Citation: Jiahong WANG, Zekun XU, Tianjiao LU, Jinming HUANG. Performance of N, Mn doped semi-coke activated carbon catalyzed ozone oxidation for the degradation of tetracycline hydrochloride in water[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(12): 2549-2560. doi: 10.11862/CJIC.20250120 shu

Performance of N, Mn doped semi-coke activated carbon catalyzed ozone oxidation for the degradation of tetracycline hydrochloride in water

School of Environmental Science and Engineering (School of Carbon-Neutral Science and Technology), Shaanxi University of Science & Technology, Xi′an 710021, China

Corresponding author: Jiahong WANG, wangjiahong@sust.edu.cn
Received Date: 20 January 2025
Revised Date: 22 October 2025

Figures(11)

N and Mn modified semi-cake activated carbon (SC) catalysts (N_xMn_y-SC, x∶y was the mass ratio of N and Mn) were synthesized via an impregnation method and applied in the catalytic ozonation of tetracycline hydrochloride (TC) in aqueous solution. The results demonstrated that the manganese loading amount was positively correlated with both surface Mn content and structural disorder. The catalyst N₁Mn₃-SC prepared with an N and Mn mass ratio of 1∶3 exhibited the optimal catalytic performance. The effects of reaction conditions on degradation efficiency were systematically investigated. Increasing catalyst dosage, ozone (O₃) flow rate, and reaction temperature promoted TC degradation, whereas a high initial TC concentration inhibited the process. The influence of solution pH showed a promoting-inhibiting transition with increasing pH values, with the best performance achieved at pH 7. Under the optimal conditions (catalyst: 200 mg·L^-1, TC: 30 mg·L^-1, pH: 7, temperature: 25 ℃, O₃ flow rate: 30 mL·min^-1), N₁Mn₃-SC achieved 93.46% degradation rate of TC within 20 min, with a pseudo-first-order reaction rate constant of 0.138 2 min^-1, significantly higher than that of pristine semi-coke (0.080 1 min^-1). The presence of humic acid, HCO₃^-, and Cl^- slightly suppressed degradation due to competitive consumption of hydroxyl radical (·OH). After five consecutive reaction cycles, the degradation efficiency remained at 84.13%, although the specific surface area decreased to 21 m²·g^-1. A reduction in surface Mn, N, and oxygen-containing functional groups was observed, along with a decrease in the intensity ratio (I_D/I_G) of defect to graphitized Raman peaks intensity to 0.983, indicating increased structural ordering. Radical quenching experiments confirmed the involvement of ·OH, superoxide radical (·O₂^-), and singlet state oxygen (¹O₂) in the catalytic process. Intermediate analysis suggested that TC degradation primarily proceeded via dealkylation and deamidation pathways, leading to eventual mineralization into CO₂ and H₂O.
- semi-coke,
- N, Mn doping,
- catalytic ozone oxidation,
- tetracycline,
- mechanism
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