F127辅助制备介孔Fe/TiO<sub>2</sub>催化剂用于中温NH<sub>3</sub>选择性催化还原反应

引用本文: 李昱琳, 韩小金, 侯亚芹, 郭耀萍, 刘勇进, 向宁, 崔燕, 黄张根. F127辅助制备介孔Fe/TiO₂催化剂用于中温NH₃选择性催化还原反应[J]. 催化学报, 2017, 38(11): 1831-1841. doi: 10.1016/S1872-2067(17)62897-3 shu

Citation: Yulin Li, Xiaojin Han, Yaqin Hou, Yaoping Guo, Yongjin Liu, Ning Xiang, Yan Cui, Zhanggen Huang. In situ preparation of mesoporous Fe/TiO₂ catalyst using Pluronic F127-assisted sol-gel process for mid-temperature NH₃ selective catalytic reduction[J]. Chinese Journal of Catalysis, 2017, 38(11): 1831-1841. doi: 10.1016/S1872-2067(17)62897-3 shu

F127辅助制备介孔Fe/TiO₂催化剂用于中温NH₃选择性催化还原反应

a 中国科学院山西煤炭化学研究所煤炭转化国家重点实验室, 山西太原 030001;
b 中国科学院大学, 北京 100049
基金项目:
中国科学院战略性先导科技专项（XDA07030300）.

摘要: NO_x是大气污染物的重要组成部分，能够造成酸雨、光化学烟雾和臭氧层破坏等一系列环境问题，严重危害人类健康.选择性催化还原（SCR）是控制NO_x排放的主要技术，当前工业上普遍采用的是钒钛催化剂，然而该催化剂活性温度窗口较窄（300-400 ℃），N₂选择性较低，而且钒物种本身有毒.因此开发新型SCR催化剂成为研究热点.
Fe/TiO₂催化剂具有稳定的化学性质，环境污染少且价格低廉，近年来受到广泛关注.为了提高Fe/TiO₂催化活性，人们采用了各种不同的制备方法.本文以F127作为结构导向剂，结合溶胶-凝胶法原位合成了具有介孔结构、工作温度在150-300 ℃的Fe/TiO₂脱硝催化剂，并与普通浸渍法和共沉淀法制备的催化剂进行了对比.利用N₂吸附脱附、紫外-可见光谱、X射线电子能谱、NH₃程序升温脱附和原位红外光谱等技术研究了制备方法对Fe/TiO₂催化剂物理结构及脱硝性能的影响.结果表明，相较于浸渍法和共沉淀法，模板法制备的催化剂具有较高的脱硝效率和抗H₂O和SO₂性能.作为结构导向剂，F127能够诱导催化剂形成均匀的介孔结构，有利于提高催化剂比表面积，促进反应物分子的扩散和转移，从而提高催化剂脱硝效率.
进一步研究发现，模板法能够明显促进活性组分Fe物种的分散和NH₃吸附，载体与活性组分具有较强的相互作用，因而有利于催化剂产生较多的活性位.结合XPS结果，较多的活性位点有利于表面吸附氧（O_α）在催化剂表面的吸附.O_α有利于NO到NO₂的转化，从而促进快速SCR反应：NO+NO₂+2NH₃→2N₂+3H₂O.通过原位红外机理分析证明，吸附在模板法制备的催化剂表面的NO物种具有较强的稳定性，当温度超过200 ℃时，仍然保持一定的吸附强度；吸附NH₃红外结果表明，Lewis酸性位比Brønsted酸性位具有更强的稳定性，当温度超过150 ℃仍然具有较强的Lewis酸吸附.催化剂表面稳定的NO物种和Lewis酸位上强的NH₃吸附是催化剂催化活性增加的重要原因.

关键词:

English

In situ preparation of mesoporous Fe/TiO₂ catalyst using Pluronic F127-assisted sol-gel process for mid-temperature NH₃ selective catalytic reduction

a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China;
b University of Chinese Academy of Sciences, Beijing 100049, China
Received Date: 12 June 2017
Revised Date: 29 July 2017
Fund Project:
This work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA07030300).

