P-doped biochar regulates nZVI nanocracks formation for superefficient persulfate activation

In this study, a novel P-doped biochar loaded with nano zero-valent iron (nZVI) composite (nZVI@P-BC), with abundant nanocracks from inside to outside in nZVI particles, was designed for ultra-efficient persulfate (PS) activation and gamma-hexachlorocyclohexane (γ-HCH) degradation. Results showed that P-doping treatment significantly enhanced specific surface area, hydrophobicity and adsorption capacity of biochar. Systematic characterizations revealed that the additional electrostatic stress and continuously generated multiple new nucleation sites of P-doped biochar were the main mechanism for the formation of nanocracked structure. nZVI@P-BC with KH₂PO₄ as P precursor showed superefficient PS activation and γ-HCH degradation, by which 92.6 % of 10 mg/L γ-HCH was removed within 10 min using 1.25 g/L catalyst and 4 mM PS, being 10.5-fold greater than that of without P-doping. Electron spin resonance and radical quenching test showed that •OH and ¹O₂ were the dominant active species, and further revealed that the unique nanocracked nZVI, high adsorption capacity and abundant P sites in nZVI@P-BC enhanced their generation and mediated extra direct surface electron transfer. nZVI@P-BC also exhibited high tolerance to different anions, humic acid and wide pH conditions. This work provides a new strategy and mechanism insight for the rational design of nZVI and diversified application of biochar.