Polar electric field-modulated peroxymonosulfate selective activation for removal of organic contaminants via non-radical electron transfer process

Abstract

Nonradical electron transfer process (ETP) in peroxomonosulfate (PMS) based advanced oxidation processes (AOPs) is regarded promising for selective degradation of organic contaminants in water, however, the subjective modulation strategy and the definitive mechanistic elucidation of ETP are still lacking. Herein, we proposed a heretofore unreported yet efficient ETP indution approach by construction of polar electrical field on biochar via nonmetallic elements co-doping. Physicochemical characterizations and density functional theory (DFT) calculations verified the electronegativity difference among boron, nitrogen, and sulfur elements bestowed robust local electric fields on biochar surface (BC-BNS), which effectively enhanced the adsorption complexation and charge transfer between biochar and PMS. Compared to the other single-doped or co-doped biochar, BC-BNS exhibited superior catalytic performance of PMS activation for degradation of atrazine (ATZ) (kobs=0.036 min−1), as well as various kinds of electron-rich organics. The remarkable catalytic degradation capacity was further verified in various aqueous matrices and background factors, representing the excellent selectivity. Analysis of contribution from reactive oxygen species and electrochemical testing together substantiated the role of polar electric fields in facilitating the modulation from singlet oxygen (1O2) to ETP as a prevailing mechanism. DFT calculations and apparent interactions revealed the dissociation of S-O bond was thermodynamically favored within this potent localized electric field, which further induced the cleavage of OO bond and ultimately promoted the dual electron transfer between ATZ and PMS. The superiority of BC-BNS/PMS system was further validated with the low ecotoxicity caused by enhanced dechlorination, the low energy consumption, and the long-term effectiveness. The novel modulation principle and atomic-level mechanism exploration gave suggestions for advancing ETP-dominated AOP to remove recalcitrant contaminants during water treatment and restoration.