One-Step Fe/N Co-Doping for Efficient Catalytic Oxidation and Selective Non-Radical Pathway Degradation in Sludge-Based Biochar

This study presents the preparation of iron and nitrogen co-doped sludge-based biochar (FeCN-MSBC) and iron oxide-doped biochar (FeO-MSBC) by ball milling municipal sludge with different iron precursors (K3Fe(CN)6and Fe2O3), followed by pyrolysis. These biochars were utilized to activate persulfate (PMS) for the degradation of phenolic pollutants. The results demonstrate that FeCN-MSBC, formed by the introduction of K3Fe(CN)6, contains Fe/N phases, with surface Fe sites exhibiting a lower oxidation state, which significantly enhances PMS activation efficiency. In contrast, FeO-MSBC, due to the aggregation of Fe2O3/Fe3O4, shows relatively lower catalytic activity. The FeCN-MSBC/PMS system degrades pollutants via a synergistic mechanism involving non-radical pathways mediated by1O2and electron transfer processes (ETP) catalyzed by surface Fe. Electrochemical oxidation and quenching experiments confirm that ETP is the dominant pathway. FeCN-MSBC, prepared at a pyrolysis temperature of 600 °C and an Fe loading of 3 mmol/g TSS, exhibited the best performance, achieving a phenol degradation rate constant (kobs) of 0.127 min−1, 4.5 times higher than that of undoped biochar (MSBC). FeCN-MSBC/PMS maintained high efficiency across a wide pH range and in complex water matrices, exhibiting excellent stability over multiple cycles, demonstrating strong potential for practical applications. This study provides an effective strategy for simultaneous Fe and N doping in sludge-derived biochar and offers mechanistic insights into Fe/N synergistic activation of PMS for practical water treatment.