高热稳定性TiO<sub>2</sub>空心微球高效光催化氧化丙酮

引用本文: 梁丽, 李开宁, 吕康乐, 何永基, 段有雨. 高热稳定性TiO₂空心微球高效光催化氧化丙酮[J]. 催化学报, 2017, 38(12): 2085-2093. doi: 10.1016/S1872-2067(17)62952-8 shu

Citation: Li Liang, Kaining Li, Kangle Lv, Wingkei Ho, Youyu Duan. Highly photoreactive TiO₂ hollow microspheres with super thermal stability for acetone oxidation[J]. Chinese Journal of Catalysis, 2017, 38(12): 2085-2093. doi: 10.1016/S1872-2067(17)62952-8 shu

高热稳定性TiO₂空心微球高效光催化氧化丙酮

a 中南民族大学资源与环境学院催化材料科学国家民委-教育部重点实验室, 湖北武汉 430074;
b 香港教育大学科学与环境学系, 香港新界大埔
基金项目:
国家自然科学基金（51672312，21373275）；武汉市科技计划（2016010101010018，2015070504020220）；香港教育大学院长研究基金（04257）.

摘要: 空心结构材料具有低密度、高通透性和易于回收的优点，因此人们对空心球的TiO₂，如TiO₂空心微球（TiO₂-HMSs）的制备非常感兴趣.但是普通TiO₂-HMSs的热稳定性较差，一般在600℃以上就由活性较高的锐钛矿相相变成活性很差的金红石相.考虑到氟离子能够抑制TiO₂相变，因此我们以Ti（SO₄）₂为钛源，在NH₄F和H₂O₂的共同作用下，于180℃水热制备了由空心颗粒自组装成的表面氟化的TiO₂-HMSs，并考察了其热稳定性与光催化氧化分解丙酮的性能.
研究发现，当焙烧温度从300℃上升到1000℃时，TiO₂平均粒径从79.0 nm逐渐增大到97.7 nm，结晶度从1.00增大到1.53.这是由于热处理促进了TiO₂颗粒的晶化.当进一步升温到1100℃时，XRD谱开始出现金红石相TiO₂的特征衍射峰，此时约18.4%的锐钛矿相开始向金红石相转化.因此，本文制备的二氧化钛锐钛矿相可以稳定到1000℃，显示出优良的高热稳定性.
扫描电镜显示，水热制备的TiO₂-HMSs是由高能（001）面暴露的TiO₂十面体纳米晶组装而成.随着焙烧温度提高到900℃，空心微球外观没有显著改变，但是组装体纳米晶暴露出来的空洞逐渐变小，晶粒变得圆滑；至1100℃时，空心微球组装体的纳米晶变成了球形颗粒，但是空心微球的空心结构没有坍塌，空心微球结构依然得到保留.
我们用丙酮的紫外光催化氧化分解来评价不同温度焙烧的TiO₂空心微球的光催化活性.结果显示，前驱体TiO₂空心微球于300℃焙烧2 h，丙酮的氧化速率从1.39×10^-3 min^-1（前驱体）降至0.82×10^-3 min^-1（T300样品），这是因为样品表面吸附的氟离子受热挥发所致；当焙烧温度从300℃提高到900℃时，催化剂活性从0.82×10^-3 min^-1升至2.09×10^-3 min^-1，这是由于焙烧促进了TiO₂的晶化；进一步升至1000和1100℃时，催化剂活性显著下降，这是由于催化剂的比表面积急剧减小和金红石相的生成.
总之，本文利用氟离子的化学诱导作用制备出表面氟化的空心颗粒自组装TiO₂空心微球，该TiO₂空心微球显示出超高热稳定性与高光催化活性，因此在高热环境中具有实际应用前景.

关键词:

English

Highly photoreactive TiO₂ hollow microspheres with super thermal stability for acetone oxidation

a Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, Hubei Province, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074, Hubei, China;
b Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, N. T., Hong Kong, China
Received Date: 11 October 2017
Revised Date: 30 October 2017
Fund Project:
This work is supported by the National Natural Science Foundation of China (51672312, 21373275), the Science and Technology Program of Wuhan, China (2016010101010018, 2015070504020220), and the Dean's Research Fund-04257 from the Education University of Hong Kong.

