Coupling of sulfur and boron in carbonaceous material to strengthen persulfate activation for antibiotic degradation: Active sites, mechanism, and toxicity assessment

Carbon-mediated persulfate advanced oxidation processes (PS-AOPs) are appealing in contaminant remediation. For the first time, S,B-co-doped carbon-based persulfate activators were synthesized through direct carbonization of sodium lignosulfonate and boric acid. By degrading sulfamethoxazole (SMX), CSB-750 obtained 98.7% removal and 81.4% mineralization within 30 min. In comparison with solo S or B doping, S and B co-doped carbon showed the coupling effect for enhanced catalysis. The rate constant (k_obs) of 0.1679 min^–1 was 22.38- and 279.83-fold higher than those of CS-750 (0.0075 min^–1) and CB-750 (0.0006 min^–1), respectively. The degradation was efficient at strong acidic and weak basic conditions (pH 3–9). Substantial inhibition effect was presented at strong basic condition (pH 10.95) and in presence of CO₃^2–. The CO₃^2–-caused inhibition was the combined result of the cooperation of pH and quenching O₂^·–. Thiophene sulfur, BC₃, BC₂O, and structural defects were identified as the active sites for PS activation. Radical and nonradical pathways were both involved in the CSB-750/PS/SMX system, where ¹O₂ dominated the degradation, SO₄^·–, ^·OH and direct electron transfer played the subordinate role, and O₂^·– served as a precursor for the formation of partial ¹O₂. The toxicity of degradation system, the effect of real water matrix, and the reusability of carbocatalysts were comprehensively analyzed. Nine possible degradation pathways were proposed. This work focuses on the catalytic performance improvement through the coupling effect of S,B co-doping, and develops an advanced heteroatom doping system to fabricate carbonaceous persulfate activators. © 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of MateriaMedica, Chinese Academy of Medical Sciences.