Abstract: An Fe/TiO₂ catalyst with uniform mesopores was synthesized using Pluronic F127 as a struc-ture-directing agent. This catalyst was used for selective catalytic reduction of NO with NH₃. The catalytic activity and resistance to H₂O and SO₂ of Fe/TiO₂ prepared by a template method were better than those of catalysts synthesized using impregnation and coprecipitation. The samples were characterized using N₂-physisorption, transmission electron microscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared Fouri-er-transform spectroscopy. The results showed that Pluronic F127 acted as a structural and chemi-cal promoter; it not only promoted the formation of a uniform mesoporous structure, leading to a higher surface area, but also improved dispersion of the active phase. In addition, the larger number of Lewis acidic sites, indicated by the presence of coordinated NH₃ species (1188 cm^-1) and the N-H stretching modes of coordinated NH₃ (3242 and 3388 cm^-1), were beneficial to mid-temperature selective catalytic reduction reactions.

Key words:

Fe/TiO₂
/ Mesopore structure
/ Interaction
/ Mid-temperature NH₃ selective catalytic reduction

1. [1] Z. M. Liu, Y. X. Liu, Y. Li, H. Su, L. L. Ma, Chem. Eng. J., 2016, 283, 1044-1050.
2. [2] G. Ramis, G. Busca, C. Cristiani, L. Lietti, P. Forzatti, F. Bregani, Langmuir, 1992, 8, 1744-1749.
3. [3] G. Busca, L. Lietti, G. Ramis, F. Berti, Appl. Catal. B, 1998, 18, 1-36.
4. [4] Y. Peng, C. X. Liu, X. Y. Zhang, J. H. Li, Appl. Catal. B, 2013, 140-141, 276-282.
5. [5] J. P. Chen, M. C. Hausladen, R. T. Yang, J. Catal., 1995, 151, 135-146.
6. [6] R. Q. Long, R. T. Yang, J. Catal., 1999, 188, 332-339.
7. [7] R. Q. Long, R. T. Yang, Catal. Lett., 2001, 74, 201-205.
8. [8] B. Li, Z. N. Huang, X. D. Huang, S. Z. Kou, F. Liu, X. B. Zhang, H. S. Yang, RSC Adv., 2016, 6, 6300-6307.
9. [9] F. D. Liu, H. He, C. B. Zhang, Chem. Commun., 2008, 2043-2045.
10. [10] Z. B. Xiong, Q. Hu, D. Y. Liu, C. Wu, F. Zhou, Y. Z. Wang, J. Jin, C. M. Lu, Fuel, 2016, 165, 432-439.
11. [11] F. J. J. G. Janssen, F. M. G. Van den Kerkhof, H. Bosch, J. R. H. Ross, J. Phys. Chem., 1987, 91, 5921-5927.
12. [12] Y. Y. He, M. E. Ford, M. H. Zhu, Q. C. Liu, U. Tumuluri, Z. L. Wu, I. E. Wachs, Appl. Catal. B, 2016, 193, 141-150.
13. [13] X. M. Huang, S. L. Zhang, H. N. Chen, Q. Zhong, J. Mol. Struct., 2015, 1098, 289-297.
14. [14] H. Kamata, H. Ohara, K. Takahashi, A. Yukimura, Y. Seo, Catal. Lett., 2001, 73, 79-83.
15. [15] I. Georgiadou, C. Papadopoulou, H. K. Matralis, G. A. Voyiatzis, A. Lycourghiotis, C. Kordulis, J. Phys. Chem. B, 1998, 102, 8459-8468.
16. [16] N. Y. Topsoe, Science, 1994, 265, 1217-1219.
17. [17] D. W. Kwon, K. H. Park, S. C. Hong, Chem. Eng. J., 2016, 284, 315-324.
18. [18] F. Nakajima, I. Hamada, Catal. Today, 1996, 29, 190-115.
19. [19] C. A. Sierra-Pereira, E. A. Urquieta-Gonzalez, Fuel, 2014, 118, 137-147.
20. [20] F. D. Liu, H. He, C. B. Zhang, Z. C. Feng, L. R. Zheng, Y. N. Xie, T. D. Hu, Appl. Catal. B, 2010, 96, 408-420.
21. [21] K.T. Ranjit, B. Viswanathan, J. Photochem. Photobiol. A, 1997, 108, 79-84.
22. [22] Y. Y. He, M. E. Ford, M. H. Zhu, Q. C. Liu, Z. L. Wu, I. E. Wachs, Appl. Catal. B, 2016, 188, 123-133.