Abstract: TiO₂ hollow microspheres (TiO₂-HMSs) have attracted much attention because of their high photoreactivity, low density, and good permeability. However, anatase TiO₂-HMSs have poor thermal stability. In this study, surface-fluorinated TiO₂-HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO₄)₂-NH₄HF-H₂O₂ solution at 180℃. The effect of the calcination temperature on the structure and photoreactivity of the TiO₂-HMSs was systematically investigated, which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation. We found that after calcination at 300℃, the photoreactivity of the TiO₂-HMSs decreases from 1.39×10^-3 min^-1 (TiO₂-HMS precursor) to 0.82×10^-3 min^-1 because of removal of surface-adsorbed fluoride ions. With increasing calcination temperature from 300 to 900℃, the building blocks of the TiO₂-HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles, and the photoreactivity of the TiO₂-HMSs steady increases from 0.82×10^-3 to 2.09×10^-3 min^-1 because of enhanced crystallization. Further increasing the calcination temperature to 1000 and 1100℃ results in a decrease of the photoreactivity, which is ascribed to a sharp decrease of the Brunau-er-Emmett-Teller surface area and the beginning of the anatase-rutile phase transformation at 1100℃. The effect of surface-adsorbed fluoride ions on the thermal stability of the TiO₂-HMSs is also discussed.

Key words:

1. [1] K. Trzciński, M. Szkoda, M. Sawczak, J. Karczewski, A. Lisowska-Oleksiak, Appl. Surf. Sci., 2016, 385, 199-208.
2. [2] R. R. Hao, G. H. Wang, C. J. Jiang, H. Tang, Q. C. Xu, Appl. Surf. Sci., 2017, 411, 400-410.
3. [3] X. F. Wang, T. Y. Li, R. Yu, H. G. Yu, J. G. Yu, J. Mater. Chem. A, 2016, 4, 8682-8689.
4. [4] Y. Xu, Y. P. Mo, J. Tian, P. Wang, H. G. Yu, J. G. Yu, Appl. Catal. B, 2016, 181, 810-817.
5. [5] Q. J. Xiang, F. Y. Cheng, D. Lang, ChemSusChem, 2016, 9, 996-1002.
6. [6] L. J. Zhang, R. Zheng, S. Li, B. K. Liu, D. J. Wang, L. L. Wang, T. F. Xie, ACS Appl. Mater. Interfaces, 2014, 6, 13406-13412.
7. [7] D. Lang, F. Y. Cheng, Q. J. Xiang, Catal. Sci. Technol., 2016, 6, 6207-6216.
8. [8] M. S. Akple, J. X. Low, Z. Y. Qin, S. Wageh, A. A. Al-Ghamdi, J. G. Yu, S. W. Liu, Chin. J. Catal., 2015, 36, 2127-2134.
9. [9] F. Wang, Y. Zhou, P. Li, L. B. Kuai, Z. G. Zou, Chin. J. Catal., 2016, 37, 863-868.
10. [10] W. K. Wang, D. F. Xu, B. Cheng, J. G. Yu, C. J. Jiang, J. Mater. Chem. A, 2017, 5, 5020-5029.
11. [11] M. S. Akple, J. X. Low, S. W. Liu, B. Cheng, J. G. Yu, W. K. Ho, J. CO₂ Utilization, 2016, 16, 442-449.
12. [12] R. W. Yang, J. H. Cai, K. L. Lv, X. F. Wu, W. G. Wang, Z. H. Xu, M. Li, Q. Li, W. Q. Xu, Appl. Catal. B, 2017, 210, 184-193.
13. [13] G. Liu, H. G. Yang, J. Pan, Y. Q. Yang, G. Q. Lu, H. M. Cheng, Chem. Rev., 2014, 114, 9559-9612.
14. [14] T. Froschl, U. Hormann, P. Kubiak, G. Kucerova, M. Pfanzelt, C. K. Weiss, R. J. Behm, N. Husing, U. Kaiser, K. Landfesterd, M. Wohlfahrt-Mehrens, Chem. Soc. Rev., 2012, 41, 5313-5360.
15. [15] C. Liu, F. Raziq, Z. J. Li, Y. Qu, A. Zada, L. Q. Jing, Chin. J. Catal., 2017, 38, 1072-1078.
16. [16] D. A. Erdogan, E. Ozensoy, Appl. Surf. Sci., 2017, 403, 159-167.
17. [17] X. L. Wang, S. Shen, Z. C. Feng, C. Li, Chin. J. Catal., 2016, 37, 2059-2068.
18. [18] J. Q. Wen, X. Li, W. Liu, Y. P. Fang, J. Xie, Y. H. Xu, Chin. J. Catal., 2015, 36, 2049-2070.
19. [19] Z. Li, S. Cong, Y. M. Xu, ACS Catal., 2014, 4, 3273-3280.
20. [20] M. Addamo, M. Bellardita, A. Di. Paola, L. Palmisano, Chem. Commun., 2006, 4943-4945.
21. [21] J. G. Yu, H. T. Guo, S. Davis, S. Mann, Adv. Funct. Mater., 2006, 16, 2035-2041.
22. [22] H. G. Yang, H. C. Zeng, J. Phys. Chem. B, 2004, 108, 3492-3495.
23. [23] X. X. Li, Y. J. Xiong, Z. Q. Li, Y. Xie, Inorg. Chem., 2006, 45, 3493-3495.
24. [24] X. J. Cheng, M. Chen, L. M. Wu, G. X. Gu, Langmuir, 2006, 22, 3858-3863.
25. [25] J. H. Pan, X. W. Zhang, A. J. Du, D. D. Sun, J. O. Leckie, J. Am. Chem. Soc., 2008, 130, 11256-11257.
26. [26] C. Dwivedi, V. Dutta, Appl. Surf. Sci., 2012, 258, 9584-9588.
27. [27] N. Guo, Y. M. Liang, S. Lan, L. Liu, G. J. Ji, S. C. Gan, H. F. Zou, X. C. Xu, Appl. Surf. Sci., 2014, 305, 562-574.
28. [28] W. Y. Hu, W. Zhou, K. F. Zhang, X. C. Zhang, L. Wang, B. J. Jiang, G. H. Tian, D. Y. Zhao, H. G. Fu, J. Mater. Chem. A, 2016, 4, 7495-7502.
29. [29] Y. Xia, Q. Li, K. L. Lv, M. Li, Appl. Surf. Sci., 2017, 398, 81-88.
30. [30] X. F. Wang, R. Yu, K. Wang, G. Q. Yang, H. G. Yu, Chin. J. Catal., 2015, 36, 2211-2218.
31. [31] S. F. Chen, H. Q. Wang, L. J. Zhu, J. F. Li, J. F. Sun, Appl. Surf. Sci., 2014, 321, 86-93.
32. [32] G. T. Dai, L. Zhao, J. Li, L. Wan, F. Hu, Z. X. Xu, B. H. Dong, H. B. Lu, S. M. Wang, J. G. Yu, J. Colloid Interf. Sci., 2012, 365, 46-52.
33. [33] Z. K. Zheng, B. B. Huang, X. Y. Qin, X. Y. Zhang, Y. Dai, Chem. Eur. J., 2010, 16, 11266-11270.
34. [34] J. F. Lan, X. F. Wu, K. L. Lv, L. L. Si, K. J. Deng, Chin. J. Catal., 2015, 36, 2237-2243.
35. [35] K. L. Lv, Q. J. Xiang, J. G. Yu, Appl. Catal. B, 2011, 104, 275-281.
36. [36] A. A. Shutilov, G. A. Zenkovets, V. Yu. Gavrilov, S. V. Tsybulya, Ma-ter. Today:Proceed., 2017, 4, 11486-11489
37. [37] Y. Kumari, L. K. Jangir, A. Kumar, M. Kumar, K. Awasthi, Solid State Commun., 2017, 263, 1-5.
