Peroxymonosulfate activated by natural porphyrin derivatives for rapid degradation of organic pollutants via singlet oxygen and high-valent iron-oxo species

Abstract

The activation of peroxymonosulfate (PMS) by sodium ferric chlorophyllin (SFC), a natural porphyrin derivative extracted from chlorophyll-rich substances, was systematically investigated for facile degradation of bisphenol A (BPA). SFC/PMS is capable of degrading 97.5% of BPA in the first 10 min with the initial BPA concentration of 20 mg/L and pH = 3, whereas conventional Fe²⁺/PMS could only remove 22.6% of BPA under identical conditions. It demonstrates a prominent flexibility to a broad pH range of 3-11 with complete pollutant degradation. A remarkable tolerance toward concomitant high concentration of inorganic anions (100 mM) was also observed, among which (bi)carbonates can even accelerate the degradation. The nonradical oxidation species, including high-valent iron-oxo porphyrin species and ¹O₂, are identified as dominant species. Particularly, the generation and participation of ¹O₂ in the reaction is evidenced by experimental and theoretical methods, which is vastly different from the previous study. The specific activation mechanism is unveiled by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The results shed light on effective PMS activation by iron (III) porphyrin and the proposed natural porphyrin derivative would be a promising candidate for efficient abatement of recalcitrant pollutants toward complicated aqueous media in wastewater treatment.

Keywords: Biomimetic oxidation; High-valent iron species; Iron(III) porphyrin; Nonradical pathway; PMS; Singlet oxygen.