通过一种新型共前驱体的方法简单合成能增强TiO<sub>2</sub>可见光光催化活性的C修饰及Fe,N共掺杂的TiO<sub>2</sub>材料

引用本文: 蒋华麟, 刘军, 厉梦琳, 田磊, 丁攻圣, 陈萍华, 罗旭彪. 通过一种新型共前驱体的方法简单合成能增强TiO₂可见光光催化活性的C修饰及Fe,N共掺杂的TiO₂材料[J]. 催化学报, 2018, 39(4): 747-759. doi: 10.1016/S1872-2067(18)63038-4 shu

Citation: Hualin Jiang, Jun Liu, Menglin Li, Lei Tian, Gongsheng Ding, Pinghua Chen, Xubiao Luo. Facile synthesis of C-decorated Fe, N co-doped TiO₂ with enhanced visible-light photocatalytic activity by a novel co-precursor method[J]. Chinese Journal of Catalysis, 2018, 39(4): 747-759. doi: 10.1016/S1872-2067(18)63038-4 shu

通过一种新型共前驱体的方法简单合成能增强TiO₂可见光光催化活性的C修饰及Fe,N共掺杂的TiO₂材料

a 江西省持久性污染物控制和资源循环利用重点实验室, 江西南昌 330063;
b 南昌航空大学环境与化学工程学院, 江西南昌 330063
基金项目:
国家自然科学基金（51368044，51568051，51668046）；国家优秀青年基金（51422807）；江西省科技支持计划（20151BBG70018）；江西省杰出青年学者自然科学基金（20162BCB23041）；江西省青年科学基金重点项目（20171ACB21034）；江西省教育部科技项目（GJJ160700）；江西省自然科学基金（20161BAB216102）；江西省教育改革项目（JXJG-16-8-7）；南昌航空大学教育改革项目（JY1604，JY1605KCPY-1511）.

摘要: 为了提高TiO₂的可见光光催化活性，研究者做了很多努力.晶格掺杂和表面修饰是提高TiO₂可见光光催化活性的两种重要方法，但由于这两种方法实施的条件不一样，所以很难将它们在同一个制备过程中统一起来.为了解决这个问题，我们通过邻菲罗啉与Fe²⁺络合形成Fe（Ⅱ）-phenanthroline配合物，然后以这种配合物作为Fe，N，C的共同来源，通过水热-煅烧的方法合成Fe，N共掺杂且C表面修饰的TiO₂材料（Fe，N co-doped TiO₂/C）.通过其在可见光照射下降解4-NP来评估材料的性能，同时也以XRD，FT-IR，XPS，EPR等手段对材料进行表征，结合实验结果推测了其可能的光催化机理.由可见光光催化降解动力学数据可知，Fe，N co-doped TiO₂/C表现出来的性能最佳，其反应速率常数为0.00963min^-1，约是纯TiO₂的5.9倍，约是以三种单独来源分别引入Fe，N，C三种元素样品（（Fe，N，C）-TiO₂）的5.1倍.这说明不同引入元素之间的强烈相互作用可以协同地提高TiO₂光催化能力.HRTEM图片显示Fe，N co-doped TiO₂/C中存在异质结结构，它是锐钛矿和板钛矿的混合晶相，TiO₂的这种混合晶型有利于增强其光催化性能.结合Fe，N co-doped TiO₂/C的XPS、拉曼和FT-IR数据进行分析，结果显示C元素是修饰在TiO₂晶体表面，N元素是完全掺杂到TiO₂晶格中，Fe元素大部分掺杂到晶格中，少部分修饰在晶体表面（这在Fe掺杂TiO₂的研究中较常见）.另外，从XPS元素相对含量分析可知，用邻菲罗啉作为C，N的共同来源同时引入C，N，引入量比以往的报道提高了2倍左右，这表明我们报道的这种方法可以高水平地同时向TiO₂引入C和N元素，为同时高水平地向TiO₂中引入这两种元素提供了新的思路.结合EPR，时间-电流图，电化学阻抗图谱（EIS），光致发光图谱，Mott-Schottky图谱，XPS导带分析，活性自由基中间体捕获实验等多种表征的结果，我们推测Fe，N co-doped TiO₂/C的光催化机理如下：在可见光照射下，Fe，N co-doped TiO₂/C被激发而产生电子与空穴（h⁺），电子与氧气反应形成O₂^·-，然后O₂^·-和h⁺把污染物分子氧化并降解它们，而材料表面所修饰的C物质受之前所转移过来电子的保护，而不至于被强烈氧化.本研究实现了TiO₂晶格掺杂与表面修饰在同一制备过程的结合，为制备高性能无机-有机元素共掺杂，内部-外部共改性的TiO₂光催化材料提供了新的思路.