38. [38] P. Periyat, S. C. Pillai, D. E. McCormack, J. Colreavy, S. J. Hinder, J. Phys. Chem. C, 2008, 112, 7644-7652.
39. [39] P. Periyat, D. E. McCormack, S. J. Hinder, S. C. Pillai, J. Phys. Chem. C, 2009, 113, 3246-3253.
40. [40] S. W. Liu, J. G. Yu, S. Mann, J. Phys. Chem. C, 2009, 113, 10712-10717.
41. [41] Y. Y. Lv, L. H. Yu, H. Y. Huang, H. L. Liu, Y. Y. Feng, Appl. Surf. Sci., 2009, 255, 9548-9552.
42. [42] J. C. Yu, J. G. Yu, W. K. Ho, Z. T. Jiang, L. Z. Zhang, Chem. Mater., 2002, 14, 3808-3816.
43. [43] S. C. Padmanabhan, S. C. Pillai, J. Colreavy, S. Balakrishnan, D. E. McCormack, T. S. Perova, Y. Gunko, S. J. Hinder, J. M. Kelly, Chem. Mater., 2007, 19, 4474-4481.
44. [44] J. H. Cai, Z. Y. Wang, K. L. Lv, Y. Zheng, J. G. Yu, M. Li, RSC Adv., 2013, 3, 15273-15281.
45. [45] R. Rahimi, S. Zargari, A. Yousefi, M. Yaghoubi Berijani, A. Ghaf-farinejad, A. Morsali, Appl. Surf. Sci., 2015, 355, 1098-1106.
46. [46] L. L. Yin, M. Zhao, H. L. Hu, J. H. Ye, D. F. Wang, Chin. J. Catal., 2017, 38, 1307-1314.
47. [47] T. T. Wu, X. D. Kang, M. W. Kadi, I. Ismail, G. Liu, H. M. Cheng, Chin. J. Catal., 2015, 36, 2103-2108.
48. [48] K. L. Lv, J. G. Yu, K. J. Deng, X. H. Li, M. Li, J. Phys. Chem. Solid, 2010, 71, 519-522.
49. [49] J. G. Yu, Y. R. Su, B. Cheng, Adv. Funct. Mater., 2007, 17, 1984-1990.
50. [50] C. X. Lei, X. L. Jiang, X. Huang, X. Liu, D. Q. Zeng, Y. T. Ma, L. S. Wang, D. L. Peng, Appl. Surf. Sci., 2015, 359, 860-867.
51. [51] H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M. Cheng, G. Q. Lu, Nature, 2008, 453, 638-641.
52. [52] Y. Wang, H. M. Zhang, Y. H. Han, P. R. Liu, X. D. Yao, H. J. Zhao, Chem. Commun., 2011, 47, 2829-2831.
53. [53] Q. J. Xiang, K. L. Lv, J. G. Yu, Appl. Catal. B, 2010, 96, 557-564.
54. [54] Z. Y. Wang, K. L. Lv, G. H. Wang, K. J. Deng, D. G. Tang, Appl. Catal. B, 2010, 100, 378-385.
55. [55] F. He, F. Ma, T. Li, G. X. Li, Chin. J. Catal., 2017, 34, 2263-2270.
56. [56] K. L. Lv, X. F. Li, K. J. Deng, J. Sun, X. H. Li, M. Li, Appl. Catal. B, 2010, 95, 383-392.
57. [57] J. C. Yu, W. K. Ho, J. G. Yu, S. K. Hark, K. Iu, Langmuir, 2003, 19, 3889-3896.
58. [58] L. L. Si, Z. A. Huang, K. L. Lv, D. G. Tang, C. J. Yang, J. Alloys Compd., 2014, 601, 88-93.
59. [59] J. H. Cai, Z. A. Huang, K. L. Lv, J. Sun, K. J. Deng, RSC Adv., 2014, 4, 19588-19593.
60. [60] K. L. Lv, B. Cheng, J. G. Yu, G. Liu, Phys. Chem. Chem. Phys., 2012, 14, 5349-5362.
61. [61] J. G. Yu, H. G. Yu, B. Cheng, X. J. Zhao, J. C. Yu, W. K. Ho, J. Phys. Chem. B, 2003, 107, 13871-13879.
62. [62] Z. Zhang, O. Bondarchuk, B. D. Kay, J. M. White, Z. Dohnalek, J. Phys. Chem. B, 2006, 110, 21840-21845.
63. [63] C. Minero, G. Mariella, V. Maurino, E. Pelizzetti, Langmuir, 2000, 16, 2632-2641.
64. [64] A. Y. Nosaka, J. Nishino, T. Fujiwara, T. Ikegami, H. Yagi, H. Akutsu, Y. Nosaka, J. Phys. Chem. B, 2006, 110, 8380-8385.
65. [65] L. Ren, Y. Z. Li, J. T. Hou, X. J. Zhao, C. X. Pan, ACS Appl. Mater. Interfaces, 2014, 6, 1608-1615.
66. [66] Y. Wang, J. G. Yu, W. Xiao, Q. Li, J. Mater. Chem. A, 2014, 2, 3847-3855.
67. [67] J. S. Park, W. Choi, Langmuir, 2004, 20, 11523-11527.
68. [68] K. L. Lv, J. G. Yu, K. J. Deng, J. Sun, Y. X. Zhao, D. Y. Du, M. Li, J. Haz-ard. Mater., 2010, 173, 539-543.
69. [69] C. Minero, G. Mariella, V. Maurino, D. Vione, E. Pelizzetti, Langmuir, 2000, 16, 8964-8972.

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沈阳化工大学材料科学与工程学院沈阳 110142

高热稳定性TiO₂空心微球高效光催化氧化丙酮

English

Highly photoreactive TiO₂ hollow microspheres with super thermal stability for acetone oxidation

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高热稳定性TiO2空心微球高效光催化氧化丙酮

English

Highly photoreactive TiO2 hollow microspheres with super thermal stability for acetone oxidation

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