亚微米级Cu0/Fe3O4复合物多相催化过一硫酸盐降解有机污染物

引用本文: 聂刚, 黄佳, 胡冶州, 丁耀彬, 韩小彦, 唐和清. 亚微米级Cu⁰/Fe₃O₄复合物多相催化过一硫酸盐降解有机污染物[J]. 催化学报, 2017, 38(2): 227-239. doi: 10.1016/S1872-2067(16)62566-4 shu

Citation: Gang Nie, Jia Huang, Yezhou Hu, Yaobin Ding, Xiaoyan Han, Heqing Tang. Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu⁰/Fe₃O₄ submicron composites[J]. Chinese Journal of Catalysis, 2017, 38(2): 227-239. doi: 10.1016/S1872-2067(16)62566-4 shu

亚微米级Cu⁰/Fe₃O₄复合物多相催化过一硫酸盐降解有机污染物

中南民族大学资源与环境学院, 国家民委-教育部共建催化材料重点实验室, 湖北武汉 430074
基金项目:
国家自然科学基金（21377169，21507168）；湖北省自然科学基金（2014CFC1119，2015CFB505）；中央高校基本科研基金（CZW15078）.

摘要: 过一硫酸盐催化活化技术因其可产生强氧化性活性氧化物种，可快速氧化降解并矿化有机污染物的优异性能而备受关注.本文成功制备了亚微米级Cu⁰/Fe₃O₄复合物，发现其能多相催化过一硫酸盐产生单线态氧降解有机污染物.首先，以CuCl₂·2H₂O，FeCl₂·4H₂O和FeCl₃·6H₂O为铜源和铁源，水合肼为还原剂，采用水热法在180℃反应24 h制备了亚微米级磁性Cu⁰/Fe₃O₄复合物.表征结果显示，所制材料为Cu⁰和Fe₃O₄的复合物，颗粒大小约为220 nm；单一相Cu⁰和Fe₃O₄晶体粒径分别为33.8和106.2 nm，而Cu⁰/Fe₃O₄复合物中Cu⁰和Fe₃O₄晶体粒径分别减为20.8和31.9 nm.这表明Cu⁰和Fe₃O₄复合降低了Cu⁰和Fe₃O₄晶体粒径，有利于Cu⁰和Fe₃O₄的分散.BET测试结果表明，Cu⁰/Fe₃O₄复合物比表面积为4.6 m²/g，与Cu⁰颗粒的（4.2 m²/g）相当，但远小于Fe₃O₄的（15.6 m²/g）.制备的Cu⁰/Fe₃O₄复合物可有效催化过一硫酸盐产生单线态氧降解罗丹明B、亚甲基蓝、金橙II、苯酚和对氯酚.当Cu⁰/Fe₃O₄复合物的用量为0.1 g/L，过一硫酸盐浓度为0.5 mmol/L和初始pH为7时，Cu⁰/Fe₃O₄复合物可在30 min内完全降解20 μmol/L的罗丹明B、亚甲基蓝、金橙II以及0.1 mmol/L的苯酚和对氯酚.对比试验显示，在相同条件下，Cu⁰和Fe₃O₄颗粒分别可以降解28%和20%的罗丹明B.这表明Cu⁰/Fe₃O₄复合物中的Cu⁰和Fe₃O₄晶体在催化过一硫酸盐降解污染物的反应中具有协同作用，这主要来源于Cu⁰/Fe₃O₄复合物中Cu⁰和Fe₃O₄的晶体粒径变小和更好的分散.采用分光光度法测定了降解反应液中铜和铁离子的溶出量.当Cu⁰/Fe₃O₄复合物的用量为0.1 g/L，过一硫酸盐浓度为0.5 mmol/L和初始pH为7时，反应60 min后，降解液中铜和铁离子的浓度分别为0.22和0.1 mg/L，仅占复合物中总铜和总铁量的1.1%和0.2%，表明Cu⁰/Fe₃O₄复合物具有较强的化学稳定性.所制Cu⁰/Fe₃O₄复合物具有超顺磁性，借助磁场实现快速分离回收，可循环利用五次，表明其优越的催化稳定性.通过加入乙醇和叠氮化钠，考察了Cu⁰/Fe₃O₄复合物催化活化过一硫酸盐体系中的活性氧化物种.发现100 mmol/L乙醇的加入对污染物的降解无明显影响，而加入同等量的叠氮化钠可完全抑制污染物的降解，表明Cu⁰/Fe₃O₄复合物催化活化过一硫酸盐产生的主要活性氧物种为单线态氧.采用电子顺磁共振谱进一步证实了单线态氧的生成.
基于以上研究，Cu⁰/Fe₃O₄复合物催化活化过一硫酸盐的机理为Cu⁰/Fe₃O₄作为一个电子媒介加速过一硫酸盐和污染物之间的电子转移，从而导致污染物被快速降解.该反应机理不同于常见的金属催化过一硫酸盐产生硫酸根和羟自由基的反应机理.我们推测，电导性优良的Cu⁰在此催化反应中起着关键性作用.本催化方法可作为一种绿色的氧化技术用于环境污染物的氧化降解处理.

关键词:

English

Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu⁰/Fe₃O₄ submicron composites

Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074, Hubei China
Received Date: 14 September 2016
Revised Date: 28 October 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21377169, 21507168), the Fundamental Research Funds for the Central Universities (CZW15078), and the Natural Science Foundation of Hubei Province of China (2014CFC1119, 2015CFB505).

Abstract: Magnetic Cu⁰/Fe₃O₄ submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate (PMS) and the degradation of organic pollutants. The as-prepared magnetic Cu⁰/Fe₃O₄ submicron composites were composed of Cu⁰ and Fe₃O₄ crystals and had an average size of approximately 220 nm. The Cu⁰/Fe₃O₄ composites could efficiently catalyze the activation of PMS to generate singlet oxygen, and thus induced the rapid degradation of rhodamine B, methylene blue, orange II, phenol and 4-chlorophenol. The use of 0.1 g/L of the Cu⁰/Fe₃O₄ composites induced the complete removal of rhodamine B (20 μmol/L) in 15 min, methylene blue (20 μmol/L) in 5 min, orange II (20 μmol/L) in 10 min, phenol (0.1 mmol/L) in 30 min and 4-chlorophenol (0.1 mmol/L) in 15 min with an initial pH value of 7.0 and a PMS concentration of 0.5 mmol/L. The total organic carbon (TOC) removal higher than 85% for all of these five pollutants was obtained in 30 min when the PMS concentration was 2.5 mmol/L. The rate of degradation was considerably higher than that obtained with Cu⁰ or Fe₃O₄ particles alone. The enhanced catalytic activity of the Cu⁰/Fe₃O₄ composites in the activation of PMS was attributed to the synergistic effect of the Cu⁰ and Fe₃O₄ crystals in the composites. Singlet oxygen was identified as the primary reactive oxygen species responsible for pollutant degradation by electron spin resonance and radical quenching experiments. A possible mechanism for the activation of PMS by Cu⁰/Fe₃O₄ composites is proposed as electron transfer from the organic pollutants to PMS induces the activation of PMS to generate ¹O₂, which induces the degradation of the organic pollutants. As a magnetic catalyst, the Cu⁰/Fe₃O₄ composites were easily recovered by magnetic separation, and exhibited excellent stability over five successive degradation cycles. The present study provides a facile and green heterogeneous catalysis method for the oxidative removal of organic pollutants.

Key words:

