Effect of persulfate dosage on organic degradation using N‐doped biochar: Reaction pathway and environmental implications

Abstract Persulfate‐based advanced oxidation processes (PS‐AOPs) catalyzed by carbon‐based catalysts are promising for removing organic pollutants via radical/non‐radical pathways. However, the activation efficiency of peroxymonosulfate (PMS) or peroxydisulfate (PDS) usage and the reaction mechanism remain insufficiently understood. In this study, the effects of PMS/PDS dosage on the degradation of bisphenol A (BPA, 10 mg/L) were evaluated using N‐doped biochar (N‐BC, 0.2 g/L) assisted PS‐AOPs. The reaction pathways were comprehensively investigated through a combination of characterization techniques and molecular simulations. With low PS dosages (0.05 and 0.1 mM), the degradation rate constants () were higher in N‐BC/PDS (0.04 and 0.07 min −1 ) compared to N‐BC/PMS (0.02 and 0.04 min −1 ), likely due to higher PDS utilization, which enhanced the contribution of the non‐radical pathway. Interestingly, with higher PS dosages (0.5 and 1.5 mM), the values were 0.16 min −1 and 0.18 min −1 in N‐BC/PMS, respectively, significantly exceeding those determined in N‐BC/PDS (0.11 and 0.11 min −1 ). This result stemmed from the greater adsorption capacity of N‐BC for PMS compared to PDS, leading to increased formation of 1 O 2 . The contribution of non‐radical pathways for both PMS and PDS increased with higher PS dosage. The results highlighted that BPA degradation improved significantly with the increase in PMS dosage; meanwhile, BPA degradation was insensitive to PDS dosage. The optimal PMS dosage for BPA degradation was found to be 1.5 mM and 0.1 mM for PDS. This study offered valuable insights for optimizing PS‐AOPs in environmental remediation, helping to guide the selection of appropriate oxidants and dosages for maximizing pollutant removal. Practitioner Points Effect of PMS/PDS dosage on BPA degradation by N‐doped biochar was revealed. Contribution of dominated non‐radical pathway increased as PMS/PDS dosage increased. The greater PDS utilization and non‐radical pathway resulted in the higher at low dosage. N‐BC adsorbed more PMS than PDS, leading to an increase in at high dosage.