C-Cl共掺杂TiO<sub>2</sub>/凹凸棒复合催化剂的制备及其可见光催化性能

引用本文: 邓丽娟, 谢毅, 张高科. C-Cl共掺杂TiO₂/凹凸棒复合催化剂的制备及其可见光催化性能[J]. 催化学报, 2017, 38(2): 379-388. doi: 10.1016/S1872-2067(17)62774-8 shu

Citation: Lijuan Deng, Yi Xie, Gaoke Zhang. Synthesis of C-Cl-codoped titania/attapulgite composites with enhanced visible-light photocatalytic activity[J]. Chinese Journal of Catalysis, 2017, 38(2): 379-388. doi: 10.1016/S1872-2067(17)62774-8 shu

C-Cl共掺杂TiO₂/凹凸棒复合催化剂的制备及其可见光催化性能

a 武汉理工大学硅酸盐建筑材料国家重点实验室, 湖北武汉 430070;
b 武汉理工大学资源与环境工程学院, 湖北省矿物资源加工与环境重点实验室, 湖北武汉 430070
基金项目:
国家重点基础研究发展计划（973计划，2007CB613302）；湖北省自然科学基金（2016CFA078）.

摘要: TiO₂光催化剂具有无毒、物理化学性质稳定及光催化活性较高等优点，因而在能源及环境净化等领域备受关注.但是，TiO₂纳米颗粒作为催化剂仍存在以下不足：（1）TiO₂带隙较宽，只能吸收利用太阳光能的紫外光部分，而照射到地球表面的太阳光大部分为可见光；（2）光生载流子（电子/空穴）的复合使得光催化活性不高；（3）纳米催化剂的回收利用困难；（4）单独使用TiO₂，成本较高；（5）针对低浓度有机污染，常见TiO₂催化剂比表面积较小，吸附富集能力较差，导致光催化降解效率较低.TiO₂自身这些缺陷大大限制了其进一步的实际应用.
针对上述这些问题，我们在本研究中设计了一种简便易行的溶胶凝胶法，在较低的温度（70℃）下合成了非金属C-Cl共掺杂的TiO₂/凹凸棒（TiO₂/ATT）复合催化剂.XRD及HRTEM分析证明，通过调节反应溶液的pH可以分别合成含锐钛矿/金红石、锐钛矿/金红石/板钛矿的两相和三相的混合相TiO₂，且锐钛矿/金红石比例可以通过改变pH而进行调节.XPS分析证明，C和Cl同时成功掺进TiO₂/ATT复合催化剂.UV-Vis漫反射结果显示，非金属C和Cl的掺杂使得所合成复合催化剂的光吸收性能明显拓展到可见光区，因而可以充分利用可见光能进行有机污染物催化降解，而ATT作为TiO₂的载体，减少了TiO₂使用量，改善了TiO₂的表面特性和孔结构，且有利于光催化剂的回收利用.
以酸性红G为目标有机污染物，在可见光照射下对复合催化剂的可见光催化活性进行了测试.结果表明，当合成反应体系的pH值为3.0时，所获得的锐钛矿/金红石/板钛矿三相TiO₂/ATT复合催化剂具有良好的可见光吸收特性，其可见光催化活性远远高于市售P25型TiO₂，对难降解的酸性红溶液G具有优异的脱色效果和良好的TOC去除性能.循环光催化实验和FTIR表征结果表明，在5次循环利用后，TiO₂/ATT复合催化剂仍表现出很高的催化活性，表明其稳定性优异.荧光分析和自由基捕获实验表明，光催化降解反应中的主要活性物种是羟基自由基、空穴和超氧自由基.
TiO₂/ATT复合催化剂高效稳定的可见光催化性能主要归因于：（1）非金属C和Cl的共掺杂改善了其可见光吸收性能；（2）催化剂中的TiO₂由金红石、锐钛矿和板钛矿混合相组成，有利于抑制光生载流子的复合；（3）多孔结构的ATT作为载体提高了TiO₂的比表面积，增加了反应活性位，同时改善了孔结构，从而有利于模拟有机污染物（酸性红G）分子的吸附和降解，有利于反应产物扩散，从而提高了催化剂的可见光催化效率.

关键词:

English

Synthesis of C-Cl-codoped titania/attapulgite composites with enhanced visible-light photocatalytic activity

a State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China;
b Hubei Key Laboratory of Mineral Resources Processing, Hubei Provincial Collaborative Innovation Center for High Efficient Utilization of Vanadium Resources, and School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China
Received Date: 21 October 2016
Revised Date: 23 December 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Basic Research Program of China (973 Program, 2007CB613302) and the Natural Science Foundation of Hubei Province (2016CFA078).