1. [1] S. Esplugas, D. M. Bila, L. G. T. Krause, M. Dezotti, J. Hazard. Mater., 2007, 149, 631-642.
2. [2] H. Hori, A. Yamamoto, E. Hayakawa, S. Taniyasu, N. Yamashita, S. Kutsuna, H. Kiatagawa, R. Arakawa, Environ. Sci. Technol., 2005, 39, 2383-2388.
3. [3] W. Luo, L. H. Zhu, N. Wang, H. Q. Tang, M. J. Cao, Y. B. She, Environ. Sci. Technol., 2010, 44, 1786-1791.
4. [4] G. P. Anipsitakis, D. D. Dionysiou, Environ. Sci. Technol., 2003, 37, 4790-4797.
5. [5] G. P. Anipsitakis, D. D. Dionysiou, Environ. Sci. Technol., 2004, 38, 3705-3712.
6. [6] S. Y. Yang, P. Wang, X. Yang, L. Shan, W. Y. Zhang, X. T. Shao, R. Niu, J. Hazard. Mater., 2010, 179, 552-558.
7. [7] O. S. Furman, A. L. Teel, R. J. Watts, Environ. Sci. Technol., 2010, 44, 6423-6428.
8. [8] C. D. Qi, X. T. Liu, J. Ma, C. Y. Lin, X. W. Li, H. J. Zhang, Chemosphere, 2016, 151, 280-288.
9. [9] D. Lison, CRC Crit. Rev. Toxicol., 1996, 26, 585-616.
10. [10] P. Nfodzo, H. Choi, Chem. Eng. J., 2011, 174, 629-634.
11. [11] J. Madhavan, P. Maruthamuthu, S. Murugesan, S. Anandan, Appl. Catal. B, 2008, 83, 8-14.
12. [12] A. Rastogi, S. R. Al-Abed, D. D. Dionysiou, Appl.Catal. B, 2009, 85, 171-179.
13. [13] Y. R. Wang, W. Chu, Appl. Catal. B, 2012, 123-124, 151-161.
14. [14] F. Ji, C. L. Li, L. Deng, Chem. Eng. J., 2011, 178, 239-243.
15. [15] J. Liu, J. H. Zhou, Z. X. Ding, Z. W. Zhao, X. Xu, Z. D. Fang, Ultrason. Sonochem., 2017, 34, 953-959.
16. [16] C. Q. Tan, N. Y. Gao, Y. Deng, J. Deng, S. Q. Zhou, J. Li, X. Y. Xin, J. Hazard. Mater., 2014, 276, 452-460.
17. [17] Y. F. Rao, D. Xue, H. M. Pan, J. T. Feng, Y. J. Li, Chem. Eng. J., 2016, 283, 65-75.
18. [18] H. Lin, J. Wu, H. Zhang, Chem. Eng. J., 2014, 244, 514-521.
19. [19] J. Zou, J. Ma, L. W. Chen, X. C. Li, Y. H. Guan, P. C. Xie, C. Pan, Environ. Sci. Technol., 2013, 47, 11685-11691.
20. [20] L. J. Xu, J. L. Wang, Environ. Sci. Technol., 2012, 46, 10145-10153.
21. [21] Y. B. Ding, L. H. Zhu, N. Wang, H. Q. Tang, Appl. Catal. B, 2013, 129, 153-162.
22. [22] C. Cai, H. Zhang, X. Zhong, L. W. Hou, J. Hazard. Mater., 2015, 283, 70-79.
23. [23] Y. B. Ding, H. B. Tang, S. H. Zhang, S. B. Wang, H. Q. Tang, J. Hazard. Mater., 2016, 317, 686-694.
24. [24] Y. Feng, D. L. Wu, Y. Deng, T. Zhang, K. Shih, Environ. Sci. Technol., 2016, 50, 3119-3127.
25. [25] J. Liu, Z. W. Zhao, P. H. Shao, F. Y. Cui, Chem. Eng. J., 2015, 262, 854-861.
26. [26] Y. J. Yao, Y. M. Cai, G. D. Wu, F. Y. Wei, X. Y. Li, H. Chen, S. B. Wang, J. Hazard. Mater., 2015, 296, 128-137.
27. [27] X. G. Duan, Z. M. Ao, L. Zhou, H. Q. Sun, G. X. Wang, S. B. Wang, Appl. Catal. B, 2016, 188, 98-105.
