YAO Shaowu1a,2,QIAN Weimin2 ,WANG Yubo1a ,HU Xiaolong1a ,ZHANG Wenbin2 ,SONG Junying1b ,DONG Xiongbo3
1 a. College of Energy and Mining Engineering, b. College of Safety and Environmental Engineering,Shandong University of Science and Technology, Qingdao 266590, China;
2. Huzhou Xinkaiyuan Aggregate Co. , Ltd. , Huzhou 313002, China;
3. Engineering Research Center of Nano-Geomaterials of Ministry of Education, China University of Geosciences (Wuhan), Wuhan 430074, China.
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
Get Citation: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.
Received:2023-10-19.Revised:2024-05-17,Online:2024-10-30.
Funding Project: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
First Author: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。
Corresponding Author: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。
DOI:10.13732/j.issn.1008-5548.2024.06.006
CLC No:TB44; TD985 Type Code:A
Serial No:1008-5548(2024)06-0001-12