PTIO as a redox mediator to enhance organic contaminants oxidation by permanganate

Although permanganate (Mn(VII)) is extensively utilized as a strong oxidizer for the purification of water, the direct reaction rates between some refractory pollutants and Mn(VII) are moderate or relatively low. In this study, we found that 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO), could act as a redox mediator to enhance bisphenol A (BPA) degradation by Mn(VII) at pH 5.0 - 9.0, with a removal higher than 80% over 5 min. Moreover, the Mn(VII)/PTIO system is highly efficient toward a broad spectrum of contaminants. Mechanism was elucidated as following: PTIO was oxidized by Mn(VII) to PTIO⁺, an oxoammonium cation. As a newly generated reactive species, PTIO⁺ could oxidize organics and be reduced to PTIOH (PTIO hydroxylamine) or PTIO simultaneously. The redox cycle of PTIO in consecutive runs as an electron shuttle proved its stability and reusability in Mn(VII) oxidation. In addition to being an electron shuttle, PTIO also acts as an activator of Mn(VII) to promote the production of MnO₂, which plays a vital role in enhancing BPA abatement at the acidic condition. For the purpose of further understanding the interaction between PTIO and target contaminants, three corresponding degradation pathways for BPA were proposed. Notably, the transformation products of BPA coupling with PTIO were detected, indicating PTIO inhibited the self-coupling of BPA and facilitated the ring-opening pathway. In addition, the ubiquitous humic acid has a positive effect on the Mn(VII)/PTIO system, suggesting a high promise of this system for practical application.