表面Mo修饰提高CeTiO<sub><i>x</i></sub>催化剂低温脱硝性能

引用本文: 李露露, 李佩晓, 谭伟, 马凯莉, 邹伟欣, 汤常金, 董林. 表面Mo修饰提高CeTiO_x催化剂低温脱硝性能[J]. 催化学报, 2020, 41(2): 364-373. doi: S1872-2067(19)63437-6 shu

Citation: Lulu Li, Peixiao Li, Wei Tan, Kaili Ma, Weixin Zou, Changjin Tang, Lin Dong. Enhanced low-temperature NH₃-SCR performance of CeTiO_x catalyst via surface Mo modification[J]. Chinese Journal of Catalysis, 2020, 41(2): 364-373. doi: S1872-2067(19)63437-6 shu

表面Mo修饰提高CeTiO_x催化剂低温脱硝性能

a 南京大学环境学院, 江苏南京 210093;
b 南京大学化学化工学院, 江苏南京 210093;
c 南京大学现代分析中心, 江苏省机动车尾气污染控制重点实验室, 江苏南京 210093;
d 南水北调中线渠首环境检测应急中心, 河南南阳 473061
基金项目:
国家自然科学基金（21773106，21707066，21677069，21806077）和中国博士后科学基金（2018M642206）.

摘要: 近年来，以雾霾为代表的大气污染问题严重影响到经济社会的可持续发展.其中，氮氧化物（NO_x）的大量排放是导致雾霾天气的重要原因之一.氨选择性催化还原（NH₃-SCR）是目前消除氮氧化物的主流技术，低温NH₃-SCR更是广泛应用于钢铁、焦化、水泥、玻璃、陶瓷和垃圾焚烧等行业的烟气排放治理.传统的V₂O₅-WO₃/TiO₂催化剂活性温度高（300-400℃）且钒具有生物毒性，因此亟待开发环境友好的低温非钒基脱硝催化剂.
最近，CeTiO_x基催化剂由于在中高温段（250-400℃）表现出优异的脱硝性能而得到广泛关注.然而，该催化剂仍面临低温活性差及抗硫性能差的问题，制约了其工业化应用.研究显示，添加过渡金属可提高CeTiO_x基催化剂的脱硝活性和抗硫中毒性能，这主要是因为过渡金属的添加可以有效改善催化剂的氧化还原性能和表面酸性.MoO₃作为一种可以提供大量酸性位的氧化物，常被用作助剂改善钒钨钛催化剂的活性.研究显示，MoO₃的引入可以促进催化剂中钒物种的分散度以及提高表面酸性.基于此，我们制备了一系列不同Mo含量的MoO₃/CeTiO_x催化剂，以期提高CeTiO_x催化剂的低温脱硝性能及抗SO₂中毒能力，并着重研究表面Mo的修饰对CeTiO_x催化剂物理化学性质的影响.
研究发现，表面Mo修饰可以显著提高CeTiO_x的低温催化活性，其脱硝效率在150℃即可达到80%，同时抗SO₂中毒能力也得到增强.进一步借助X射线衍射、比表面积测定、氢气程序升温还原、氨气程序升温脱附和X射线光电子能谱等方法对催化剂进行了全面表征分析.结果显示，表面Mo修饰对CeTiO_x催化剂物理化学性质的影响与其脱硝性能有着密不可分的关系.首先，钼物种主要是以MoO₃的形式存在于CeTiO_x表面，其最佳的负载量为4 wt.%.其次，表面Mo的沉积显著提高了催化剂的表面酸量，尤其是Brönsted酸位的数量，而表面酸位的增加有利于催化剂吸附与活化反应物种NH₃；同时，表面Mo修饰还减弱了硝酸盐在催化剂表面的吸附，进一步促使NH₃-SCR反应按照Eley-Rideal机理顺利进行.最后，该催化剂在H₂O和SO₂存在的条件下仍具有最佳的脱硝性能，因而有望用于实际含SO₂的低温烟气脱硝.

