Insights into the mechanism of persulfate activation with biochar composite loaded with Fe for 2,4-dinitrotoluene degradation

Abstract

Iron in biochar composite loaded with Fe (Fex@biochar) is crucial for persulfate activation. However, the iron dosages-driven mechanism linked to the speciation, electrochemical property, and persulfate activation with Fex@biochar remains ambiguous. We synthesized and characterized a series of Fex@biochar and evaluated its catalytic performance in 2,4-dinitrotoluene removal experiments. With increasing FeCl₃ dosage, iron speciation in Fex@biochar changed from γ-Fe₂O₃ to Fe₃O₄, and the variation in functional groups was as follows: Fe-O, aliphatic C-O-H, O-H, aliphatic C-H, aromatic CC or CO, and C-N. The electron accepting capacity of Fex@biochar increased as the FeCl₃ dosage increased from 10 to 100 mM but decreased at 300 and 500 mM FeCl₃. 2,4-dinitrotoluene removal first increased and subsequently decreased, reaching 100% in the persulfate/Fe100@biochar system. The Fe100@biochar also showed good stability and reusability for PS activation, verified by five test cycles. The mechanism analysis indicated that the iron dosage altered the Fe (Ⅲ) content and electron accepting capacity of Fex@biochar during pyrolysis, further controlling persulfate activation and 2,4-dinitrotoluene removal. These results support the preparation of eco-friendly Fex@biochar catalysts.

Keywords: Catalysis mechanism; Electron transfer; Engineered biochar; Iron transformation; Persulfate.