稀土氧化物EuOx对Pt/CeO2材料在甲苯催化燃烧中的显著促进机制

引用本文: 赵宝明, 建艳飞, 姜泽宇, Reem Albilali, 何炽. 稀土氧化物EuO_x对Pt/CeO₂材料在甲苯催化燃烧中的显著促进机制[J]. 催化学报, 2019, 40(4): 543-552. doi: S1872-2067(19)63292-4 shu

Citation: Baoming Zhao, Yanfei Jian, Zeyu Jiang, Reem Albilali, Chi He. Revealing the unexpected promotion effect of EuO_x on Pt/CeO₂ catalysts for catalytic combustion of toluene[J]. Chinese Journal of Catalysis, 2019, 40(4): 543-552. doi: S1872-2067(19)63292-4 shu

稀土氧化物EuO_x对Pt/CeO₂材料在甲苯催化燃烧中的显著促进机制

a 西安近代化学研究所, 陕西西安 710065, 中国;
b 西安交通大学能源与动力工程学院, 动力工程多相流国家重点实验室, 陕西西安 710049, 中国;
c 伊玛目阿卜杜勒拉曼本费萨尔大学科学学院化学系, 达曼 31441, 沙特阿拉伯;
d 中国科学院大学, VOCs污染控制材料与技术国家工程实验室, 北京 101408, 中国
基金项目:
国家重点研发计划（2016YFC0204201）；国家自然科学基金（21677114，21477095，21876139）；中央高校基本科研业务费专项基金（xjj2017170）.

摘要: 挥发性有机污染物是大气环境中一类重要的污染物质，其污染控制问题已成为21世纪大气污染控制的优先方向之一.甲苯作为一种典型芳香烃在医药、农药、染料合成等多个化工行业中常用作有机化工原料并被排入大气环境，对人类的生产和生活造成极大危害.由于其高致癌性，甲苯在2017年被世界卫生组织国际癌症研究机构列为3类致癌物.在甲苯的催化燃烧降解中，负载型铂基催化剂由于其高效的低温催化活性被学者广泛研究.CeO₂作为一种典型的稀土金属氧化物具有较强的储放氧能力和高温稳定性，被视为负载型贵金属催化剂的优良载体.近期研究表明，EuO_x具有良好的催化氧化活性，并能促进金属氧化物表面氧缺位的形成.为了进一步研究EuO_x与CeO₂之间的协同效应对贵金属基催化剂低温催化性能的影响，我们利用表面模板剂法合成了具有不同Eu负载量的Pt/Eu₂O₃-CeO₂材料并应用于甲苯的深度催化氧化.研究表明，EuO_x的加入显著提高了Pt/CeO₂材料的催化性能，当Eu含量为2.5 at%时（Pt/EC-2.5）该材料拥有最佳的低温氧化活性，可在200℃实现对0.09%甲苯的完全降解，在160℃时反应速率和转化频次分别高达0.9mmol g^-1 s^-1和5.52×10² s^-1.相比于Pt/CeO₂催化剂，EuO_x与CeO₂之间的协同作用极大提高了催化剂的氧化还原性能，增大了材料表面晶格氧和Ce³⁺的含量，并显著提高了贵金属活性相的分散度.通过原位漫反射红外光谱在线分析了甲苯在Pt/Eu₂O₃-CeO₂材料表面的深度降解机理.与甲苯在Pt/CeO₂材料表面的氧化行为相比，甲苯在Pt/EC-2.5催化剂表面的降解遵循典型的Mars-van Krevelen（MvK）机理.当吸附于稀土金属氧化物载体后，在Pt活性位点、晶格氧及表面酸性位点的联合作用下，甲苯以酮类和醛类为主要的中间产物，被迅速深度氧化为H₂O和CO₂.

关键词:

English

Revealing the unexpected promotion effect of EuO_x on Pt/CeO₂ catalysts for catalytic combustion of toluene

a Xi'an Modern Chemistry Research Institute, Xi'an 710065, Shaanxi, China;
b State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China;
c Department of Chemistry, College of Science, Imam Abdulrahman Bin Faisal University, P. O. Box 1982, Dammam 31441, Saudi Arabia;
d National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing 101408, China
Received Date: 21 November 2018
Revised Date: 22 December 2018

Abstract: Pt/Eu₂O₃-CeO₂ materials with different Eu concentrations were prepared and applied to toluene destruction, and the remarkable promotion impact of EuO_x on Pt/CeO₂ can be observed. The characterization results reveal that the presence of EuO_x significantly enhances the redox property, lattice O concentration, and Ce³⁺ ratio of the Pt/CeO₂ material, which facilitates the dispersion and activity of Pt active sites and thus accelerates the decomposition process of toluene. Among all catalysts, a sample with an Eu content of 2.5 at.% (Pt/EC-2.5) possesses the best catalytic activity with 0.09 vol% of toluene completely destructed at 200℃ under a relatively high GHSV of 50000 h^-1. The possible reaction pathway and mechanism of toluene combustion over Pt/Eu₂O₃-CeO₂ samples are presented according to in-situ DRIFTS, which confirms that the toluene oxidation process obeys the Mars-van Krevelen mechanism with aldehydes and ketones as primary organic intermediates.

Key words:

1. [1] Y. X. Liu, J. G. Deng, S. H. Xie, Z. W. Wang, H. X. Dai, Chin. J. Catal., 2016, 37, 1193-1205.
2. [2] M. J. Tian, Y. F. Jian, M. D. Ma, C. He, C. W. Chen, C. Liu, J. W. Shi, Appl. Catal. A, 2019, 570, 62-72.
3. [3] H. Deng, S. Y. Kang, C. Y. Wang, H. He, C. B. Zhang, Chem. Eng. J., 2018, 348, 361-369.
4. [4] Z. Sihaib, F. Puleo, J. M. Garcia-Vargas, L. Retailleau, C. Descorme, L. F. Liotta, J. L. Valverde, S. Gil, A. Giroir-Fendler, Appl. Catal. B, 2017, 209, 689-700.
5. [5] C. Y. Chen, F. Chen, L. Zhang, S. X. Pan, C. Q Bian, X. M. Zheng, X. J. Meng, F. S. Xiao, Chem. Commun., 2015, 51, 5936-5938.
6. [6] W. Li, H. Q. Ye, G. G. Liu, H. C. Ji, Y. H. Zhou, K. Han, Chin. J. Catal., 2018, 39, 946-954.
7. [7] C. B. Zhang, F. D. Liu, Y. P. Zhai, H. Ariga, N. Yi, Y. C. Liu, K. Asakura, M. Flytzani-Stephanopoulos, H. He, Angew. Chem. Int. Ed., 2012, 51, 9628-9632.
8. [8] L. H. Nie, J. G. Yu, M. Jaroniec, F. F. Tao, Catal. Sci. Technol., 2016, 6, 3649-3669.
9. [9] B. Y. Bai, Q. Qiao, J. H. Li, J. M. Hao, Chin. J. Catal., 2016, 37, 102-122.
10. [10] S. Royer, D. Duprez, F. Can, X. Courtois, C. Batiot-Dupeyrat, S. Laassiri, H. Alamdari, Chem. Rev., 2014, 114, 10292-10368.
11. [11] L. F. Liotta, Appl. Catal. B, 2010, 100, 403-412.
12. [12] Z. Y. Jiang, C. He, N. F. Dummer, J. W. Shi, M. J. Tian, C. Y. Ma, Z. P. Hao, S. H. Taylor, M. D. Ma, Z. X. Shen, Appl. Catal. B, 2018, 226, 220-233.
13. [13] H. Mistry, F. Behafarid, E. Zhou, L. K. Ono, L. Zhang, B. Roldan Cuenya, ACS Catal., 2014, 4, 109-115.
14. [14] H. P. Zhou, H. S. Wu, J. Shen, A. X. Yin, L. D. Sun, C. H. Yan, J. Am. Chem. Soc., 2010, 132, 4998-4999.
15. [15] L. Nie, D. H. Mei, H. F. Xiong, B. Peng, Z. B. Ren, X. I. P. Hernandez, A. De La Riva, M. Wang, M. H. Engelhard, L. Kovarik, A. K. Datye, Y. Wang, Science, 2017, 358, 1419-1423.
16. [16] R. S. Peng, S. J. Li, X. B. Sun, Q. M. Ren, L. M. Chen, M. L. Fu, J. L. Wu, D. Q. Ye, Appl. Catal. B, 2018, 220, 462-470.