关键词:

English

Enhanced low-temperature NH₃-SCR performance of CeTiO_x catalyst via surface Mo modification

a School of the Environment, Nanjing University, Nanjing 210093, Jiangsu, China;
b School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, Jiangsu, China;
c Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing 210093, Jiangsu, China;
d Emergency Center for Environmental Monitoring at Canal Head of Middle Route of South-to-North Water Transfer Project, Nanyang 473061, Henan, China
Received Date: 20 May 2019
Revised Date: 05 July 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21773106, 21707066, 21677069, and 21806077) and the China Postdoctoral Science Foundation (2018M642206).

Abstract: The effect of molybdenum oxide on the activity and durability of CeO₂-TiO₂ catalyst for NO reduction by NH₃ was examined. It was found that the introduction of Mo could improve the low-temperature NH₃-SCR activity and SO₂/H₂O durability of the CeO₂-TiO₂ catalyst and an optimal loading of Mo was 4 wt.%. The best MoO₃/CeO₂-TiO₂ catalyst displayed over 90% NO conversion from 200℃ to 400℃ and obtained 4-fold increase in NO conversion compared to CeO₂-TiO₂ at 150℃. The characterization results revealed that the number of Brönsted acid sites over MoO₃/CeO₂-TiO₂ was significantly increased, and the adsorption of nitrate species was dramatically weakened because of the coverage of MoO₃, which were favorable for the high NH₃-SCR performance. It is believed that the MoO₃/CeO₂-TiO₂ catalyst is a suitable substitute for the NH₃-SCR reaction.

Key words:

1. [1] C. X. Li, M. Q. Shen, J. Q. Wang, J. Wang, Y. P. Zhai, Ind. Eng. Chem. Res., 2018, 57, 8424-8435.
2. [2] J. K. Lai, I. E. Wachs, ACS Catal., 2018, 8, 6537-6551.
3. [3] T. F. Xu, X. D. Wu, Y. X. Gao, Q. W. Lin, J. F. Hu, D. Weng, Catal. Commun., 2017, 93, 33-36.
4. [4] T. H. Vuong, J. Radnik, J. Rabeah, U. Bentrup, M. Schneider, H. Atia, U. Armbruster, W. Grünert, A. Brückner, ACS Catal., 2017, 7, 1693-1705.
5. [5] I. Song, S. Youn, H. Lee, S. G. Lee, S. J. Cho, D. H. Kim, Appl. Catal. B, 2017, 210, 421-431.
6. [6] G. Gao, J. W. Shi, C. Liu, C. Gao, Z. Y. Fan, C. M. Niu, Appl. Surf. Sci., 2017, 411, 338-346.
7. [7] C. Liu, G. Gao, J. W. Shi, C. He, G. D. Li, N. Bai, C. M. Niu, Catal. Commun., 2016, 86, 36-40.
8. [8] Z. Y. Sheng, D. R. Ma, D. Q. Yu, X. Xiao, B. J. Huang, L. Yang, S. Wang, Chin. J. Catal., 2018, 39, 821-830.
9. [9] W. Li, C. Zhang, X. Li, P. Tan, A. L. Zhou, Q. Y. Fang, G. Chen, Chin. J. Catal., 2018, 39, 1653-1663.
10. [10] S. Zhang, S. J. Liu, W. S. Hu, X. B. Zhu, R. Y. Qu, W. H. Wu, C. H. Zheng, X. Gao, Appl. Surf. Sci., 2019, 466, 99-109.
11. [11] L. Kang, L. Han, J. He, H. Li, T. Yan, G. Chen, J. Zhang, L. Shi, D. Zhang, Environ. Sci. Technol., 2019, 53, 938-945.
12. [12] L. Han, M. Gao, C. Feng, L. Shi, D. Zhang, Environ. Sci. Technol., 2019, 53, 5946-5956.
13. [13] L. Han, M. Gao, J. Y. Hasegawa, S. Li, Y. Shen, H. Li, L. Shi, D. Zhang, Environ. Sci. Technol., 2019, 53, 6462-6473.
14. [14] L. Zhang, L. L. Li, Y. Cao, Y. Xiong, S. G. Wu, J. F. Sun, C. J. Tang, F. Gao, L. Dong, Catal Sci. Technol., 2015, 5, 2188-2196.
15. [15] D. W. Kwon, S. C. Hong, Appl. Surf. Sci., 2015, 356, 181-190.
16. [16] X. L. Li, Y. H. Li, S. S. Deng, T. A. Rong, Catal. Commun., 2013, 40, 47-50.
17. [17] W. Q. Xu, Y. B. Yu, C. B. Zhang, H. He, Catal. Commun., 2008, 9, 1453-1457.
18. [18] X. Gao, Y. Jiang, Y. C. Fu, Y. Zhong, Z. Y. Luo, K. F. Cen, Catal. Commun., 2010, 11, 465-469.
19. [19] Z. Liu, J. Zhu, J. Li, L. Ma, S. I. Woo, ACS Appl. Mater. Interfaces, 2014, 6, 14500-14508.
20. [20] W. P. Shan, F. D. Liu, H. He, X. Y. Shi, C. B. Zhang, Appl. Catal. B, 2012, 115-116, 100-106.
21. [21] X. Gao, X. S. Du, L. W. Cui, Y. C. Fu, Z. Y. Luo, K. F. Cen, Catal. Commun., 2010, 12, 255-258.
22. [22] M. E. Yu, C. T. Li, G. M. Zeng, Y. Zhou, X. N. Zhang, Y. E. Xie, Appl. Surf. Sci., 2015, 342, 174-182.
23. [23] Z. M. Liu, Y. X. Liu, B. H. Chen, T. L. Zhu, L. L. Ma, Catal. Sci. Technol., 2016, 6, 6688-6696.
24. [24] Y. Qiu, B. Liu, J. Du, Q. Tang, Z. H. Liu, R. L. Liu, C. Y. Tao, Chem. Eng. J., 2016, 294, 264-272.
25. [25] Y. Jiang, Z. M. Xing, X. C. Wang, S. B. Huang, Q. Y. Liu, J. S. Yang, J. Ind. Eng. Chem., 2015, 29, 43-47.
26. [26] L. L. Li, W. Tan, X. Q. Wei, Z. X. Fan, A. N. Liu, K. Guo, K. L. Ma, S. H. Yu, C. Y. Ge, C. J. Tang, L. Dong, Catal. Commun., 2018, 114, 10-14.
27. [27] X. Li, X. Li, J. Li, J. Hao, J. Hazard. Mater., 2016, 318, 615-622.
28. [28] Z. M. Liu, S. X. Zhang, J. H. Li, L. L. Ma, Appl. Catal. B, 2014, 144, 90-95.
29. [29] Z. Y. Fei, Y. R. Yang, M. H. Wang, Z. L. Tao, Q. Liu, X. Chen, M. F. Cui, Z. X. Zhang, J. H. Tang, X. Qiao, Chem. Eng. J., 2018, 353, 930-939.
30. [30] Z. M. Liu, H. Su, J. H. Li, Y. Li, Catal. Commun., 2015, 65, 51-54.
31. [31] W. Yu, J. Zhu, L. Qi, C. Sun, F. Gao, L. Dong, Y. Chen, J. Colloid Interfaces Sci., 2011, 364, 435-442.
32. [32] J. Zhu, F. Gao, L. H. Dong, W. J. Yu, L. Qi, Z. Wang, L. Dong, Y. Chen, Appl. Catal. B, 2010, 95, 144-152.
33. [33] X. J. Yao, T. T. Kong, L. Chen, S. M. Ding, F. M. Yang, L. Dong, Appl. Surf. Sci., 2017, 420, 407-415.
34. [34] X. J. Yao, K. L. Ma, W. X. Zou, S. G. He, J. B. An, F. M. Yang, L. Dong, Chin. J. Catal., 2017, 38, 146-159.
35. [35] Y. Peng, R. Qu, X. Zhang, J. Li, Chem. Commun., 2013, 49, 6215-6217.
36. [36] X. L. Hu, Q. Shi, H. Zhang, P. F. Wang, S. H. Zhan, Y. Li, Catal. Today, 2017, 297, 17-26.
37. [37] X. X. Wang, Y. Shi, S. J. Li, W. Li, Appl. Catal. B, 2018, 220, 234-250.
38. [38] Y. R. Yang, M. H. Wang, Z. L. Tao, Q. Liu, Z. Y. Fei, X. Chen, Z. X. Zhang, J. H. Tang, M. F. Cui, X. Qiao, Catal. Sci. Technol., 2018, 8, 6396-6406.
39. [39] H. Liu, Z. X. Fan, C. Z. Sun, Appl. Catal. B, 2019, 244, 671-683
40. [40] X. J. Yao, R. D. Zhao, L. Chen, J. Du, C. Y. Tao, F. M. Yang, L. Dong, Appl. Catal. B, 2017, 208, 82-93.
41. [41] Y. Li, Y. Wan, Y. P. Li, S. H. Zhan, Q. X. Guan, Y. Tian, Appl. Catal. A, 2016, 528, 150-160.
42. [42] Z. L. Wu, A. J. Rondinone, L. N. Ivanov, S. H. Overbury, J. Phys. Chem. C, 2011, 115, 25368-25378.
43. [43] Y. Xiong, C. J. Tang, X. J. Yao, L. Zhang, L. L. Li, X. B. Wang, Y. Deng, F. Gao, L. Dong, Appl. Catal. A, 2015, 495, 206-216.
44. [44] K. Liu, F. D. Liu, L. J. Xie, W. P. Shan, H. He, Catal. Sci. Technol., 2015, 5, 2290-2299.
45. [45] Y. Peng, K. Z. Li, J. H. Li, Appl. Catal. B, 2013, 140-141, 483-492.
46. [46] S. M. Lee, K. H. Park, S. C. Hong, Chem. Eng. J., 2012, 195-196, 323-331.
47. [47] X. M. Wang, X. Y. Li, Q. D. Zhao, W. B. Sun, M. Tade, S. M. Liu, Chem. Eng. J., 2016, 288, 216-222.
48. [48] X. J. Yao, L. Chen, J. Cao, F. M. Yang, W. Tan, L. Dong, Ind. Eng. Chem. Res., 2018, 57, 12407-12419.
49. [49] F. D. Liu, H. He, Catal. Today, 2010, 153, 70-76.
50. [50] T. Zhang, R. Y. Qu, W. K. Su, J. H. Li, Appl. Catal. B, 2015, 176-177, 338-346.
51. [51] W. Shan, F. Liu, H. He, X. Shi, C. Zhang, Chem. Commun., 2011, 47, 8046-8048.
52. [52] X. L. Li, Y. H. Li, J. Mol. Catal. A, 2014, 386, 69-77.
53. [53] K. B. Nam, D. W. Kwon, S. C. Hong, Appl. Catal. A, 2017, 542, 55-62.
54. [54] J. Liu, X. Y. Li, Q. D. Zhao, J. Ke, H. N. Xiao, X. J. Lv, S. M. Liu, M. Tadé, S. B. Wang, Appl. Catal. B, 2017, 200, 297-308.
55. [55] S. P. Ding, F. D. Liu, X. Y. Shi, K. Liu, Z. H. Lian, L. J. Xie, H. He, ACS Appl. Mater. Interfaces, 2015, 7, 9497-9506.
56. [56] Z. R. Ma, X. D. Wu, Z. C. Si, D. Weng, J. Ma, T. F. Xu, Appl. Catal. B, 2015, 179, 380-394.

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沈阳化工大学材料科学与工程学院沈阳 110142

表面Mo修饰提高CeTiO_x催化剂低温脱硝性能

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Enhanced low-temperature NH₃-SCR performance of CeTiO_x catalyst via surface Mo modification

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