23. [23] B. Q. Jiang, Y. Liu, Z. B. Wu, J. Hazard. Mater., 2009, 162, 1249-1254.
24. [24] Z. M. Wang, G. Yang, P. Biswas, W. Bresser, P. Boolchand, Powder Technol., 2001, 114, 197-204.
25. [25] Y. N. Shi, S. Chen, H. Sun, Y. Shu, X. Quan, Catal. Commun., 2013, 42, 10-13.
26. [26] D. A. Kotadia, S. S. Soni, Appl. Catal. A, 2014, 488, 231-238.
27. [27] S. H. Zhan, D. D. Zhu, S. S. Yang, M. Y. Qiu, Y. Li, H. B. Yu, Z. Q. Shen, J. Sol-Gel Sci. Technol., 2015, 73, 443-451.
28. [28] S. Buddee, S. Wongnawa, U. Sirimahachai, W. Puetpaibool, Mater. Chem. Phys., 2011, 126, 167-177.
29. [29] X. Liu, J. H. Li, X. Li, Y. Peng, H. Wang, X. M. Jiang, L. W. Wang, Chin. J. Catal., 2016, 37, 878-887.
30. [30] Y. Q. Cong, M. M. Chen, T. Xu, Y. Zhang, Q. Wang, Appl. Catal. B, 2014, 147, 733-740.
31. [31] Y. Peng, W. W. Yu, W. K. Su, X. Huang, J. H. Li, Catal. Today, 2015, 242, 300-307.
32. [32] T. Zhang, J. Liu, D. X. Wang, Z. Zhao, Y. C. Wei, K. Cheng, G. Y. Jiang, A. J. Duan, Appl. Catal. B, 2014, 148-149, 520-531.
33. [33] M. Kantcheva, J. Catal., 2001, 204, 479-494.
34. [34] Z. M. Liu, H. Su, B. H. Chen, J. H. Li, S. I. Woo, Chem. Eng. J., 2016, 299, 255-262.
35. [35] G. S. Qi, R. T. Yang, R. Chang, Appl. Catal. B, 2004, 51, 93-106.
36. [36] L. Chen, J. H. Li, M. F. Ge, Environ. Sci. Technol., 2010, 44, 9590-9596.
37. [37] C. Ciardelli, I. Nova, E. Tronconi, D. Chatterjee, T. Burkhardt, M. Weibel, Chem. Eng. Sci., 2007, 62, 5001-5006.
38. [38] J. M. Gallardo Amores, V. Sanchez. Escribano, G. Ramis, G. Busca, Appl. Catal. B, 1997, 13, 45-58.
39. [39] L. Lietti, J. L. Alemany, P. Forzatti, G. Busca, G. Ramis, E. Giamello, F. Bregani, Catal. Today, 1996, 29, 143-148.
40. [40] M. A. Larrubia, G. Ramis, G. Busca, Appl. Catal. B, 2000, 27, L145-L151.
41. [41] N. Y. Topsoe, J. A. Dumesic, H. Topsoe, J. Catal., 1995, 151, 241-252.
42. [42] G. S. Qi, R. T. Yang, J. Phys. Chem. B, 2004, 108, 15738-15747.
43. [43] W. D. Shan, F. D. Liu, H. He, X. Y. Shi, C. B. Zhang, Appl. Catal. B, 2012, 115-116, 100-106.
44. [44] G. T. Went, L. J. Leu, S. J. Lombardo, A. T. Bell, J. Phys. Chem, 1992, 96, 2235-2241.
45. [45] S. G. Wu, L. Zhang, X. B. Wang, W. X. Zou, Y. Cao, J. F. Sun, C. J. Tang, F. Gao, Y. Deng, L. Dong, Appl. Catal. A, 2015, 505, 235-242.
46. [46] P. G. Smirniotis, D. A. Peña, B. S. Uphade, Angew. Chem. Int. Ed., 2001, 40, 2479-2482.

扫一扫看文章

计量

PDF下载量: 7
文章访问数: 889
HTML全文浏览量: 50

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

F127辅助制备介孔Fe/TiO₂催化剂用于中温NH₃选择性催化还原反应

English

In situ preparation of mesoporous Fe/TiO₂ catalyst using Pluronic F127-assisted sol-gel process for mid-temperature NH₃ selective catalytic reduction

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

F127辅助制备介孔Fe/TiO2催化剂用于中温NH3选择性催化还原反应

English

In situ preparation of mesoporous Fe/TiO2 catalyst using Pluronic F127-assisted sol-gel process for mid-temperature NH3 selective catalytic reduction

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

F127辅助制备介孔Fe/TiO₂催化剂用于中温NH₃选择性催化还原反应

In situ preparation of mesoporous Fe/TiO₂ catalyst using Pluronic F127-assisted sol-gel process for mid-temperature NH₃ selective catalytic reduction

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs