·CO3-在基于太阳光驱动的TiO2-贝壳粉降解盐酸四环素中的作用:降解机理和转化路径

引用本文: 王佳琦, 钱庆荣, 陈庆华, 刘欣萍, 罗永晋, 薛珲, 李朝晖. ·CO₃^-在基于太阳光驱动的TiO₂-贝壳粉降解盐酸四环素中的作用:降解机理和转化路径[J]. 催化学报, 2020, 41(10): 1511-1521. doi: S1872-2067(19)63525-4 shu

Citation: Jiaqi Wang, Qingrong Qian, Qinghua Chen, Xin-Ping Liu, Yongjin Luo, Hun Xue, Zhaohui Li. Significant role of carbonate radicals in tetracycline hydrochloride degradation based on solar light-driven TiO₂-seashell composites: Removal and transformation pathways[J]. Chinese Journal of Catalysis, 2020, 41(10): 1511-1521. doi: S1872-2067(19)63525-4 shu

·CO₃^-在基于太阳光驱动的TiO₂-贝壳粉降解盐酸四环素中的作用:降解机理和转化路径

a 福建师范大学环境科学与工程学院, 福建省污染控制与资源循环利用重点实验室, 福建福州 350007;
b 福建师范大学福清分校, 福建福清 350007;
c 福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州 350116
基金项目:
国家自然科学基金（21875037，51502036）；国家重点研发计划（2016YFB0302303）.

摘要: 抗生素的滥用和不当排放对水陆生生态系统造成了严重威胁，在世界各地水环境污染物调研中普遍检测到盐酸四环素的存在.如何解决水体中高稳定、难降解的盐酸四环素污染问题是当前环境领域重点研究的课题之一.在各种去除方法中，利用光化学反应生成活性氧物种如·CO₃^-，·OH，·O₂^-，·SO₄^-和¹O₂等实现对有机污染物的降解在众多研究方法中脱颖而出.·CO₃^-在水体中具有较高的稳态浓度且其对有机物降解具有高选择性.CO₃^2-或HCO₃^-与活性物种如·OH，h⁺，·O₂^-，·SO₄^-等反应可以生成·CO₃^-.传统的半导体光催化剂TiO₂在光照下会产生·OH，·O₂^-及h⁺等活性物种，能有效地降解有机污染物，已有研究发现添加CO₃^2-/HCO₃^-有利于提高UV/TiO₂体系降解有机物的反应速率.
贝壳中含有95%以上的碳酸钙，由于其具有低成本、生态友好、无毒性等特点而越来越受到人们的关注.贝壳与TiO₂复合，利用贝壳在水相中提供的CO₃^2-/HCO₃^-与TiO₂在光照下产生的·OH，·O₂^-及h⁺等活性物种反应生成·CO₃^-促进光催化反应速率的提高，对盐酸四环素的有效去除具有显著意义.
本文通过溶胶-凝胶法合成TiO₂-贝壳粉，采用X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、红外光谱和氮气吸附-脱附测试等技术对所得样品进行了表征.考察了TiO₂-贝壳粉在模拟太阳光下对盐酸四环素的降解性能.结果表明，在模拟太阳光的作用下，40% TS-300在30min内能降解94.0%的盐酸四环素，优于纯TiO₂的降解效率（88.6%）.通过自由基捕获实验比较了TiO₂和TiO₂-贝壳粉体系降解盐酸四环素机理的差异，在TiO₂光催化降解盐酸四环素体系中，·O₂^-和h⁺是主要活性物种.而在TiO₂-贝壳粉体系中，TiO₂在光照条件下产生的·OH，·O₂^-及h⁺通过与贝壳粉在水相中提供的CO₃^2-/HCO₃^-进一步产生·CO₃^-，·CO₃^-、·O₂^-和h⁺协同作用实现盐酸四环素的有效降解.采用HRESI-TOF-MS研究了40% TS-300光降解盐酸四环素的中间转化产物，提出TiO₂-贝壳粉光降解盐酸四环素可能的降解路径.对40% TS-300样品进行了光降解盐酸四环素长效循环测试，结果表明该样品能够保持稳定有效的降解盐酸四环素性能，此为该材料今后的潜在应用奠定了可靠基础.

关键词:

English

Significant role of carbonate radicals in tetracycline hydrochloride degradation based on solar light-driven TiO₂-seashell composites: Removal and transformation pathways

a College of Environmental Science and Engineering, Fujian Key Laboratory of Pollution Control&Resource Reuse, Fujian Normal University, Fuzhou 350007, Fujian, China;
b Fuqing Branch of Fujian Normal University, Fuqing 350300, Fujian, China;
c State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian, China
Received Date: 26 January 2020
Revised Date: 03 March 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (21875037, 51502036), and the National Key R&D Program of China (2016YFB0302303).

Abstract: TiO₂-seashell composites prepared via a sol-gel method were used to generate carbonate radicals (·CO₃^-) under solar light irradiation.·CO₃^-, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO₂-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO₂-seashell composite. This study is expected to provide a new facile pathway for the application of·CO₃^- radicals to degrade special organic pollutants in water.

