2</sub>O<sub>2</sub> production\nat millimolar concentrations is practically challenging, particularly\nfor organic semiconductors. In this context, achieving a maximum H<sub>2</sub>O<sub>2</sub> production rate of 31.60 mmol·g<sup>–1</sup>·h<sup>–1</sup> by using porous aromatic frameworks (PAFs)\nrepresents a significant accomplishment. We report the unusual photoactivity\nof tetraphenylmethane-BINOL-linked PAFs in triplet oxygen activation\nto facilitate the generation of reactive oxygen species (ROS), as\nconfirmed by their optical and electrochemical responses, despite\nthe absence of a conventional chromophoric moiety. Moreover, an in\nsitu BINOL formation strategy was used to synthesize these PAFs during\npolymerization in contrast to the reported protocols involving chiral\nBINOLs as precursors. The as-synthesized polymers had a capsule-like\nmorphology (for <b>TPM-BINOL-6</b>), high thermal stability\nup to 348 °C, and a high Brunauer–Emmett–Teller\n(BET) surface area of up to 1382 m<sup>2</sup>/g (for <b>TPM-BINOL-4</b>). Interestingly, they showed sunlight-driven production of H<sub>2</sub>O<sub>2</sub> via an oxygen reduction reaction of up to 17.05\nmmol·g<sup>–1</sup>·h<sup>–1</sup> in 1:10\nisopropanol in water for <b>TPM-BINOL-6</b>, which was quantified\nby titration with ceric sulfate. It also exhibited exemplary photocatalytic\nefficiency with an H<sub>2</sub>O<sub>2</sub> production rate of 6.65\nmmol·g<sup>–1</sup>·h<sup>–1</sup> in seawater.\nInterestingly, the H<sub>2</sub>O<sub>2</sub> production rate reached\na maximum of 18.03 mmol·g<sup>–1</sup>·h<sup>–1</sup> with an SCC efficiency of 4.5% under an AM 1.5G solar simulator\nand apparent quantum yield (AQY) of 15.8% (at λ = 456 nm) for <b>TPM-BINOL-6</b> in ethanol:water = 1:10. Moreover, the exceptionally\nhigh H<sub>2</sub>O<sub>2</sub> production rate of 31.60 mmol·g<sup>–1</sup>·h<sup>–1</sup> was achieved in 1:1 ethanol\nin water under 50 W blue LED light. Furthermore, these PAFs generated\nadequate ROS, which were utilized in the photocatalytic degradation\nof tetracycline via the superoxide intermediate. Additionally, the\nas-formed H<sub>2</sub>O<sub>2</sub> was further channelized in the\npollution abatement catalytic system for the fast degradation of ciprofloxacin\n(within 4 h) and the reduction of toxic oxometallate Cr(VI) within\n10 min, which is one of the earliest reports of utilizing photosynthesized\nH<sub>2</sub>O<sub>2</sub> for environmental detoxification.