College of Environmental Science and Engineering, Hunan University

针对四环素类抗生素污染物在水中不断累积,对人体健康和生态环境造成严重危害这一问题,本研究制备了 CoFe2O4 / MnO2新型复合材料,并将其作为高效过一硫酸盐(PMS)活化剂, 用于降解水体中的盐酸四环素(TCH)。 降解结果表明 CoFe2O4 / MnO2 -PMS 体系具有突出的 TCH去除效率,反应 40 min 后,去除率可达 92.7%,远高于单一催化剂-PMS 体系。 影响因素实验结果显示, CoFe2O4 / MnO2-PMS 降解体系具有广泛的 pH 适用性, 并且在各种阴离子的存在下仍能保持较高的降解活性。 此外,CoFe2O4 / MnO2-PMS 降解体系具有良好的稳定性和可重复利用性,在 5 次循环后仍保持较高的催化活性和 TCH 降解率。 机理分析表明 CoFe2O4 / MnO2复合材料在催化 PMS 降解 TCH 的过程中,存在 Co2+ / Co3+、Fe3+ / Fe2+和 Mn3+ / Mn4+的价态循环并参与电子转移过程,从而使得活化过程中 SO-4·和·OH 被充分释放,并通过一系列典型的链式反应高效降解 TCH。

To address the issue that tetracycline antibiotic pollutants are accumulating in water andcausing serious harm to human health and the ecological environment, this study prepared a novel com⁃posite material of CoFe2O4 / MnO2 and used it as a highly efficient permonosulfate (PMS) activator forthe degradation of tetracycline hydrochloride (TCH) in the water body. The degradation results showedthat the CoFe2 O4 / MnO2 - PMS system had outstanding TCH removal efficiency, which could reach92.7% after 40 min of reaction, much higher than that of the single catalyst-PMS system. The resultsof the influencing factor experiments showed that the CoFe2O4 / MnO2 -PMS degradation system had awide range of pH suitability and a stable degradation activity in the presence of various anions. In addi⁃tion, the CoFe2 O4 / MnO2 -PMS degradation system had good stability and reusability, showing highcatalytic activity and TCH degradation rate after 5 cycles. Mechanistic analysis showed that the valencecycles of Co2+ / Co3+, Fe3+ / Fe2+ and Mn3+ / Mn4+ existed in the CoFe2O4 / MnO2 composites to participatein the electron transfer process during the catalytic PMS degradation of TCH, leading to the full releaseof SO4· and ·OH during the activation process and the effective degradation of TCH through a seriesof typical chain reactions.

国家自然科学基金(51979103, 52100181, 51909085);湖南省自然科学基金(2022JJ10011, 2022JJ40077, 2020RC5012)

张贤胜, 孙婧雯, 刘智峰. CoFe2O4 / MnO2 活化过一硫酸盐降解盐酸四环素的研究[J]. 能源环境保护,2023, 37(5): 57-70.

ZHANG Xiansheng, SUN Jingwen, LIU Zhifeng. Degradation of tetracycline hydrochloride by CoFe2O4 / MnO2activated permonosulfate[J]. Energy Environmental Protection, 2023, 37(5): 57-70.