耿上帅^1,2, 王皓企¹, 梁 飞³, 王立君^4,5, 魏 东¹, 闫 涛¹, 闫良国¹

(1. 济南大学 水利与环境学院, 山东 济南 250022; 2. 山东省核与辐射安全监测中心, 山东 济南 250117;3. 山东水务投资有限公司, 山东 济南 250101; 4. 山东省机械设计研究院, 山东 济南 250031;5. 齐鲁工业大学 机械工程学院, 山东 济南 250031)

引用格式:

耿上帅, 王皓企, 梁飞, 等. 钴锰共掺杂金属有机框架催化过一硫酸盐降解四环素的性能[ J]. 中国粉体技术, 2024,30(2): 113-122.

GENG S S, WANG H Q, LIANG F, et al. Cobalt-manganese co-doped metal-organic framework compound activates peroxymonosulfate for tetracycline degradation[J]. China Powder Science and Technology, 2024, 30(2): 113-122.

收稿日期: 2023-11-09,修回日期:2023-12-26,上线日期:2024-01-18。

基金项目:国家自然科学基金项目,编号:52270071;山东省自然科学基金项目,编号:ZR2020MB091。

第一作者简介:耿上帅(1993—),男,硕士生,研究方向为金属有机框架材料催化过一硫酸盐降解水中污染物。 E-mail: 1055389780@qq.com。

通信作者简介:闫涛(1980—),男,副教授,博士,硕士生导师,研究方向为环境功能材料。 E-mail: yantujn@163.com。

摘要: 【目的】制备高效固体催化剂,实现水中污染物四环素( tetracycline,TC)的高效降解。 【方法】采用溶剂热法制备钴、 锰共掺杂的金属有机框架化合物 MIL-88B(Co-Mn),并用于催化过一硫酸盐去除水中 TC,分别考察钴、 锰不同物质的量比对催化剂性能的影响,进行实验条件优化。 【结果】在催化剂 Co(NO₃ )₂·6H₂O 和 Mn(NO₃ )₂·4H₂O 的物质的量比为 3∶ 2,反应体系 pH 为 5,TC 质量浓度为 10 mg / L,催化剂质量浓度为 20 mg / L,过一硫酸盐浓度为 2 mmol / L,反应时间为 60 min 时,TC 去除率可达 94%以上;所制备的 MIL-88B(Co-Mn)催化剂具有良好的循环利用性,经过 4 次循环,TC 去除率仍大于 90%。 【结论】制备的 MIL-88B(Co-Mn)是一种高效催化剂,在处理抗生素废水的过程中证明是可行的,能有效催化过一硫酸盐去除水中 TC。

关键词: 溶剂热法; 钴锰共掺杂; 金属有机框架; 过硫酸根; 四环素

Objective Due to the complex molecular structure of antibiotics, their recalcitrance to degradation poses a significant environmental threat, harmful to human life and safety. More seriously, this accumulation also has a crucial impact on human survival and the sustainable development of the ecological environment. Advanced oxidation technology based on sulfate radical has been used as an effective treatment option for the removal of antibiotics. In recent years, the use of metal-organic frameworks (MOFs) to catalyze peroxymonosulfate has attracted extensive attention from researchers. Importantly, the catalyst prepared by pre-modification or post-modification of MOFs-based material exhibit key features, includinga porous structure, multiple active sites and good stability. Therefore, a high-efficiency solid catalyst, Co-Mn co-doped metal-organic framework compounds, is studied in this paper for the efficient degradation of TC in water.

Methods In this paper, Co-doped metal-organic framework compound (MIL-88B(Co-Mn)) is prepared by solvothermal method. Firstly, Co(NO₃)₂·6H2O and Mn(NO₃)₂·4H₂O with a total mass of 320 mg were dissolved in the DMF solution containing terephthalic acid according to different molar ratios and the mixture was stirred for 30 minutes; Then, the resultant light red solution was reacted in a muffle furnace at 160 ℃ for 24 h. After cooling down, the obtained product was washed three times with DMF, methanol and deionized water respectively and dried in an oven at 60 ℃ for 12 h. Finally, catalysts with different molar ratios of cobalt and manganese were synthesized.

Results and Discussion X-ray diffraction (XRD) pattern of MIL-88B(Co_x-Mn_1-x) shows the similar diffraction mode with that of MIL-88B (Figure 1), in which distinct characteristic peaks appear at around 14°, 16°, 18°, 27° and 45° respectively.Moreover, the characteristic peaks of MIL-88B(Co_x-Mn_1-x) with different composite proportions are consistent with those of MIL-88B XRD pattern, indicating that the catalysts are successfully prepared. The micro-morphology and element distribution of the samples are revealed by scanning electron microscopy. Figures 2a-2c show that MIL-88B(Co_x-Mn_1-x ) materials all exhibit a relatively uniform and well-defined three-dimensional honeycomb structure. Meanwhile, element mapping images ( Figure 2d) prove the distribution of Co,Mn,C and O elements in MIL-88B(Co_0.6-Mn_0.4 ) material, which further indicates the presence of cobalt-manganese metal and carbon oxygen elements in the catalyst. To determine the valence state and surface element composition of the catalysts, the composition of MIL - 88B ( Co_0.6- Mn_0.4 ) is studied by X-ray photoelectron spectroscopy ( XPS).Elements such as Co, Mn, C, and O are detected in the full spectrum of MIL-88B(Co_0.6-Mn_0.4 ) (Figure 3a). In addition, the XPS spectra of Mn 2p and Co 2p are analyzed, confirming that in the MIL-88B(Co_0.6-Mn_0.4 ) catalyst, Co and Mn elements mainly exist in the form of Co²⁺, Co³⁺, Mn²⁺ and Mn³⁺. The introduction of Co and Mn bimetallic active sites in MIL-88B can further improve the electron transfer efficiency of the catalytic PMS process, thereby promotes the formation of SO₄·^- ,ultimately improving the removal performance of pollutants. The catalytic performance of the catalyst is appraised through TC elimination over MIL-88B(Co_0.6-Mn_0.4 ) in the presence of PMS. As shown in Figure 4a, the prepared MIL-88B(Co_0.6-Mn_0.4 ) catalyst in the experiment exhibits excellent catalytic performance. After the reaction, the degradation rate of TC in the MIL-88B (Co_0.6-Mn_0.4 )-PMS systems reaches 91. 2%. Furthermore, the effect of different molar ratio cobalt-manganese doping amount on the performance of the catalyst is investigated, and the experimental conditions are optimized. The results shows that when the molar ratio of Co(NO₃)₂·6H₂O and Mn(NO₃)₂·4H₂O is 3∶ 2, pH= 5, the TC mass concentration is 10 mg·L^-1, the catalyst mass concentration is 20 mg·L^-1, and the molar mass of peroxymonosulfate is 2 mmol·L^-1, the removal rate of TC can reach more than 94%. Meanwhile, the stability of the catalyst is evaluated through cycling experiments. After the fourth cycle (Figure 8), the MIL-88B(Co-Mn) catalyst maintains approximately 90% of its original catalytic performance, indicating the favorable durability of MIL-88B(Co-Mn).

Conclusion In this study, a cobalt-manganese co-doped metal-organic framework compound MIL-88B(Co_0.6-Mn_0.4 ) is prepared by the solvothermal method. And it is used to remarkably catalyze the removal of tetracycline from water by peroxymonosulfate.The reason is that the appropriate ratio of cobalt-manganese atoms to metals can significantly enhance the bimetallic synergy of metal-organic framework materials, thereby improving the ability of catalysts to activate peroxymonosulfate. Based on cycling experiments, the removal rate of TC can still reach 90. 6%, which proves that MIL-88B (Co_0.6-Mn_0.4) is a new catalyst with high efficiency and reusability. This work also directs a feasible technology for treating actual antibiotic wastewater, and effectively removing TC from water by catalyzing peroxymonosulfate.

Keywords: solvothermal method; cobalt manganese co-doping; metal-organic framework; peroxymonosulfate radical; tetracycline

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