【摘要】 为了实现医药废水中新污染物四环素（Tetracycline,TC）的有效降解,研究采用水热共沉淀法制备了MnFe₂O₄@MIL-101复合材料,并将其用于活化过一硫酸盐（Peroxymonosulfate,PMS）以降解TC。研究考察了PMS用量、MnFe₂O₄@MIL-101用量、溶液pH值和四环素初始浓度对水中四环素去除的影响。结果显示,当PMS质量浓度为0.2 g/L、MnFe₂O₄@MIL-101质量浓度为0.2 g/L、TC质量浓度为20 mg/L,pH值为7时,在吸附催化协同作用下反应120 min后,MnFe₂O₄@MIL-101/PMS吸附/催化体系对TC的去除率达到86%。值得关注的是,在反应结束后,电感耦合等离子体质谱（ICP-MS）检测出Mn和Fe的浸出质量浓度均低于0.02 mg/L,表明材料在降解过程中具有良好的结构稳定性,金属离子浸出风险低。同时,自由基猝灭试验及电子顺磁共振（EPR）分析显示,MnFe₂O₄@MIL-101/PMS体系中主要以自由基(SO₄^·-、·OH、O₂^·-)和非自由基（¹O₂）两种机制的协同作用降解TC,其中¹O₂是主导活性物种。此外,该体系对亚甲基蓝（Methylene Blue,MB）、双酚A（Bisphenol A,BPA）和双氯芬酸（Diclofenac,DCF）3种新污染物均具有良好的降解效果（去除率>80%）。因此,MnFe₂O₄@MIL-101在活化PMS方面表现出对新污染物良好的降解能力,具有潜在应用价值。更多还原

【Abstract】 To effectively degrade Tetracycline（TC）, a novel pollutant in pharmaceutical wastewater, this study developed a MnFe₂O₄@MIL-101 composite material activated by Peroxymonosulfate（PMS） using the hydrothermal co-precipitation method. Initially, we investigated the effects of PMS dosage, MnFe₂O₄@MIL-101 dosage, solution pH, and the initial mass concentration of tetracycline on the removal efficiency of tetracycline from water. The results indicate that under the conditions of a PMS mass concentration of 0.2 g/L, a MnFe₂O₄@MIL-101 dosage of 0.2 g/L, an initial TC mass concentration of 20 mg/L, and a pH value of 7, the TC removal efficiency reached 86% after 120 minutes of reaction in the MnFe₂O₄@MIL-101/PMS adsorption/catalysis system, owing to the synergistic effect of adsorption and catalysis. Notably, post-reaction analysis revealed that the leaching concentrations of Mn and Fe were both below 0.02 mg/L, as detected by Inductively Coupled Plasma Mass Spectrometry（ICP-MS）. This finding indicates the material’s excellent structural stability during the degradation process and a low risk of metal ion leaching. Additionally, radical quenching experiments and Electron Paramagnetic Resonance（EPR） analysis demonstrated that the MnFe₂O₄@MIL-101/PMS system primarily degrades Tetracycline（TC） through the synergistic action of two mechanisms: radicals（SO■, ·OH, O■） and non-radicals（¹O₂）, with ¹O₂ being the dominant reactive species. Furthermore, the system exhibited effective degradation of other emerging pollutants, including Methylene Blue（MB）, Bisphenol A（BPA）, and Diclofenac（DCF）, with removal efficiencies exceeding 80% for all compounds. This demonstrates that MnFe₂O₄@MIL-101 is highly effective in degrading emerging pollutants when combined with activated PMS, highlighting its promising application potential. Additionally, the degradation pathways of Tetracycline（TC） were proposed, and the toxicity of the intermediates was evaluated. Three possible degradation pathways for TC were identified, primarily involving demethylation, decarbonylation, deamidation, and ring-opening reactions. These processes effectively break down toxic structures in TC, resulting in the formation of less toxic intermediate products.更多还原