Coupling Ionic Polarization, Electron Sponge Effect by One‐Pot Hypercrosslinking, Pyridiniumnation of Photosensitizer‐Based Porous Organic Polymers for Enhancing Advanced Oxidation Process

Abstract Porous organic polymers (POPs) are emerging as up‐and‐coming photocatalysts for energy conversion, and environmental treatment. However, attention to simultaneously improving photoinduced charge separation, transfer, and interfacial reaction is markedly lagged. Herein, the strategy of coupling ionic polarization, electron sponge effect for enhancing the built‐in electric field (BIEF), and surface mass transfer process of the POPs is proposed, which can be realized by a one‐pot post‐pyridiniumnation, Friedel‐Craft reaction. This method endows the ionic polarization effect for elevating BIEF for boosting charge separation/migration. The pyridiniumnation not only induces the electron sponge effect to allow the shallow trap of free electrons but also effectively reduces the oxygen adsorption energy, the free energy of the pertinent reaction intermediates, thus leading to stronger BIEF in 2.73‐fold of the neutral polymer and strengthened O 2 activation. Additionally, the photothermal performance with up to 15 °C increment contributes to the enhancement of photocatalysis. Consequently, iBPyP‐33 exhibits an unprecedentedly efficient photodegradation of 100 ppm bisphenol A (BPA) in just 20 min, photosynthesis of H 2 O 2 with the rate of 3070 µmol g −1 h −1 in air, up to 6583 µmol g −1 h −1 aided by sodium ethylenediaminetetraacetic acid. This study provides fresh, valuable insights into the design of photocatalysts with high interfacial reaction efficiency.