关键词:

English

Facile synthesis of C-decorated Fe, N co-doped TiO₂ with enhanced visible-light photocatalytic activity by a novel co-precursor method

a Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang 330063, Jiangxi, China;
b College of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063, Jiangxi, China
Received Date: 24 December 2017
Revised Date: 18 January 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (51368044, 51568051, 51668046), the National Science Fund for Excellent Young Scholars (51422807), the Science and Technology Supporting Program of Jiangxi Province (20151BBG70018), the Natural Science Foundation of Jiangxi Province for Distinguished Young Scholars (20162BCB23041), the Science Foundation for Young Scientists of Jiangxi Province-Key Project (20171ACB21034), the Science and Technology Project of Jiangxi Provincial Education Department (GJJ160700), the Natural Science Foundation of Jiangxi Province (20161BAB216102), the Jiangxi Province Educational Reform Project (JXJG-16-8-7), and the Nanchang Hangkong University Educational Reform Project (JY1604, JY1605, KCPY-1511).

Abstract: Lattice-doping and surface decoration are prospective routes to improve the visible-light photocatalytic ability of TiO₂, but the two techniques are difficult to combine into one preparation process because they are usually conducted under different conditions, which limits the efficiency of TiO₂ modification. In this study, TiO₂ was successfully modified by simultaneous lattice-doping and surface decoration, and the visible-light photocatalytic capacity was largely improved. Upon comparing the method reported here with previous ones, the most significant difference is that Fe(Ⅱ)-phenanthroline was first used as the co-precursor of the introduced elements of C, N, and Fe. These three elements were simultaneously introduced to TiO₂ at high levels by this co-precursor method. The as-synthesized photocatalysts were systemically investigated and analyzed by several characterization methods such as XRD, FT-IR, XPS, Raman spectroscopy, EPR, UV-Vis DRS, photoluminescence spectra, photocurrent, electrochemical impedance spectra, TEM, and HRTEM. The photocatalytic degradation of 4-NP under visible-light irradiation was used to evaluate the photocatalytic activity of the photocatalysts. Based on the experimental data, a probable mechanism for the photocatalytic degradation by the photocatalysts is proposed. This is a novel method of using one source to simultaneously introduce metal and non-metal elements to TiO₂ at high levels, which may provide a new way to prepare highly effective TiO₂ photocatalysts.

Key words:

