Chloride ion (Cl-) is ubiquitous in diverse water bodies, yet poses a longstanding challenge in water pollution control by hindering the efficiency of pollutant degradation. Herein, we proposed a novel concept involving the direct utilization of endogenous Cl- ions in water for rapid water purification within a non-redox zirconium oxide (ZrO2)-activated peroxymonosulfate (PMS) system. In this process, PMS was complexed on the ZrO2 surface through inner-sphere coordination, and effectively activated by the partial electron cloud deviation from Zr(IV) sites to PMS, thereby forming a metastable surface complex with an elevated redox potential. Afterwards, the coexistence of Cl- could trigger the transformation of the reactive complex into free chlorine species, thus leading to a 255.0-fold enhancement in the elimination rate of micropollutants compared with the ZrO2/PMS system. Quantitative structure-activity relationship analysis revealed that the ZrO2/PMS/Cl- system displayed strong target-dependence towards electron-rich compounds, showcasing a faster oxidation rate for pollutants with higher EHOMO energy levels. Significantly, the novel system performed robust resistance to complex water matrices, achieved low oxidant consumption for pollutant removal, and demonstrated adaptation across a broad range of Cl- concentrations (1.0-100.0 mM). Overall, our findings provide new mechanistic insights into the influence of Cl- ions on PMS activation, which refresh the understanding of the role of Cl- ions on pollutant degradation, and help to guide the treatment design for chloride-containing wastewater.
Keywords: Chloride-containing wastewater; Free chlorine; Micropollutants; Peroxymonosulfate; Zirconium oxide.
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