Selective production of singlet oxygen from zinc-etching hierarchically porous biochar for sulfamethoxazole degradation

Porous carbons are appealing low-cost and metal-free catalysts in persulfate-based advanced oxidation processes. In this study, a family of porous biochar catalysts (ZnBC) with different porous structures and surface functionalities are synthesized using a chemical activation agent (ZnCl₂). The functional biochars are used to activate persulfate for sulfamethoxazole (SMX) degradation. ZnBC-3 with the highest content of ketonic group (CO, 1.25 at%) exhibits the best oxidation efficiency, attaining a rate constant (kₒbₛ) of 0.025 min⁻¹. The correlation coefficient of the density of CO to kₒbₛ (R² = 0.992) is much higher than the linearity of the organic adsorption capacity to kₒbₛ (R² = 0.694), implying that CO is the intrinsic active site for persulfate activation. Moreover, the volume of mesopore (R² = 0.987), and Zeta potential (R² = 0.976) are also positive factors in PS adsorption and catalysis. In the mechanistic study, we identified that singlet oxygen is the primary reactive oxygen species. It can attack the –NH₂ group aligned to the benzene ring to form dimer products which could be adsorbed on the biochar surface to reach complete removal of the SMX. The optimal pH range is 4–6 which will minimize the electrostatic repulsion between ZnBCs and the reactants. The SMX degradation in ZnBC/PS system was immune to inorganic anions but would compete with organic impurities in the real wastewater. Finally, the biochar catalysts are filled in hydrogel beads and packed in a flow-through packed-bed column. The continuous system yields a high removal efficiency of over 86% for 8 h without decline, this work provided a simple biochar-based persulfate catalyst for complete antibiotics removal in salty conditions.