1. [1] H. L. Jiang, M. L. Li, J. Liu, X. Q. Li, L. Tian, P. H. Chen, Ceram. Int., 2018, 44, 2709-2717.
2. [2] Y. Zhang, J. R. Chen, L. Hua, S. J. Li, X. X. Zhang, W. C. Sheng, S. S. Cao, J. Hazard. Mater., 2017, 340, 309-318.
3. [3] J. Shao, W. C. Sheng, M. S. Wang, S. J. Li, J. R. Chen, Y. Zhang, S. S. Cao, Appl. Catal. B, 2017, 209, 311-319.
4. [4] Y. Zhang, Z. Y. Zhao, J. R. Chen, L. Cheng, J. Chang, W. C. Sheng, C. Y. Hu, S. S. Cao, Appl. Catal. B, 2015, 165, 715-722.
5. [5] L. C. Jia, C. C. Wu, Y. Y. Li, S. Han, Z. B. Li, B. Chi, J. Pu, L. Jian, Appl. Phys. Lett., 2011, 98, 2815-2817.
6. [6] Y. H. Zhang, F. Z. Lv, T. Wu, L. Yu, R. Zhang, B. Shen, X. H. Meng, Z. F. Ye,P. K. Chu, J. Sol-Gel Sci. Technol., 2011, 59, 387-391.
7. [7] N. R. Mathews, M. A. Cortes Jacome, C. Angeles-Chavez, J. A. Toledo Antonio, J. Mater. Sci. Matter. Electron., 2015, 26, 5574-5584.
8. [8] Z. Y. Huang, Z. G. Gao, S. M. Gao, Q. Y. Wang, Z. Y. Wang, B. B. Huang, Y. Dai, Chin. J. Catal., 2017, 38, 821-830.
9. [9] L. J. Deng, Y. Xie, G. K. Zhang, Chin. J. Catal., 2017, 38, 379-388.
10. [10] X. F. Wu, S. Fang, Y. Zheng, J. Sun, K. L. Lü, Molecules, 2016, 21, 181/1-181/3.
11. [11] K. L. Lü, J. C. Hu, X. H. Li, M. Li, J. Mol. Catal. A, 2012, 356, 78-84.
12. [12] K. Pathakoti, S. Morrow, C. Han, M. Pelaez, X. J. He, D. D. Dionysiou, H. M. Hwang, Environ. Sci. Technol., 2013, 47, 9988-9996.
13. [13] L. G Devi, R. Kavitha, Appl. Catal. B, 2013, 140-141, 559-587.
14. [14] D. H. Wang, L. Jia, X. L. Wu, L.Q. Lu, A. W. Xu, Nanoscale, 2012, 4, 576-584.
15. [15] P. Zabek, J. Eberl, H. Kisch, Photochem. Photobiol. Sci., 2009, 8, 264-269.
16. [16] X. J. Yu, J. J. Liu, Y. C. Yu, S. L. Zuo, B. S. Li, Carbon, 2014, 68, 718-724.
17. [17] S. Larumbe, M. Monge b, C. Gómez-Polo, Appl. Surf. Sci., 2015, 327, 490-497.
18. [18] K. Liu, Y. Wang, P. Chen, W. B. Zhong, Q. Z. Liu, M. F. Li, Y. D. Wang, W. W. Wang, Z. T. Lu, D. Wang, Appl. Catal. B, 2016, 196, 223-231.
19. [19] S. M. Alshehri, T. Almuqati, N. Almuqati, E. Al-Farraj, N. Alhokbany, T. Ahamad, Carbohyd. Polym., 2016, 151, 135-143.
20. [20] Y. C. Zhang, M. Yang, G. S. Zhang, D. D. Dionysiou, Appl. Catal. B, 2013, 142-143, 249-258.
21. [21] Z. Dai, F. Qin, H. P. Zhao, F. Tian, Y. L. Liu, R. Chen, Nanoscale, 2015, 7, 11991-11999.
22. [22] T. A. Kandiel, L. Robben, A. Alkaim, D. Bahnemann, Photochem. Photobiol. Sci., 2013, 12, 602-609.
23. [23] J. Cao, B. Y. Xu, B. D. Luo, H. L. Lin, S. F. Chen, Catal. Commun., 2011, 13, 63-68.
24. [24] X. B. Luo, F. Deng, L. J. Min, S. L. Luo, B. Guo, G. S. Zeng, C. Au, Envi-ron. Sci. Technol., 2013, 47, 7404-7412.
25. [25] J. Yang, R. S. Hu, W. W. Meng, Y. F. Du, Chem. Comm., 2016, 52, 2620-2623.
26. [26] J. P. Zou, L. C. Wang, J. M. Luo, Y. C. Nie, Q. J. Xing, X. B. Luo, H. M. Du, S. L. Luo, S. L. Suib, Appl. Catal. B, 2016, 193, 103-109.
27. [27] G. Zhou, M. F. Wu, Q. J. Xing, F. Li, H. Liu, X. B. Luo, J. P. Zou, J. M. Luo, A. Q. Zhang, Appl. Catal. B, 2018, 220, 607-614.
28. [28] Z. B. Zhang, C. C. Wang, R. Zakaria, J. Y. Ying, J. Phys. Chem. B, 1998, 102, 10871-10878.
29. [29] W. Choi, A. Termin, M. R. Hoffmann, J. Phys. Chem., 1994, 98, 13669-13679.
30. [30] S. Sood, A. Umar, S. K. Mehta, S. K. Kansal, J. Colloid Interf. Sci., 2015, 450, 213-223.
31. [31] M. H. Zhou, J. G. Yu, B. Cheng, J. Hazard, Mater., 2006, 137, 1838-1847.
32. [32] F. Zhou, R. Shi, Y. Zhu, J. Mol. Catal. A, 2011, 340, 77-82.
33. [33] A. Ishikawa, T. Takata, J. N. Kondo, M. Hara, H. Kobayashi, K. Domen, J. Am. Chem. Soc., 2002, 124, 13547-13553.
34. [34] M. Y. Xing, J. L. Zhang, F. Chen, Appl. Catal. B, 2009, 89, 563-569.
35. [35] G. D. Yang, Z. Jiang, H. H. Shi, T. C. Xiao, Z. F. Yan, J. Mater. Chem., 2010, 20, 5301-5309.
36. [36] P. Zabek, J. Eberl, H. Kisch, Photochem. Photobiol. Sci., 2009, 8, 264-269.
37. [37] J. Wang, D. N. Tafen, J. P. Lewis, Z. L. Hong, A. Manivannan, M. J. Zhi, M. Li, N. Q. Wu, J. Am. Chem. Soc., 2009, 131, 12290-12297.
38. [38] G. M. Wang, H. Y. Wang, Y. C. Ling, Y. C. Tang, X. Y. Yang, R. C. Fitzmorris, C. C. Wang, J. Z. Zhang, Y. Li, Nano. Lett., 2011, 11, 3026-3033.
39. [39] H. Y. Li, D. J. Wang, H. M. Fan, P. Wang, T. F. Jiang, T. F. Xie, J. Colloid Interf. Sci., 2011, 354, 175-180.
40. [40] F. Z. Jia, Z. P. Yao, Z. H. Jiang, C. X. Li, Catal. Commun., 2011, 12, 497-501.
41. [41] D. M. Chen, Z. Y. Jiang, J. Q. Geng, Q. Wang, D. Yang, Ind. Eng. Chem. Res., 2007, 46, 2741-2746.
42. [42] L. Zhao, X. F. Chen, X. C. Wang, Y. J. Zhang, W. Wei, Y. H. Sun, M. Antonietti, M. M. Titirici, Adv. Mater., 2010, 22, 3317-3321.
43. [43] X. Nie, G. Y. Li, P. K. Wong, H. J. Zhao, T. C. An, Catal. Today, 2014, 230, 67-73.
44. [44] H. Q. Wang, Z. B. Wu, Y. Liu, J. Phys. Chem. C, 2009, 113, 13317-13324.
45. [45] X. Y. Zhang, H. P. Li, X. L. Cui, Y. H. Lin, J. Mater. Chem., 2010, 20, 2801-2806.
46. [46] H. Zhang, X. J. Lu, Y. M. Li, Y. Wang, J. H. Li, ACS Nano, 2010, 4, 380-386.
47. [47] V. Etacheri, M. K. Seery, S. J. Hinder, S. C. Pillai, Chem. Mater., 2010, 22, 3843-3853.
48. [48] M. Sathish, B. Viswanathan, R. P. Viswanath, C. S. Gopinath, Chem. Mater., 2005, 17, 6349-6353.
49. [49] F. Spadavecchia, G. Cappelletti, S. Ardizzone, C. L. Bianchi, S. Cappelli, C. Oliva, P. Scardi, M. Leoni, P. Fermo, Appl. Catal. B, 2010, 96, 314-322.
50. [50] J. G. Yu, Q. J. Xiang, M. H. Zhou, Appl. Catal. B, 2009, 90, 595-602.
51. [51] Z. Ambrus, N. Balazs, T. Alapi, G. Wittmann, P. Sipos, A. Dombi, K. Mogyorosi, Appl. Catal. B, 2008, 81, 27-37.
52. [52] Y. Shao, C. S. Cao, S. L. Chen, M. He, J. L. Fang, J. Chen, X. F. Li, D. Z. Li, Appl. Catal. B, 2015, 179, 344-351.
53. [53] J. Yang, R. S. Hu, W. W. Meng, Y. F. Du, Chem. Commun., 2016, 12, 2620-2623.
54. [54] Z. M. Yang, G. F. Huang, W. Q. Huang, J. M. Wei, X. G. Yan, Y. Y. Liu, C. Jiao, Z. Wan, A. L. Pan, J. Mater. Chem. A, 2014, 2, 1750-1756.
55. [55] N. Liang, J. T. Zai, M. Xu, Q. Zhu, X. Wei, X. F. Qian, J. Mater. Chem. A, 2014, 2, 4208-4216.
56. [56] G. L. Liu, C. Han, M. Pelaez, D. W. Zhu, S. J. Liao, V. Likodimos, N. Ioannidis, A. G Kontos, P. Falaras, P. S. M. Dunlop, J. A. Byrne, D. D. Dionysiou, Nanotechnology, 2012, 23, 294003/1-294013/10.