17. [17] M. Y. Mao, H. Q. Lv, Y. Z. Li, Y. Yang, M. Zeng, N. Li, X. J. Zhao, ACS Catal., 2016, 6, 418-427.
18. [18] M. Florea, M. Alifanti, V. Kuncser, D. Macovei, N. Apostol, P. Granger, V. I. Parvulescu, J. Catal., 2014, 316, 130-140.
19. [19] Z. Y. Jiang, C. W. Chen, M. D. Ma, Z. Guo, Y. K. Yu, C. He, Catal. Sci. Technol., 2018, 8, 5933-5942.
20. [20] K. M. Ji, H. X. Dai, J. G. Deng, H. Y. Jiang, L. Zhang, H. Zhang, Y. J. Cao, Chem. Eng. J., 2013, 214, 262-271.
21. [21] H. F. Li, N. Zhang, P. Chen, M. F. Luo, J. Q. Lu, Appl. Catal. B, 2011, 110, 279-285.
22. [22] G. L. Zou, H. Lan, R. Y. Song, H. M. Xie, Q. X. Du, RSC Adv., 2014, 4, 50840-50850.
23. [23] J. M. Wu, L. Zeng, D. G. Cheng, F. Q. Chen, X. L. Zhan, J. L. Gong, Chin. J. Catal., 2016, 37, 83-90.
24. [24] C. He, B. T. Xu, J. W. Shi, N. L. Qiao, Z. P. Hao, J. L. Zhao, Fuel Process. Technol., 2015, 130, 179-187.
25. [25] C. He, Z. Y. Jiang, M. D. Ma, X. D. Zhang, M. Douthwaite, J. W. Shi, Z. P. Hao, ACS Catal., 2018, 8, 4213-4229.
26. [26] M. D. Ma, H. Huang, C. W. Chen, Q. Zhu, L. Yue, R. Albilali, C. He, Mol. Catal., 2018, 455, 192-203.
27. [27] H. F. Lu, Y. Zhou, W. F. Han, H. F. Huang, Y. F. Chen, Catal. Sci. Technol., 2013, 3, 1480-1484.
28. [28] D. R. Carvalho, I. B. Aragao, D. Zanchet, J. Nanosci. Nanotechnol., 2018, 18, 3405-3412.
29. [29] Y. F. Jian, M. D. Ma, C. W. Chen, C. Liu, Y. K. Yu, Z. P. Hao, C. He, Catal. Sci. Technol., 2018, 8, 3863-3875.
30. [30] M. J. Tian, C. He, Y. K. Yu, H. Pan, L. Smith, Z. Y. Jiang, N. B. Gao, Y. F. Jian, Z. P. Hao, Q. Zhu, Appl. Catal. A, 2018, 553, 1-14.
31. [31] H. Pan, Y. F. Jian, C. W. Chen, C. He, Z. P Hao, Z. X. Shen, H. X. Liu, Environ. Sci. Technol., 2017, 51, 6288-6297.
32. [32] S. X. Cai, D. S. Zhang, L. Zhang, L. Huang, H. R. Li, R. H. Gao, L. Y. Shi, J. P. Zhang, Catal. Sci. Technol., 2014, 4, 93-101.
33. [33] T. Boningari, P. R. Ettireddy, A. Somogyvari, Y. Liu, A. Vorontsov, C. A. McDonald, P. G. Smirniotis, J. Catal., 2015, 325, 145-155.
34. [34] R. D. Zhang, D. J. Shi, N. Liu, Y. Cao, B. H. Chen, Appl. Catal. B, 2014, 146, 79-93.
35. [35] Y. T. Lai, T. C. Chen, Y. K. Lan, B. S. Chen, J. H. You, C. M. Yang, N. C. Lai, J. H. Wu, C. S. Chen, ACS Catal., 2014, 4, 3824-3836.
36. [36] C. S. Chen, Y. T. Lai, T. C. Chen, C. H. Chen, J. F. Lee, C. W. Hsu, H. M. Kao, Nanoscale, 2014, 6, 12644-12654.
37. [37] F. Zasada, J. Janas, W. Piskorz, M. Gorczynska, Z. Sojka, ACS Catal., 2017, 7, 2853-2867.
38. [38] H. Y. Kim, G. Henkelman, J. Phys. Chem. Lett., 2013, 4, 216-221.

扫一扫看文章

计量

PDF下载量: 6
文章访问数: 1508
HTML全文浏览量: 112

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

稀土氧化物EuO_x对Pt/CeO₂材料在甲苯催化燃烧中的显著促进机制

English

Revealing the unexpected promotion effect of EuO_x on Pt/CeO₂ catalysts for catalytic combustion of toluene

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