姚绍武1a，2 ，钱伟民2 ，王誉博1a ，胡小龙1a ，张文彬2 ，宋俊颖1b ，董雄波3
1. 山东科技大学 a. 能源与矿业工程学院， b. 安全与环境工程学院，山东 青岛 266590；2. 湖州新开元碎石有限公司，浙江 湖州 313002；3. 中国地质大学（武汉） 教育部纳米地质材料工程研究中心，湖北 武汉 430074
引用格式：
姚绍武，钱伟民，王誉博，等. CuO-高岭石活化PMS降解诺氟沙星性能［J］. 中国粉体技术，2024，30（6）：1-12.
YAO Shaowu， QIAN Weimin， WANG Yubo， et al. Catalytic performance of CuO-kaolinite composite for norfloxacin degradation by activating peroxymonosulfate［J］. China Powder Science and Technology，2024，30（6）：1−12.
DOI：10.13732/j.issn.1008-5548.2024.06.006
收稿日期：2023-10-19，修回日期：2024-05-17，上线日期：2024-10-30。
基金项目：国家自然科学基金项目，编号：52204289；山东省自然科学基金项目，编号：ZR2022QE236；青岛市自然科学基金项目，编号：23-2-1-107-zyyd-jch
第一作者简介：姚绍武（1977—），男，硕士，教授级高级工程师，研究方向为非金属矿山的绿色建设和矿山资源的高值化利用。E-mail：1207768437@qq. com。
通信作者简介：胡小龙（1989—），男，讲师，博士，硕士生导师，研究方向为非金属矿物功能材料。E-mail：xiaolonghu@sdust. edu. cn。
摘要：【目的】 为解决纯过硫酸盐催化剂在制备过程中易团聚的问题，分析引入高岭石载体后催化剂的结构和催化性能的变化规律，实现对抗生素废水中有机污染物的高效降解。【方法】 首先以高岭石为载体，采用水热煅烧法制备了CuO-高岭石复合材料。使用物相分析、 X射线光电子谱、扫描电子显微镜和氮吸附仪等对材料的晶体结构、表面化学态、微观形貌、比表面积以及孔结构特征进行了表征，考察不同 CuO与高岭石质量比、催化剂用量和过一硫酸盐（peroxymono⁃sulfate，PMS）用量对NOR降解效率的影响，进行实验条件优化，并系统分析CuO-高岭石复合材料催化PMS降解NOR的机制。【结果】 CuO 与高岭石质量比为 40% 时 CuO-高岭石复合材料具有最优的催化性能，在催化剂用量为 1. 5 g/L，PMS用量为 1. 0 mmol/L，NOR初始质量浓度为 10 mg/L，反应时间为 60 min时，NOR的降解效率为 76. 21%； CuO-高岭石中Cu（I）、 Cu（II）之间的价态循环参与了PMS的活化，反应体系中主要的活性物种是单线态氧1 O2，而超氧自由基O2 •-、硫酸根自由基SO4 •-和羟基自由基• OH也参与了NOR降解过程。【结论】 CuO-高岭石复合材料中，CuO纳米片能够均匀地分散并沉积在高岭石载体表面，显著减少了 CuO 纳米片的相互团聚，使得更多反应活性位点暴露，增强了复合材料对PMS的活化能力和对NOR的降解能力。
Objective Due to the overuse of pharmaceutical antibiotics， residues have been frequently detected in different environmental matrices， including surface water， sewage， and soils. The presence of antibiotics in environment can cause potential adverse effects on human and ecological system due to their acute and chronic toxicity and the development of antibiotic resistance. However， traditional wastewater purification technologies are ineffective in eliminating antibiotics. In recent years， the advanced oxidation process （AOP） based on sulfate radicals has been confirmed as the most suitable and efficient way to remove such pollutants from wastewater. The CuO-peroxymonosulfate （PMS） system， in particular， has gained considerable attention due to its strong oxidation ability. Nevertheless， the high surface energy of CuO often leads to aggregation during the synthesis process，reducing the amount of active sites and specific surface area. To address this problem， kaolinite was introduced as a support for CuO in this study， and changes in the structure and catalytic performance of the CuO-kaolinite catalyst were analyzed to achieve efficient degradation of organic pollutants in antibiotic wastewater.
Methods In this paper， CuO-kaolinite composite was fabricated using a hydrothermal calcination method. Initially，1. 0 g of sepiolite was mixed with 50 mL of distilled water and stirred for 0. 5 h. Then， different amounts of Cu （NO3）2 ·3H2O were added to the solution and stirred for 10 min. Subsequently， an ammonia-water solution （v：v=1：1） was added drop-wise to adjust the pH value to 7. 5~8 at room temperature. After stirring for 15 min， the mixture was transferred into a 100 mL Teflon-lined stainless-steel autoclave and heated at 150 ℃ for 5 h. The resulting products were washed， dried， ground， and then calcined in a muffle furnace at 250 ℃ for 3 h. Finally， after simple grinding， the CuO-kaolinite composite with different mass ratios of CuO and kaolinite was synthesized. The crystal structure， surface chemical state， microstructure， specific surface area，
Results and discussion The effects of different mass ratios of CuO and kaolinite， catalyst dosages， PMS dosages， initial concentration of norfloxacin （NOR）， initial pH of the solution， and coexisting anions on the degradation efficiency of NOR were investigated. The experimental results indicated that higher NOR degradation efficiency was achieved with the CuO-kaolinite-PMS system compared to other oxidation systems. Specifically， when the mass ratio of CuO and kaolinite was 40%， the CuO-kaolinite composite exhibited optimal catalytic performance. At a catalyst dosage of 1. 5 g/L， a PMS dosage of 1. 0 mmol/L， and an initial NOR concentration of 10 mg/L， the degradation efficiency of NOR after reacting for 60 min was about 76. 21%. An increase in catalyst dosage initially led to a significant enhancement in NOR degradation efficiency， followed by a slight increase， while excessive PMS had an inhibitory effect. A higher initial concentration of NOR gradually decreased its degradation efficiency. Within a wide pH range， high NOR removal efficiency was achieved in the composite-PMS system， demonstrating its good practical application potential. The coexisting Cl-， HCO3-， and H2PO4-in this system exhibited inhibitory effects on the NOR degradation， while NO3- had a relatively minor impact. In addition， the catalytic mechanism of the CuO-kaolinite composite for NOR degradation was systematically analyzed， revealing that the valence cycle between the Cu2+ and Cu+ in CuO-kaolinite composite was involved in the activation of PMS. The main active species in the reaction system were singlet oxygen （1 O2）， while superoxide radicals （O2 •-）， sulfate radicals （SO4 •-）， and hydroxyl radicals （• OH） also contributed to the NOR degradation.
Conclusion The introduction of kaolinite carriers allows for the formation of CuO nanosheets with smaller grain sizes， which are dispersed and deposited on the surface of kaolinite. The specific surface area and pore volume of the composite are greater than those of pure CuO. In CuO-kaolinite composite， CuO nanosheets are uniformly dispersed and deposited on the surface of kaolinite carriers， significantly reducing their self-aggregation and exposing more reactive sites， thereby enhancing the activation efficiency of PMS. As a result， more active species， such as1O2， O2 •-， SO4 •-， and•OH， are continuously produced， which contributes to the NOR degradation. In summary， this work provides a new approach for the structure design and preparation of mineral-based PMS catalysts with efficient catalytic performance and adsorption capacity， guiding their application in antibiotic wastewater treatment.
Keywords：CuO； kaolinite； peroxymonosulfate； norfloxacin
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