28. [28] X. G. Duan, H. Q. Sun, Y. X. Wang, J. Kang, S. B. Wang, ACS Catal., 2015, 5, 553-559.
29. [29] Y. Zhou, J. Jiang, Y. Gao, J. Ma, S. Y. Pang, J. Li, X. T. Lu, L. P. Yuan, Environ. Sci. Technol., 2015, 49, 12941-12950.
30. [30] K. J. Koski, J. J. Cha, B. W. Reed, C. D. Wessells, D. S. Kong, Y. Cui, J. Am. Chem. Soc., 2012, 134, 7584-7587.
31. [31] Z. Z. Wang, S. R. Zhai, J. L. Lv, H. X. Qi, W. Zheng, B. Zhai, Q. D. An, RSC Adv., 2015, 5, 74575-74584.
32. [32] N. Wang, L. H. Zhu, D. L. Wang, M. Q. Wang, Z. F. Lin, H. Q. Tang, Ultrason. Sonochem., 2010, 17, 526-533.
33. [33] X. Yuan, A. N. Pham, G. W. Xing, A. L. Rose, T. D. Waite, Environ. Sci. Technol., 2012, 46, 1527-1535.
34. [34] G. H. Dong, Z. H. Ai, L. Z. Zhang, Water Res., 2014, 66, 22-30.
35. [35] Y. S. Li, F. L. Jiang, Q. Xiao, R. Li, K. Li, M. F. Zhang, A. Q. Zhang, S. F. Sun, Y. Liu, Appl. Catal. B, 2010, 101, 118-129.
36. [36] R. Wang, Y. H. Li, R. H. Shi, M. M. Yang, J. Mol. Catal. A., 2011, 344, 122-127.
37. [37] X. Y. Zhang, Y. B. Ding, H. Q. Tang, X. Y. Han, L. H. Zhu, N. Wang, Chem. Eng. J., 2014, 236, 251-262.
38. [38] Y. Lei, C. S. Chen, J. Ai, H. Lin, Y. H. Huang, H. Zhang, RSC Adv., 2016, 6, 866-871.
39. [39] R. R. Solís, F. J. Rivas, O. Gimeno, J. L. Pérez-Bote, J. Chem. Technol. Biotechnol., 2016, 91, 51-58.
40. [40] P. Shukla, H. Q. Sun, S. B. Wang, H. M. Ang, M. O. Tadé, Catal. Today, 2011, 175, 380-385.
41. [41] Y. H. Guan, J. Ma, Y. M. Ren, Y. L. Liu, J. Y. Xiao, L. Q. Lin, C. Zhang, Water Res., 2013, 47, 5431-5438.
42. [42] Y. J. Yao, H. Chen, C. Lian, F. Y. Wei, D. W. Zhang, G. D. Wu, B. J. Chen, S. B. Wang, J. Hazard. Mater., 2016, 314, 129-139.
43. [43] L. Duan, B. Z. Sun, M. Y. Wei, S. L. Luo, F. Pan, A. H. Xu, X. X. Li, J. Hazard. Mater., 2015, 285, 356-365.
44. [44] S. L. Luo, L. Duan, B. Z. Sun, M. Y. Wei, X. X. Li, A. H. Xu, Appl. Catal. B, 2015, 164, 92-99.
45. [45] Z. L. Wang, Y. C. Du, Y. L. Liu, B. H. Zou, J. Y. Xiao, J. Ma, RSC Adv., 2016, 6, 11040-11048.
46. [46] W. D. Oh, Z. L. Dong, Z. T. Hu, T. T. Lim, J. Mater. Chem. A, 2015, 3, 22208-22217.
47. [47] Y. C. Du, W. J. Ma, P. X. Liu, B. H. Zou, J. Ma, J. Hazard. Mater., 2016, 308, 58-66.
48. [48] T. Zeng, X. L. Zhang, S. H. Wang, H. Y. Niu, Y. Q. Cai, Environ. Sci. Technol., 2015, 49, 2350-2357.
49. [49] Y. B. Ding, P. Zhou, H. Q. Tang, Chem. Eng. J., 2016, 291, 149-160.

扫一扫看文章

计量

PDF下载量: 4
文章访问数: 1610
HTML全文浏览量: 203

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

亚微米级Cu⁰/Fe₃O₄复合物多相催化过一硫酸盐降解有机污染物

English

Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu⁰/Fe₃O₄ submicron composites

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处