一步低温法制备可见光响应的棕色纳米TiO<sub>2</sub>及其光催化性能

引用本文: 王婷, 黎婉雯, 许丹丹, 吴轩民, 曹丽伟, 孟建新. 一步低温法制备可见光响应的棕色纳米TiO₂及其光催化性能[J]. 催化学报, 2017, 38(7): 1184-1195. doi: 10.1016/S1872-2067(17)62855-9 shu

Citation: Ting Wang, Wanwen Li, Dandan Xu, Xuanmin Wu, Liwei Cao, Jianxin Meng. Strong visible absorption and excellent photocatalytic performance of brown TiO₂ nanoparticles synthesized using one-step low-temperature process[J]. Chinese Journal of Catalysis, 2017, 38(7): 1184-1195. doi: 10.1016/S1872-2067(17)62855-9 shu

一步低温法制备可见光响应的棕色纳米TiO₂及其光催化性能

暨南大学化学系, 广东广州 510632
基金项目:
广东省自然科学基金研究团队项目（S2013030012842）.

摘要: 光催化作为一种具有前景的技术，被广泛运用于有机物降解、废水处理、空气净化、抗菌、太阳能电池等领域.在众多的光催化材料中，纳米TiO₂因具有性质稳定、耐腐蚀、廉价和无毒等优点而受到广泛关注.但纳米TiO₂禁带宽度较大（3.2 eV）、只对紫外光有响应及电子-空穴对易复合等特性限制了它的应用.因此，提高纳米TiO₂的可见光响应一直是研究的热点.本文发展了一种在低温下制备棕色纳米TiO₂的改良溶胶-凝胶法.该法以钛酸四丁酯为钛源，无水乙醇为溶剂，形成溶胶后无需陈化和高温高压，在简单温和的条件下即可制备出棕色纳米TiO₂.比较了低温干燥和高温焙烧两种处理方法，结果表明，随着制备温度的升高，样品的粒子尺寸增大，比表面积减小，颜色从白色转变为棕色，在更高的温度又变浅.样品的可见光吸收在180℃时达到最大，随后减弱.在优化温度180℃下制备的TiO₂-180℃纳米粒子不仅具有较小的粒径（5.0 nm），较大的比表面积（213.45 m²/g），且在整个紫外-可见光区都具有较强的吸收，其禁带宽度低至1.84 eV.X-射线光电子能谱结果表明，TiO₂粒子表面的-OH/H₂O含量随制备温度升高而先增加后下降.Raman光谱中E_g峰的移动和变宽表明TiO₂晶格可能存在缺陷或氧空位，而TiO₂-180℃纳米粒子的电子顺磁共振图谱的g值在2.003左右，对应氧空位中的未成对电子，验证了以上推测.其中TiO₂-180℃纳米粒子呈现为最强的EPR信号，表明其晶格内存在最高浓度的氧空位，这是其具有强可见光吸收的原因.光催化实验结果表明，在可见光照射下，TiO₂-180℃可高效降解亚甲基蓝（MB）.当C _（MB）=10mg/L，pH=4，催化剂添加量为0.07 g时，TiO₂-180℃催化剂的光催化活性达到最佳，光照1 h后MB降解率达到99.33%，反应速率常数（0.08287 mg/（L·min））约为同条件下P25（0.01342 mg/（L·min））的6倍.同时，TiO₂-180℃催化剂在不同单色光下的光催化活性与它对单色光的光响应大致相符.循环降解实验证明TiO₂-180℃催化剂具有很好的稳定性.光猝灭实验表明，·OH在光催化降解过程占主导作用，而TiO₂-180℃样品表面含有较多的-OH，有利于·OH的产生，乃至光催化反应.研究表明，晶格内高浓度的氧空位导致的强可见光响应，得益于低温制备条件而保留了大量-OH/H₂O的纳米粒子表面以及更大的比表面积，共同促成了TiO₂-180℃优越的光催化活性.所制备的棕色纳米TiO₂经过进一步修饰后有望运用于实际应用中.

关键词:

English

Strong visible absorption and excellent photocatalytic performance of brown TiO₂ nanoparticles synthesized using one-step low-temperature process

Department of Chemistry, Jinan University, Guangzhou 510632, Guangdong, China
Received Date: 17 March 2017
Revised Date: 08 May 2017
Fund Project:
This work was supported by Teamwork Project Funded by Guangdong Natural Science Foundation (S2013030012842).

Abstract: We report a facile and modified sol-gel approach to synthesize brown TiO₂ nanoparticles at low temperature (100-600℃). The TiO₂ nanoparticles dried at 180 ℃ (TiO₂-180℃) possessed a small particle size (5.0 nm), large specific surface area (213.45 m²/g), and efficient response to broadband light over the entire ultraviolet-visible spectrum with a narrow band gap of 1.84 eV. In addition, TiO₂-180℃ exhibited the optimal reaction rate constant for the degradation of methylene blue (0.08287 mg/(L·min)), which is six times higher than that of the mixed rutile/anatase phase TiO₂ photocatalytic standard P25 (0.01342 mg/(L·min)). Furthermore, cycling photodegradation ex-periments confirmed the stability and reusability of this catalyst. The unique physicochemical properties resulting from the low-temperature preparation of TiO₂-180℃, including its broadband visible absorption associated with a high concentration of oxygen vacancies, large surface area, and enriched surface -OH/H₂O may be responsible for this excellent photocatalytic performance. The use of as-prepared TiO₂-180℃ for practical applications is expected after further optimization.

Key words:

1. [1] M. Dahl, Y. D. Liu, Y. D. Yin, Chem. Rev., 2014, 114, 9853-9889.
2. [2] J. C. Liu, H. W. Bai, Y. J. Wang, Z. Y. Liu, X. W. Zhang, D. D. Sun, Adv. Funct. Mater., 2010, 20, 4175-4181.
3. [3] J. Reszczynska, T. Grzyb, J. W. Sobczak, W. Lisowski, M. Gazda, B. Ohtani, A. Zaleska, Appl. Catal. B, 2014, 163, 40-49.
4. [4] C. Gannoun, A. Turki, H. Kochkar, R. Delaigle, P. Eloy, A. Ghorbel, E. M. Gaigneaux, Appl. Catal. B, 2011, 147, 58-64.
5. [5] H. G. Peng, J. W. Ying, J. Y. Zhang, X. H. Zhang, C. Peng, C. Rao, W. M. Liu, N. Zhang, X. Wang. Chin. J. Catal., 2017, 38, 39-47.
6. [6] S. H. Hwang, J. Y. Song, Y. J. Jung, O. Y. Kweon, H. Song, J. Jang, Chem. Commun., 2011, 47, 9164-9166.
7. [7] M. Saif, S. M. K. Aboul-Fotouh, S. A. El-Molla, M. M. Ibrahim, L. F. M. Ismail, Spectrochim. Acta. A, 2014, 128, 153-162.
8. [8] J. Reszczynska, T. Grzyb, J. W. Sobczak, W. Lisowski, M. Gazda, B. Ohtani, A. Zaleska, Appl. Surf. Sci., 2014, 307, 333-345.
9. [9] T. L. Thompson, J. T. Yates, Chem. Rev., 2016, 106, 4425-4453.
10. [10] X. B. Chen, S. S. Mao, Chem. Rev., 2017, 107, 2891-2959.
11. [11] P. Sangpour, F. Hashemi, A. Z. Moshfegh, J. Phys. Chem. C, 2010, 114, 13955-13961.
12. [12] M. Kapilashrami, Y. F. Zhang, Y. S. Liu, A. Hagfeldt, J. H. Guo, Chem. Rev., 2014, 114, 9662-9707.
13. [13] R. Asahi, T. Morikawa, H. Irie, T. Ohwaki, Chem. Rev., 2014, 114, 9824-9852.
14. [14] D. X. M. Vargas, J. R. DeLa Rosa, C. J. Lucio-Ortiz, A. Hernan-dez-Ramirez, G. A. Flores-Escamilla, C. D. Garcia, Appl. Catal. B, 2015, 179, 249-261.
15. [15] B. Z. Tian, C. Z. Li, J. L. Zhang, Chem. Eng. J., 2015, 191, 402-409.
16. [16] M. S. Zhu, C.Y. Zhai, L. Q. Qiu, C. Lu, A. S. Paton, Y. K. Du, M. C. Goh, ACS Sustain. Chem. Eng., 2015, 3, 3123-3129.
17. [17] L. L. Tan, W. J. Ong, S. P. Chai, A. R. Mohamed, Chem. Commun., 2014, 50, 6923-6926.
18. [18] L. L. Tan, W. J. Ong, S. P. Chai, A. R. Mohamed, Chem. Eng. J., 2014, 283, 1254-1263.
19. [19] J. J. Murcia, M. C. Hidalgo, J. A. Navío, J. Arana, J. M. Dona-Rodríguez, Appl. Catal. B, 2015, 179, 305-312.
20. [20] C. F. Lin, C. H. Wu, Z. N. Onn, J. Hazard. Mater., 2008, 154,1033-1039.
21. [21] Z. K. Zheng, B. B. Huang, X. Y. Qin, X. Y. Zhang, Y. Dai, M. H. Whang-bo, J. Mater. Chem., 2011, 21, 9079-9087.