Key words:

1. [1] Y. Nosaka, A. Y. Nosaka, Chem. Rev., 2017, 117, 11302-11336.
2. [2] L. Zheng, X. Yu, M. Long, Q. Li, Chin. J. Catal., 2017, 38, 2076-2084.
3. [3] X. Li, J. Xie, C. Jiang, J. Yu, P. Zhang, Front. Environ. Sci. Eng., 2018, 12, 1-32.
4. [4] X. Li, J. Yu, M. Jaroniec, X. Chen, Chem. Rev., 2019, 119, 3962-4179.
5. [5] F. Wu, X. Li, W. Liu, S. Zhang, Appl. Surf. Sci., 2017, 405, 60-70.
6. [6] K. Qi, B. Cheng, J. Yu, W. Ho, Chin. J. Catal., 2017, 38, 1936-1955.
7. [7] L. Liang, K. Li, K. Lv, W. Ho, Y. Duan, Chin. J. Catal., 2017, 38, 2085-2093.
8. [8] S. Canonica, T. Kohn, M. Mac, F. J. Real, J. Wirz, U. Von Gunten, Environ. Sci. Technol., 2005, 39, 9182-9188.
9. [9] T. Liu, K. Yin, C. Liu, J. Luo, J. Crittenden, W. Zhang, S. Luo, Q. He, Y. Deng, H. Liu, D. Zhang, Water Res., 2018, 147, 204-213.
10. [10] F. J. Millero, Geochim. Cosmochim. Acta, 1987, 51, 351-353.
11. [11] D. Vione, S. Khanra, S. C. Man, P. R. Maddigapu, R. Das, C. Arsene, R. I. Olariu, V. Maurino, C. Minero, Water Res., 2009, 43, 4718-4728.
12. [12] W. R. Haag, J. Hoigné, Chemosphere, 1985, 14, 1659-1671.
13. [13] M. Cheng, G. Zeng, D. Huang, C. Lai, P. Xu, C. Zhang, Y. Liu, Chem. Eng. J., 2016, 284, 582-598.
14. [14] Y. Liu, X. He, X. Duan, Y. Fu, D. Fatta Kassinos, D. D. Dionysiou, Water Res., 2016, 95, 195-204.
15. [15] J. Huang, S. A. Mabury, Environ. Toxicol. Chem., 2000, 19, 2181-2188.
16. [16] Z. Ruochun, S. Peizhe, T.H. Boyer, Z. Lin, H. Ching Hua, Environ. Sci. Technol., 2015, 49, 3056-3066.
17. [17] W. W. P. Lai, M. H. Hsu, A. Y. C. Lin, Water Res., 2017, 112, 157-166.
18. [18] Y. Li, L. Li, Z. X. Chen, J. Zhang, L. Gong, Y. X. Wang, H. Q. Zhao, Y. Mu, Chemosphere, 2018, 192, 372-378.
19. [19] G. Wang, Q. Zhang, Q. Chen, X. Ma, Y. Xin, X. Zhu, D. Ma, C. Cui, J. Zhang, Z. Xiao, Chem. Eng. J., 2019, 358, 1083-1090.
20. [20] M. Xu, X. Gu, S. Lu, Z. Qiu, Q. Sui, Z. Miao, X. Zang, X. Wu, J. Hazard. Mater., 2015, 286, 7-14.
21. [21] C. Busset, P. Mazellier, M. Sarakha, J. De Laat, J. Photochem. Photobiol. A, 2007, 185, 127-132.
22. [22] R. A. Larson, R. G. Zepp, Environ. Toxicol. Chem., 1987, 7, 265-274.
23. [23] J. Huang, S. A. Mabury, Environ. Toxicol. Chem., 2000, 19, 1501-1507.
24. [24] J. M. Burns, W. J. Cooper, J. L. Ferry, D. W. King, B. P. DiMento, K. McNeill, C. J. Miller, W. L. Miller, B. M. Peake, S. A. Rusak, A. L. Rose, T. D. Waite, Aquat. Sci., 2012, 74, 683-734.
25. [25] C. Luo, J. Gao, D. Wu, J. Jiang, Y. Liu, W. Zhou, J. Ma, Chem. Eng. J., 2019, 358, 1342-1350.
26. [26] J. Yang, Z. Dong, C. Jiang, H. Liu, J. Li, J. Hazard. Mater., 2019, 363, 428-438.
27. [27] B. Bhushan, Y. C. Jung, Prog. Mater. Sci., 2011, 56, 1-108.
28. [28] R. M. Erb, R. Libanori, N. Rothfuchs, A. R. Studart, Science, 2012, 335, 199-204.
29. [29] H. Jiale, L. Liqin, S. Daohua, C. Huimei, Y. Dapeng, L. Qingbiao, Chem. Soc. Rev., 2015, 44, 6330-6374.
30. [30] S. L. Zhong, J. Zhuang, D. P. Yang, D. Tang, Biosens. Bioelectron., 2017, 96, 26-32.
31. [31] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
32. [32] N. F. F. Moreira, C. Narciso da Rocha, M. Inmaculada Polo Lopez, L. M. Pastrana Martinez, J. L. Faria, C. M. Manaia, P. Fernandez Ibanez, O. C. Nunes, A. M. T. Silva, Water Res., 2018, 135, 195-206.
