Organic Polymers Enabling Concurrent Charge and Mass Transfer for Photocatalytic Hydrogen Peroxide Synthesis

Constructing polymer photocatalysts that can concurrently accomplish charge transfer and mass transport to catalytic sites remains a formidable task. In this study, by cross‐linking electron‐rich polyphenol and electron‐poor phenothiazine units, two hydrophilic and porous organic polymer photocatalysts characterized by densely packed donor–acceptor units are deliberately designed. The hydrophilic phenolic hydroxyl group in the donor moiety and the aperture channel neighboring the acceptor unit facilitate the capture of water and oxygen at the catalytic site. Meanwhile, the donor–acceptor columns serve as charge supply chains and numerous water oxidation and oxygen reduction centers. These photocatalysts are used for the photocatalytic synthesis of hydrogen peroxide from water and oxygen without the use of sacrificial reagents. Therein, the polymer containing tetramethyl groups shows high selectivity for the photogeneration of hydrogen peroxide, achieving a yield rate of 691.3 μmol g −1 h −1 (16.73 mM g −1 ) and an apparent quantum yield (AQY) of 11.9% under 630 nm irradiation. This organic polymer catalyst system exhibits considerable potential as a promising artificial photosynthesis system capable of realizing simultaneous charge transfer and mass transfer.