Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) offers a sustainable way for the simultaneous achievement of contamination abatement and resource recovery, supporting a low-carbon water purification approach. In this work, metal–organic frameworks (MOFs) glass complexes (g-ZIF-62@8) were used as a platform to enhance proton transfer through the confinement effect of nanopores, modulating proton coupled electron transfer (PCET) reaction to promote organic pollutant polymerization. The results show that the confinement effect of nanopores in ZIF-62 glass can significantly improve the proton and electron transfer behavior, the proton diffusion coefficient is increased by 4.9 times (2.91*10−3 to 1.43*10−2), the energy barrier of the PCET reaction can be reduced by 1.9 eV, and the reaction kinetic rate constant is increased from 0.0198 min−1 to 0.20118 min−1. Photogenerated holes and Fe(IV = O), as the main reactive oxygen species (ROS), undergo PCET reaction with Bisphenol A (BPA) to convert them into phenoxy radicals, which are then polymerized into macromolecular organic compounds. PCET with proton-electron synergy was identified as a key driver of pollutant polymerization. This enables low-carbon purification and organic carbon recovery in wastewater. Our work provides new insights into the application of confinement effects to enhance proton and electron behavior to regulate pollutant polymerization toward sustainable water purification.
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