Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have received high concerns due to their extreme persistence, and very few technologies have been reported for their complete destruction. For sound PFCs wastes disposal, mechanochemical method was employed using a planetary ball mill. Potassium hydroxide (KOH) was identified as the best comilling reagent and nearly complete destruction of both PFOS and PFOA was realized. The measured water-soluble fluoride accounted for most of the organic fluorine. The final products of PFOS after treatment were shown to be KF and K2SO4 by XRD analysis. The mass ratio between PFOS and KOH significantly affected the fluoride recovery but not for PFOS destruction and the sulfate recovery. The gradual formation of sulfate and fluoride reveals that the degradation of PFOS is initiated with the dissociation of the sulfonate group. FTIR spectra further showed the disappearance of the -CF3 and -CF2- groups with the generation of sulfate. The cleavage of C-F bonds in PFOS and the formation of fluoride ion were also identified by XPS spectra. On the basis of these results, possible reaction pathways were proposed. The approach was also successfully applied for the destruction of PFOS and PFOA homologues with different chain lengths.

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A rapid (1.5 h) one-step ball milling (BM) method was developed not only to modify commercial MnO2 via top-down approaches (BM0), but also to bottom-up synthesize MnO(x) by cogrinding of KMnO4 and MnC4H6O4 (BM1) or KMnO4 and MnSO4 (BM2). Catalysts activity on gaseous POPs removal was tested using hexachlorobenzene (HCBz) as surrogate. Catalytic performance decreases in the order of BM2 ≈ BM1 (T90% = 180-200 °C) > BM0 (260 °C) > CMO ≈ cryptomelane MnO2 (>300 °C). Both adsorption and destruction contribute to HCBz removal at 180 °C while destruction prevails at 200-300 °C. Mechanism studies show that destruction activity is lineally correlated with the amount of surface reactive oxygen species (Oads); stability is determined by the removal of surface chloride, which is associated with the mobility of bulk lattice oxygen (Olat); adsorption capacities are linearly correlated with surface area and pore structure. With the aid of extensive characterizations the excellent performance of BM prepared samples can be explained as (1) abundant surface vacancies enhance the generation of Oads; (2) massive bulk vacancies promote the mobility of bulk Olat; (3) large surface area and uniform pore size distribution facilitate the physisorption of HCBz.