Transformative Removal of Aqueous Micropollutants into Polymeric Products by Advanced Oxidation Processes

This perspective presents the latest advancements in selective polymerization pathways in advanced oxidation processes (AOPs) for removal of featured organic pollutants in wastewater. In radical-based homogeneous reactions, SO₄^{• -}-based systems exhibit superior oxidative activity toward aromatics with electron-donating substituents via single electron transfer and radical adduct formation (RAF). The produced organic radical cations subsequently undergo coupling and polymerization reactions to produce polymers. For ^•OH-based oxidation, metal ions facilitate the production of monomer radicals via RAF. Additionally, heterogeneous catalysts can mediate both coupling and polymerization reactions via persulfate activation without generating inorganic radicals. Metal-based catalysts will mediate a direct oxidation pathway toward polymerization. In contrast, carbon-based catalysts will induce coupling reactions to produce low-molecular-weight oligomers (≤4 units) via an electron transfer process. In comparison to mineralization, polymerization pathways remarkably reduce peroxide usage, quickly separate pollutants from the aqueous phase, and generate polymeric byproducts. Thus, AOP-driven polymerization systems hold significant promise in reducing carbon emission and realizing carbon recycling in water treatment processes.