Efficient activation of peracetic acid by mixed sludge derived biochar: Critical role of persistent free radicals

Peracetic acid (PAA)-based advanced oxidation processes (AOPs) were increasingly identified as the alternative scheme in wastewater treatment. Cost-effective and easily available catalyst for activation of PAA was in urgent demand for promoting engineering application process. In this study, a new type of biochar catalyst derived from pyrolysis of mixture of primary sludge (PSD) and secondary sludge (SSD) was prepared and showed effective PAA activation ability. The degradation of p-chlorophenol (4-CP) improved with PAA activation by mixed sludge derived biochar (PS-SDBC) than secondary sludge derived biochar (S-SDBC) and primary sludge derived biochar (P-SDBC), and the highest removal efficiency achieved by PS-SDBC with the PSD/SSD ratio of 5/5 (k_obs=0.057 1/(M·min), pH 9). Correlation analysis firstly indicated that persistent free radicals (PFRs) rather than chemical composition and material structure dominated PAA activation and organic radicals (RO•) was proved to be the major reactive species through electron paramagnetic resonance (EPR) detection. The mixture of PSD and SSD caused the synergy of inorganic metals and organic matters through pyrolysis processes, resulting in larger specific surface area (SSA) (110.71 m²/g), more abundant electron-donating groups (e.g., C = O, -OH) and massive defects (I_D/I_G = 1.519) of PS-SDBC than P-SDBC and S-SDBC, which eventually promoted PFRs formation. A fascinating phenomenon was observed in PS-SDBC/PAA system that the active sites of PFRs could be regenerated by RO• attacking onto PS-SDBC, which contributed to the wide pH applicability and continuous stability of PS-SDBC/PAA system in practical wastewater treatment. This study not only significantly deepened the understanding of the reaction mechanism between PAA and biochar, but also provided a potential PAA-based AOPs for micropollutants removal in wastewater.