22. [22] X. Y. Xin, T. Xu, J. Yin, L. Wang, C. Y. Wang, Appl. Catal. B, 2015, 176-177, 354-362.
23. [23] Z. L. Tang, J. Y. Zhang, Z. Cheng, Z. T. Zhang, Mater. Chem. Phys., 2002, 77, 314-317.
24. [24] X. B. Chen, L. Liu, P. Y. Yu, S. S. Mao, Science, 2011, 331, 746-750.
25. [25] A. Naldoni, M. Allieta, S. Santangelo, M. Marelli, F. Fabbri, S. Cap-pelli, C. L. Bianchi, R. Psaro, V. D. Santo, J. Am. Chem. Soc., 2012, 134, 7600-7603.
26. [26] Z. Wang, C. Y. Yang, T. Q. Lin, H. Yin, P. Chen, D. Y. Wan, F. F. Xu, F. Q. Huang, J. H. Lin, X. M. Xie, M. H. Jiang, Adv. Funct. Mater., 2013, 23, 5444-5450.
27. [27] T. Q. Lin, C. Y. Yang, Z. Wang, H. Yin, X. J. Lu, F. Q. Huang, J. H. Lin, X. M. Xie, M. H. Jiang, Energy Environ. Sci., 2014, 7, 967-972.
28. [28] Z. Wang, C. Y. Yang, T. Q. Lin, H. Yin, P. Chen, D. Y. Wan, F. F. Xu, F. Q. Huang, J. H. Lin, X. M. Xie, M. H. Jiang, Energy Environ. Sci., 2013, 6, 3007-3014.
29. [29] T. C. An, X. H. Zhu, Y. Xiong, Chemosphere, 2002, 46, 897-903.
30. [30] A. A. Ismail, R. A. Geioushy, H. Bouzid, S. A. A-Sayari., A. A-Hajry, D. W. Bahnemann, Appl. Catal. B, 2013, 129, 62-70.
31. [31] L. L. Tan, W. J. Ong, S. P. Chai, A. R. Mohamed, Appl. Catal. B, 2013, 166-167, 251-259.
32. [32] P. F. Wang, Y. H. Ao, C. Wang, J. Hou, J. Qian, J. Hazard. Mater., 2012, 223-224, 79-83.
33. [33] Y. H. Peng, G. F. Huang, W. Q. Huang, Adv. Powder Technol., 2012, 23, 8-12.
34. [34] N. Serpone, D. Lawless, R. Khairutdinov, J. Phys. Chem., 1995, 99,16646-16654.
35. [35] T. M. Wandre, P. N. Gaikwad, A. S. Tapase, K. M. Garadkar, S. A. Vanalakar, P. D. Lokhande, R. Sasikala, P. P. Hankare, J. Mater. Sci., 2016, 27, 825-833.
36. [36] K. Roy, S. K. Mandal, M. N. Alam, S. C. Debnath, J. Sol-Gel. Sci. Tech-nol., 2016, 77, 718-726.
37. [37] M. Wajid. Shah, Y. Q Zhu, X. Y. Fan, J. Zhao, Y. X. Li, S. Asim, C. Y. Wang, Sci. Rep., 2015, 5, 15804.
38. [38] L. Pan, J. W. Zhang, X. Jia, Y. H. Ma, X. W. Zhang, L. Wang, J. J. Zou, Chin. J. Catal., 2017, 38, 253-259.
39. [39] H. Yin, T. Q. Lin, C. Y. Yang, Z. Wang, G. L. Zhu, T. Xu, X. M. Xie, F. Q. Huang, M. H. Jiang, Chem. Eur. J., 2017, 19,13313-13316.
40. [40] X. Y. Xin, T. Xu, J. Yin, L. Wang, C. Y. Wang, Appl. Catal. B, 2015, 176-177, 354-362.
41. [41] J. Zhao, Y. X. Li, Y. Q Zhu, Y. Wang, C. Y. Wang, Appl. Catal. A, 2015, 510, 34-41.
42. [42] A. García, J. Matos, Open Mater. Sci. J., 2010, 4, 2-4.
43. [43] C. H. Chiou, C. Y. Wu, R. S. Juang, Chem. Eng. J., 2008, 139, 322-329.
44. [44] N. Kashif, F. Ouyang, J. Environ. Sci., 2009, 21, 527-533.
45. [45] M. Qamar, M. Muneer, D. Bahnemann, J. Environ. Manage, 2010, 80, 99-106.
46. [46] B. Chai, J. Li, Q. Xu, Ind. Eng. Chem. Res., 2014, 53, 8744-8752.

扫一扫看文章

计量

PDF下载量: 2
文章访问数: 1154
HTML全文浏览量: 171

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

一步低温法制备可见光响应的棕色纳米TiO₂及其光催化性能

English

Strong visible absorption and excellent photocatalytic performance of brown TiO₂ nanoparticles synthesized using one-step low-temperature process

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

一步低温法制备可见光响应的棕色纳米TiO2及其光催化性能

English

Strong visible absorption and excellent photocatalytic performance of brown TiO2 nanoparticles synthesized using one-step low-temperature process

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

一步低温法制备可见光响应的棕色纳米TiO₂及其光催化性能

Strong visible absorption and excellent photocatalytic performance of brown TiO₂ nanoparticles synthesized using one-step low-temperature process

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs