Boosting Permanganate-Initiated Pollutant Polymerization via Synergistic Dual-Oxidant Activation by In Situ-Formed Nascent MnO ₂

Polymerization-oriented moderate oxidation mediated by high-valent metals offers a promising low-carbon pathway for wastewater remediation. However, current polymerization strategies largely depend on heterogeneous catalysts that require precise coordination and energy-intensive synthesis, while permanganate (Mn(VII)) alone exhibits limited polymerization capability. Here, we demonstrate that coupling Mn(VII) with supplementary oxidants (e.g., periodate, peroxymonosulfate, and peroxydisulfate) significantly enhances polymer precursor formation and polymeric product yield. This enhancement is governed by in situ-formed nascent MnO 2 (nMnO 2 ), which synergistically activates both Mn(VII) and the co-oxidant without generating radicals. Theoretical and experimental analyses reveal that electron transfer-mediated activation of Mn(VII) by nMnO 2 elevates the Mn 3dz 2 energy level and compresses the MnO 6 lattice. The resulting structural strain lowers electron transfer resistance and enhances interfacial affinity toward the supplementary oxidant, enabling dual-oxidant synergy. This mechanism is universal across various MnO 2 materials and oxidant combinations. The developed nMnO 2 -dominated dual-oxidant system achieves complete bisphenol F removal, over 80% total organic carbon elimination, effective detoxification, and strong anti-interference performance. This work presents a practical pathway to implement Mn(VII)-initiated polymerization in water treatment and offers a generalizable catalyst–substrate interaction-driven framework for designing efficient oxidation technologies.