57. [57] H. B. Liu, Y. M. Wu, J. L. Zhang, ACS Appl. Mater. Interfaces, 2011, 3, 1757-1764.
58. [58] C. Chen, W. M. Cai, M. C. Long, B. X. Zhou, Y. H. Wu, D. Y. Wu,Y. J. Feng, ACS Nano, 2010, 4, 6425-6432.
59. [59] F. Z. Jia, Z. P. Yao, Z. H. Jiang, C. X. Li, Catal. Commun., 2011, 12, 497-501.
60. [60] Y. H. Zhang, Z. R. Tang, X. Z. Fu, Y. J. Xu, ACS Nano, 2011, 5, 7426-7435.
61. [61] J. K. Wassei, K. C. Cha, V. C. Tung, Y. Yang, R. B. Kaner, J. Mater. Chem., 2011, 21, 3391-3396.
62. [62] P. Xu, J. Lu, T. Xu, S. U. Gao, B. B. Huang, Y. Dai, J. Phys. Chem. C, 2010, 114, 9510-9517.
63. [63] P. Ząbek, J. Eberl, H. Kisch, Photochem. Photobiol. Sci., 2009, 8, 264-269.
64. [64] J. H. Chang, Q. G. Dong, Spectrum Principle and the Analysis, Science Press, Beijing, 2006.
65. [65] J. P. Zou, D. D. Wu, J. M. Luo, Q. J. Xing, X. B. Luo, W. H. Dong, S. L. Luo, H. M. Du, S. L. Suib, ACS Catal., 2016, 6, 6861-6867.
66. [66] W. H. Dong, D. D. Wu, J. M. Luo, Q. J. Xing, H. Liu, J. P. Zou, X. B. Luo, X. B. Min, H. L. Liu, S. L. Luo, C. T. Au, J. Catal., 2017, 349, 218-225.
67. [67] M. Y. Xing, J. L. Zhang, F. Chen, B. Z. Tian, Chem. Commun., 2011, 47, 4947-4949.
68. [68] S. Livraghi, M. C. Paganini, E. Giamello, A. Selloni, C. D. Valentin, G. Pacchioni, J. Am. Chem. Soc., 2006, 128, 15666-15671.
69. [69] P. Triggs, Helv, Phys. Acta, 1985, 58, 657-714.
70. [70] X. W. Zhang, L. C. Lei, Mater. Lett., 2008, 62, 895-897.
71. [71] D. Mitoraj, H. Kisch, Angew. Chem. Int. Ed., 2008, 47, 9975-9978.
72. [72] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science, 2001, 293, 269-271.
73. [73] S. Yin, Y. Aita, M. Komatsu, J. S. Wang, Q. Tang, T. Sato, J. Mater. Chem., 2005, 15, 674-682.
74. [74] F. Spadarecohia, G. Cappelletti, S. Ardizzone, C. L.Bianchi, S. Cappelli, C. Oliva, P. Scardi, M. Leoni, P. Fermo, Appl. Catal. B, 2010, 96, 314-322.
75. [75] L. L. He, Z. F. Tong, Z. H. Wang, M. Chen, J. Colloid Interf. Sci., 2018, 509,448-456.
76. [76] H. Huang, N. Huang, Z. H. Wang, G. Q. Xia, M. Chen, L. L. He, Z. F. Teng, C. G. Ren, J. Colloid Interf. Sci., 2017, 502, 77-88.
77. [77] L. Jia, D. H. Wang, Y. X. Huang, A. W. Xu, H. Q. Yu, J. Phys. Chem. C, 2011, 115, 11466-11473.

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 1495
HTML全文浏览量: 107

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

通过一种新型共前驱体的方法简单合成能增强TiO₂可见光光催化活性的C修饰及Fe,N共掺杂的TiO₂材料

English

Facile synthesis of C-decorated Fe, N co-doped TiO₂ with enhanced visible-light photocatalytic activity by a novel co-precursor method

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

通过一种新型共前驱体的方法简单合成能增强TiO2可见光光催化活性的C修饰及Fe,N共掺杂的TiO2材料

English

Facile synthesis of C-decorated Fe, N co-doped TiO2 with enhanced visible-light photocatalytic activity by a novel co-precursor method

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

通过一种新型共前驱体的方法简单合成能增强TiO₂可见光光催化活性的C修饰及Fe,N共掺杂的TiO₂材料

Facile synthesis of C-decorated Fe, N co-doped TiO₂ with enhanced visible-light photocatalytic activity by a novel co-precursor method

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs