广西师范大学学报（自然科学版） ›› 2024, Vol. 42 ›› Issue (1): 156-167.doi: 10.16088/j.issn.1001-6600.2023050807

• 研究论文 • 上一篇    下一篇

复合催化剂S-CuCo2O4的制备及其活化PMS降解CIP性能研究

张孟洋1, 侯东睿1, 罗静2, 孙庆功2, 杨豪1, 王剑峰1*   

  1. 1.郑州大学 生态与环境学院, 河南 郑州 450001;
    2.郑州大学 化工学院, 河南 郑州 450001
  • 收稿日期:2023-05-08 修回日期:2023-05-18 出版日期:2024-01-25 发布日期:2024-01-19
  • 通讯作者: 王剑峰(1972—),女,河南淇县人,郑州大学副教授,博士。E-mail:1514903022@qq.com
  • 基金资助:
    国家自然科学基金(22178326)

Preparation of S-CuCo2O4 Composite Catalysts and Study on Its Performance of Activating Peroxymonosulfate to Degrade Ciprofloxacin

ZHANG Mengyang1, HOU Dongrui1, LUO Jing2, SUN Qinggong2, YANG Hao1, WANG Jianfeng1*   

  1. 1. School of Ecology and Environment, Zhengzhou University, Zhengzhou Henan 450001, China;
    2. School of Chemical Engineering, Zhengzhou University, Zhengzhou Henan 450001, China
  • Received:2023-05-08 Revised:2023-05-18 Online:2024-01-25 Published:2024-01-19

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摘要： 采用水热法,以硫脲为硫源对CuCo2O4进行硫化处理合成S-CuCo2O4,对复合催化剂S-CuCo2O4进行XRD、FT-IR、SEM、XPS、ICP-OES、EPR表征,并考察其活化过一硫酸盐(PMS)降解环丙沙星(ciprofloxacin,CIP)的效果。实验结果表明:成功制备出S-CuCo2O4催化剂,在其表面富含Co(Ⅱ)和Cu(Ⅰ);当催化剂投加量为0.06 g/L、PMS投加量为0.2 g/L、pH=6.4时,复合催化剂S-CuCo2O4在25 min后对CIP的降解效率可达96.8%,降解效果明显优于CuCo2O4、CuCo2S4。自由基淬灭实验和EPR测试表明,SO-4·和1O2是反应体系的主要活性氧物种,其可能的催化机理是:Cu(Ⅰ)和Co(Ⅱ)能直接与PMS反应生成自由基,同时Cu(Ⅰ)能还原Co(Ⅲ)生成Co(Ⅱ),促进Co(Ⅱ)/Co(Ⅲ)循环,催化剂表面存在的氧空位也可与PMS反应生成1O2,在活性氧物种的共同作用下CIP被高效降解。复合催化剂S-CuCo2O4在4次循环使用后对CIP的降解效率仍可达93.5%,证明其循环稳定性较好;对其他污染物也有较好的降解效率,具有较好的通用性,在废水处理中具有良好的应用前景。

关键词: 环丙沙星, 过一硫酸盐, 活化, 降解, 非均相催化剂, CuCo2O4, 硫化

Abstract: S-CuCo2O4 was prepared by using thiourea as sulfur source to vulcanize CuCo2O4 via a simple hydrothermal method. The composite catalyst S-CuCo2O4 was characterized by XRD, FT-IR, SEM, XPS, ICP-OES and EPR, and the degradation effect of ciprofloxacin by activating PMS was investigated. The experimental results showed that S-CuCo2O4 catalyst has been prepared successfully, and its surface is rich in Co(Ⅱ) and Cu(Ⅰ); when the dosage of catalyst was 0.06 g/L, the dosage of PMS was 0.2 g/L and pH was 6.4, the S-CuCo2O4 showed superior behavior for degradation of ciprofloxacin with the efficiency as high as 96.8% in 25 min, better than that of CuCo2O4 and CuCo2S4. Finally, it was proved that SO-4· and 1O2 were the main reactive oxygen species in the reaction system by free radical quenching experiment and EPR test. The possible catalytic mechanism is as follows: Cu(Ⅰ) and Co(Ⅱ) can react directly with persulfate (PMS) to form free radicals, and Cu(Ⅰ) can reduce Co(Ⅲ) to form Co(Ⅱ), promoting the Co(Ⅱ)/Co(Ⅲ) cycle,the oxygen vacancies on the catalyst surface can also react with PMS to form 1O2, and ciprofloxacin can be efficiently degraded under the joint action of reactive oxygen species. The degradation efficiency of the compound catalyst S-CuCo2O4 for ciprofloxacin was still up to 93.5% after four cycles, which proved that the cyclic stability was good. It also has good degradation efficiency for other pollutants, and excellent generality, suggesting its potential in wastewater treatment.

Key words: ciprofloxacin, peroxymonosulfate, activation, degradition, heterogeneous catalyst, CuCo2O4, sulfuration

中图分类号:  X703;TQ426

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