33. [33] J. Shen, R. Wang, Q. Liu, X. Yang, H. Tang, J. Yang, Chin. J. Catal., 2019, 40, 380-389.
34. [34] X. Li, J. Xiong, Y. Xu, Z. Feng, J. Huang, Chin. J. Catal., 2019, 40, 424-433.
35. [35] L. Hu, J. Yan, C. Wang, B. Chai, J. Li, Chin. J. Catal., 2019, 40, 458-469.
36. [36] G. Zhang, X. He, M. N. Nadagouda, K. E. O'Shea, D. D. Dionysiou, Water Res., 2015, 73, 353-361.
37. [37] H. Wang, N. Wang, B. Wang, H. Fang, C. Fu, C. Tang, F. Jiang, Y. Zhou, G. He, Q. Zhao, Y. Chen, Q. Jiang, Environ. Int., 2016, 89-90, 204-211.
38. [38] X. Fu, W. A. Zeltner, Q. Yang, M. A. Anderson, J. Catal., 1997, 168, 482-490.
39. [39] Y. Li, K. Lv, W. Ho, F. Dong, X. Wu, Y. Xia, Appl. Catal. B, 2017, 202, 611-619.
40. [40] T. Phongamwong, W. Donphai, P. Prasitchoke, C. Rameshan, N. Barrabeis, W. Klysubun, G. Rupprechter, M. Chareonpanich, Appl. Catal. B, 2017, 207, 326-334.
41. [41] Z. A. Huang, Q. Sun, K. Lv, Z. Zhang, L. Mei, L. Bing, Appl. Catal. B, 2015, 164, 420-427.
42. [42] H. Xue, Y. Chen, X. Liu, Q. Qian, Y. Luo, M. Cui, Y. Chen, D. P. Yang, Q. Chen, Mater. Sci. Eng. C, 2018, 82, 197-203.
43. [43] X. L. Zhou, W. Z. Liu, C. Tian, S. Q. Mo, X. M. Liu, H. Deng, Z. Lin, Chem. Eng. J., 2018, 351, 816-824.
44. [44] B. Erdem, R. A. Hunsicker, G. W. Simmons, E. D. Sudol, V. L. Dimonie, M. S. El Aasser, Langmuir, 2001, 17, 2664-2669.
45. [45] G. Li, C. Liu, Y. Liu, Appl. Surf. Sci., 2006, 253, 2481-2486.
46. [46] H. Gao, Y. Sun, J. Zhou, R. Xu, H. Duan, ACS Appl. Mater. Interfaces, 2013, 5, 425-432.
47. [47] S. J. Abbas, P. V. R. K. Ramacharyulu, H. H. Lo, S. I. Ali, S. C. Ke, Appl. Catal. B, 2017, 210, 276-289.
48. [48] X. Wang, J. Jia, Y. Wang, Chem. Eng. J., 2017, 315, 274-282.
49. [49] Z. Zhi, Y. Yang, H. Hai, Y. Xin, H. Dong, L. Zhi, Y. Yan, C. Li, P. Huo, Catal. Sci. Technol., 2017, 7, 4092-4104.
50. [50] Y. Yang, Z. T. Zeng, C. Zhang, D. L. Huang, G. M. Zeng, R. Xiao, C. Lai, C. Y. Zhou, H. Guo, W. J. Xue, M. Cheng, W. J. Wang, J. J. Wang, Chem. Eng. J., 2018, 349, 808-821.
51. [51] S. Li, J. Hu, J. Hazard. Mater., 2016, 318, 134-144.
52. [52] Y. Chen, K. Liu, Chem. Eng. J., 2016, 302, 682-696.
53. [53] Y. Liu, X. He, X. Duan, Y. Fu, D. D. Dionysiou, Chem. Eng. J., 2015, 276, 113-121.
54. [54] G. V. Buxton, C. L. Greenstock, W. P. Helman, A. B. Ross, J. Phys. Chem. Ref. Data, 1988, 17, 513-886.
55. [55] Y. Li, L. Li, Z. X. Chen, J. Zhang, L. Gong, Y. X. Wang, H. Q. Zhao, Y. Mu, Chemosphere, 2017, 192, 372-378.
56. [56] Z. Zuo, Z. Cai, Y. Katsumura, N. Chitose, Y. Muroya, Radiat. Phys. Chem., 1999, 55, 15-23.
57. [57] F. A. Villamena, E. J. Locigno, A. Rockenbauer, C. M. Hadad, J. L. Zweier, J. Phys. Chem. A, 2007, 111, 384-391.
58. [58] F. He, W. Zhao, L. Liang, B. Gu, Environ. Sci. Technol. Lett., 2014, 1, 499-503.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

·CO₃^-在基于太阳光驱动的TiO₂-贝壳粉降解盐酸四环素中的作用:降解机理和转化路径

English

Significant role of carbonate radicals in tetracycline hydrochloride degradation based on solar light-driven TiO₂-seashell composites: Removal and transformation pathways

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