Precise polymerization of phenolic pollutants by a nanoconfined reactor with Fe-Mo dual-site

The conversion of aquatic pollutants into polymers presents a significant opportunity for wastewater resource recovery. However, the precise synthesis of polymers with controlled molecular weight and narrow dispersity remains challenging. Herein, we design a spatially decoupled Fe-Mo dual-site catalyst (FeMo-NC), which synergistically regulates phenolic pollutant transformation through enhanced peroxymonosulfate activation and proton-coupled electron transfer (PCET), thereby reducing the C-H bond dissociation energy barrier by 18.3% and redirecting phenolic pollutant removal toward controlled oligomerization. By tuning the pore size of the carbon framework, we confine polymer growth, yielding polymers with molecular weights of 418–1142 g·mol−1 and narrow dispersity (PDI < 1.2). Compared to conventional Fe₃O₄/PMS systems, PMS consumption decreases by 96.7% and carbon emissions are significantly reduced. An integrated FeMo-NC/ceramic membrane (FeMo-NC/CM) system achieves 100% phenol (PhOH) removal over continuous operation exceeding 144 h. This work highlights confinement engineering as a strategy for selective organic polymerization and wastewater resource recovery. This work demonstrates a Fe-Mo dual-site catalyst that redirects phenolic pollutant transformation toward controlled oligomerization. The resulting membrane system achieves near-complete pollutant removal over 144 h with reduced oxidant usage and carbon emissions.