Abstract: We demonstrate the synthesis of C-Cl-codoped titania/attapulgite (TiO₂/ATT) composites containing a mixture of TiO₂ phases by a facile sol-gel method at 70℃ using titanium tetraisopropoxide as the TiO₂ precursor and ATT as a support for the TiO₂ nanoparticles. The photocatalytic activity of the C-Cl-codoped TiO₂/ATT composites with mixed anatase/brookite/rutile phases obtained at pH=3.0 was much higher than that of commercially available Degussa P25 for the photocatalytic degradation of acid red G under visible-light irradiation. The excellent photocatalytic activity of the developed composite originates from the nonmetal codoping, which extends the absorption edge of TiO₂ into visible region, and the presence of multiple phases, which slow the recombination of photoexcited electron/hole pairs. The formation of hydroxyl radicals during the photocatalytic degradation process was detected by photoluminescence probing using terephthalic acid. A mechanism for photocatalysis over the C-Cl-codoped TiO₂/ATT composites was proposed.

Key words:

1. [1] D. D. Tang, G. K. Zhang, Appl. Surf. Sci., 2017, 391, 415-422.
2. [2] D. Lu, Z. Wan, G. K. Zhang, Appl. Surf. Sci., 2015, 358, 223-230.
3. [3] Z. Wan, G. K. Zhang, J. Mater. Chem. A, 2015, 3, 16737-16745.
4. [4] Q. L. Xu, J. G. Yu, J. Zhang, J. F. Zhang, G. Liu, Chem. Commun., 2015, 15, 7950-7953.
5. [5] X. Li, J. G. Yu, M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603-36.
6. [6] H. J. Huang, D. Z. Li, Q. Lin, Y. Shao, W. Chen, Y. Hu, Y. B. Chen, X. Z. Fu, J. Phys. Chem. C, 2009, 113, 14264-14269.
7. [7] W. J. Zhou, H. Liu, J. Y. Wang, D. Liu, G. J. Du, J. Cui, ACS Appl. Ma-ter. Interfaces, 2010, 2, 2385-2392.
8. [8] Y. Du, D. D. Tang, G. K. Zhang, X. Y. Wu, Chin. J. Catal., 2015, 36, 2219-2228.
9. [9] H. Xu, L. Z. Zhang, J. Phys. Chem. C, 2009, 113, 1785-1790.
10. [10] S. Sakthivel, M. Janczarek, H. Kisch, J. Phys. Chem. B, 2004, 108, 19384-19387.
11. [11] H. G. Yu, H. Irie, Y. Shimodaira, Y. Hosogi, Y. Kuroda, M. Miyauchi, K. Hashimoto, J. Phys. Chem. C, 2010, 114, 16481-16487.
12. [12] W. H. Jing, W. G. Wang, X, W. H. Xing, Chin. J. Catal., 2009, 30, 426-432.
13. [13] I. C. Kang, Q. W. Zhang, S. Yin, T. Sato, F. Saito, Appl. Catal. B, 2008, 80, 81-87.
14. [14] F. Chen, W. W. Zou, W. W. Qu, J. L. Zhang, Catal. Commun., 2009, 10, 1510-1513.
15. [15] J. Liu, G. K. Zhang, Phys. Chem. Chem. Phys., 2014, 16, 8178-8192.
16. [16] W. J. Zhang, S. L. Zhu, Y. Li, F. H. Wang, H. B. He, Chin. J. Catal., 2007, 28, 269-273.
17. [17] Y. Ma, G. K. Zhang, Chem. Eng. J., 2016, 288, 70-78.
18. [18] T. C. An, J. X. Chen, G. Y. Li, X. J. Ding, G. Y. Sheng, J. M. Fu, B. X. Mai, K. E. O'Shea, Catal. Today, 2008, 139, 69-76.
19. [19] Y. S. Liu, P. Liu, Z. X. Su, F. S. Li, F. S. Wen, Appl. Surf. Sci., 2008, 255, 2020-2025.
20. [20] H. Z. Zhang, J. F. Banfield, J. Phys. Chem. C, 2007, 111, 6621-6629.
21. [21] G. K. Zhang, F. S. He, X. Zou, J. Gong, H. B. Tu, H. Zhang, Q. Zhang, Y. Liu, J. Alloys Compd., 2007, 427, 82-86.
22. [22] A. Pottier, C. Chanéac, E. Tronc, L. Mazerolles, J. P. Jolivet, J. Mater. Chem., 2001, 11, 1116-1121.
23. [23] A. D. Paola, M. Bellardita, R. Ceccato, L. Palmisano, F. Parrino, J. Phys. Chem. C, 2009, 113, 15166-15174.
24. [24] H. Q. Wang, Z. B. Wu, Y. Liu, J. Phys. Chem. C, 2009, 113, 13317-13324.
25. [25] X. X. Wang, S. Meng, X. L. Zhang, H. T. Wang, W. Zhong, Q. G. Du, Chem. Phys. Lett., 2007, 444, 292-296.
26. [26] F. Dong, H. Wang, Z. B. Wu, J. Phys. Chem. C, 2009, 113, 16717-16723.
27. [27] H. Xu, L. Z. Zhang, J. Phys. Chem. C, 2010, 114, 11534-11541.
28. [28] X. K. Wang, C. Wang, W. Q. Jiang, W. L. Guo, J. G. Wang, Chem. Eng. J., 2012, 189, 288-294.
29. [29] J. G. Yu, G. H. Wang, B. Cheng, M. H. Zhou, Appl. Catal. B, 2007, 69, 171-180.
30. [30] H. M. Luo, T. Takata, Y. G. Lee, J. F. Zhao, K. Domen, Y. S. Yan, Chem. Mater., 2004, 16, 846-849.
31. [31] Q. Xiao, J. Zhang, C. Xiao, Z. C. Si, X. K. Tan, Sol. Energy, 2008, 82, 706-713.
32. [32] S. J. Rigby, A. H. R. Al-Obaidi, S. K. Lee, D. McStay, P. K. J. Robertson, Appl. Surf. Sci., 2006, 252, 7948-7952.
33. [33] R. Z. Ma, K. Fukuda, T. Sasaki, M. Osada, Y. Bando, J. Phys. Chem. B, 2005, 109, 6210-6214.
34. [34] V. Belessi, D. Lambropoulou, I. Konstantinou, A. Katsoulidis, P. Pomonis, D. Petridis, T. Albanis, Appl. Catal. B., 2007, 73, 292-299.
35. [35] A. Nakahira, T. Kubo, Y. Yamasaki, ACS Appl. Mater. Interfaces, 2010, 2, 1136-1140.
36. [36] J. G. Yu, L. F. Qi, M. Jaroniec, J. Phys. Chem. C, 2010, 114, 13118-13125.
37. [37] C. Nasr, K. Vinodgopal, L. Fisher, S. Hotchandani, A. K. Chatto-padhyay, P. V. Kamat, J. Phys. Chem., 1996, 100, 8436-8442.
38. [38] J. Jang, H. S. Lee, W. S. Lyoo, Fiber. Polym., 2007, 8, 19-24.
39. [39] J. Bandara, J. A. Mielczarski, J. Kiwi, Langmuir, 1999, 15, 7680-7687.
40. [40] N. Biswas, S. Umapathy, J. Phys. Chem. A, 2000, 104, 2734-2745.
41. [41] D. C. Hurum, A. G. Agrios, K. A. Gray, T. Rajh, M. C. Thurnauer, J. Phys. Chem. B, 2003, 107, 4545-4549.
42. [42] G. Liu, C. H. Sun, L. Cheng, Y. G. Jin, H. F. Lu, L. Z. Wang, S. C. Smith, G. Q. Lu, H. M. Cheng, J. Phys. Chem. C, 2009, 113, 12317-12324.
43. [43] S. C. Yan, Z. S. Li, Z. G. Zou, Langmuir, 2010, 26, 3894-3901.
44. [44] G. Liu, L. Z. Wang, C. H. Sun, X. X. Yan, X. W. Wang, Z. G. Chen, S. C. Smith, H. M. Cheng, G. Q. Lu, Chem. Mater., 2009, 21, 1266-1274.
45. [45] L. M. Yang, L. E. Yu, M. B. Ray, Environ. Sci. Technol., 2009, 43, 460-465.
46. [46] J. Yang, C. C. Chen, H. W. Ji, W. H. Ma, J. C. Zhao, J. Phys. Chem. B, 2005, 109, 21900-21907.
47. [47] S. K. Choi, S. Kim, S. K. Lim, H. Park, J. Phys. Chem. C, 2010, 114, 16475-16480.
48. [48] D. J. Yang, H. W. Liu, Z. F. Zheng, Y. Yuan, J. C. Zhao, E. R. Waclawik, X. B. Ke, H. Y. Zhu, J. Am. Chem. Soc., 2009, 131, 17885-17893.
49. [49] L. F. Yin, J. F. Niu, Z. Y. Shen, J. Chen, Environ. Sci. Technol., 2010, 44, 5581-5586.

扫一扫看文章

计量

PDF下载量: 3
文章访问数: 1502
HTML全文浏览量: 138

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

C-Cl共掺杂TiO₂/凹凸棒复合催化剂的制备及其可见光催化性能

English

Synthesis of C-Cl-codoped titania/attapulgite composites with enhanced visible-light photocatalytic activity

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

C-Cl共掺杂TiO2/凹凸棒复合催化剂的制备及其可见光催化性能

English

Synthesis of C-Cl-codoped titania/attapulgite composites with enhanced visible-light photocatalytic activity

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

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

C-Cl共掺杂TiO₂/凹凸棒复合催化剂的制备及其可见光催化性能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs