紫外拉曼光谱研究FAU到CHA和MFI分子筛的转晶过程

引用本文: 张娟, 褚月英, 刘小龙, 徐好, 冯兆池, 孟祥举, 肖丰收. 紫外拉曼光谱研究FAU到CHA和MFI分子筛的转晶过程[J]. 催化学报, 2019, 40(12): 1854-1859. doi: S1872-2067(19)63287-0 shu

Citation: Juan Zhang, Yueying Chu, Xiaolong Liu, Hao Xu, Xiangju Meng, Zhaochi Feng, Feng-Shou Xiao. Interzeolite transformation from FAU to CHA and MFI zeolites monitored by UV Raman spectroscopy[J]. Chinese Journal of Catalysis, 2019, 40(12): 1854-1859. doi: S1872-2067(19)63287-0 shu

紫外拉曼光谱研究FAU到CHA和MFI分子筛的转晶过程

张娟 ^a, ,
褚月英 ^c, ,
刘小龙 ^d, ,
徐好 ^a, ,
冯兆池 ^b, ,
孟祥举 ^a, ,
肖丰收 ^a,

a 浙江大学化学系浙江省应用化学重点实验室, 浙江杭州 310028;
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023;
c 中国科学院武汉物理与数学研究所波谱与原子分子物理国家重点实验室, 湖北武汉 430071;
d 中山大学材料科学与工程学院, 广东广州 510275
基金项目:
国家重点研发计划（2017YFB0702800）；国家自然科学基金（2152780065，91634201，21720102001）；中国科学院战略性先导科技专项（XDB17000000）.

摘要: 分子筛是一类广泛运用于工业催化的多孔无机微晶材料，尽管其制备方式和晶化机理的报道很多，但是大多局限于无机凝胶合成体系.近年来，分子筛间的转晶生长引起了广泛关注，尤其是以高硅铝比的FAU分子筛作为原料进行转晶，因其结构中含有大量有序连接的双六元环（D6R）单元，前述研究多认为D6R结构在分子筛间的转晶过程中起着重要作用，但是这种作用并未得到详尽描述.一直以来，紫外拉曼光谱都被认为是表征分子筛结构单元的有力手段，它可用以鉴定分子筛骨架或半骨架结构的特征振动.因此，本文运用紫外拉曼光谱技术监测由FAU分子筛转晶成CHA和MFI的晶化过程，并采用DFT计算进行辅助证明，观察了D6R结构的转晶行为.
紫外拉曼光谱结果表明，FAU结构中的D6R物种在分子筛间的转晶过程中对目标分子筛的形成起着关键作用.在FAU转晶成CHA的晶化过程中，紫外拉曼光谱表明FAU和CHA上均出现300 cm^-1的振动峰，该峰可归属于D6R结构的弯曲振动.在转化过程中，FAU和CHA的结晶度分别呈现出明显的降低和增长的趋势，而D6R振动峰的强度在实验误差允许范围内基本保持不变，表明尽管体系中存在着FAU溶解和CHA生成的动态平衡，但是D6R结构却始终保持相对稳定，这种现象可归因于二者都含有相同的结构单元D6R，这种结构相似性使得D6R物种更易于保持结构完整性从而进行直接转化.
然而，在FAU转晶成MFI的晶化过程中，紫外拉曼光谱表明FAU的300 cm^-1振动峰的强度随着晶化时间的延长而不断减弱，与此同时，MFI归属于单六元环（S6R）的289 cm^-1振动峰的强度在短时间内迅速增大到最大值，而归属于四元环（4R）和五元环（5R）的433，475和377 cm^-1振动峰的强度均与MFI结晶度的增长呈现相同趋势.这表明转化过程中FAU结构的D6R物种将更倾向于被分解成两个S6R而非三个4R，4R和5R只能在MFI骨架结构形成后被观察到，即发挥作用的基本结构单元是S6R而非5R，分解出来的S6R再用以进一步组装成MFI结构.为进一步验证D6R结构易于分解成S6R，采用DFT计算对从D6R结构分解成两个S6R和三个4R的生成焓进行了比较.结果表明，分解成两个S6R的生成焓（-16.3 kcal/mol）明显低于分解成三个4R的生成焓（-4.6 kcal/mol），说明D6R生成两个S6R的可能性更大，这恰好与紫外拉曼光谱的结果一致.上述研究将有助于更好地理解分子筛间的转晶行为.

关键词:

English

Interzeolite transformation from FAU to CHA and MFI zeolites monitored by UV Raman spectroscopy

a Department of Chemistry, Key Lab of Applied Chemistry of Zhejiang Province, Zhejiang University, Hangzhou 310028, Zhejiang, China;
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, Hubei, China;
d School of Materials Science and Engineering, Sun Yat-Sun University, Guangzhou 510275, Guangdong, China
Received Date: 10 January 2019
Revised Date: 25 February 2019
Fund Project:
This work was supported by the National Key R&

Abstract: As a powerful and sensitive tool for the characterization of zeolite building units, UV Raman spectroscopy has been used to monitor interzeolite transformation from FAU to CHA and MFI zeolites. The results show that the behavior of double 6-membered rings (D6Rs) in the FAU zeolite framework plays an important role during the formation of the target product in the interzeolite transformation. For the transformation of FAU to CHA, because both zeolites contain the same D6R units, direct transformation occurs, in which the D6Rs were largely unchanged. In contrast, for the transformation of FAU to MFI, the D6Rs can be divided into two single 6-membered rings (S6Rs), which further assembled into the MFI structure. In this crystallization, 5-membered rings (5Rs) are only observed in the MFI framework formation, suggesting that the basic building units in the transformation of FAU to MFI are S6Rs rather than 5Rs. These insights will be helpful for further understanding of the interzeolite transformation.

Key words:

1. [1] A. Corma, Chem. Rev., 1995, 95, 559-614.
2. [2] M. E. Davis, Nature, 2002, 417, 813-821.
3. [3] H. Gies, B. Marler, Zeolites, 1992, 12, 42-49.
4. [4] S. Mintova, J. P. Gilson, V. Valtchev, Nanoscale, 2013, 5, 6693-6703.
5. [5] M. Moliner, F. Rey, A. Corma, Angew. Chem. Int. Ed., 2013, 52, 13880-13889.
6. [6] J. Shin, M. A. Camblor, H. C. Woo, S. R. Miller, P. A. Wright, S. B. Hong, Angew. Chem. Int. Ed., 2009, 48, 6647-6649.
7. [7] N. Nakazawa, T. Ikeda, N. Hiyoshi, Y. Yoshida, Q. Han, S. Inagaki, Y. Kubota, J. Am. Chem. Soc., 2017, 139, 7989-7997.
8. [8] E. M. Gallego, M. T. Portilla, C. Paris, A. Leon-Escamilla, M. Boronat, M. Moliner, A. Corma, Science, 2017, 355, 1051-1054.
9. [9] T. Maruo, N. Yamanaka, N. Tsunoji, M. Sadakane, T. Sano, Chem. Lett., 2014, 43, 302-304.
10. [10] N. Martin, Z. B. Li, J. Martínez-Triguero, J. H. Yu, M. Moliner, A. Corma, Chem. Commun., 2016, 52, 6072-6075.
11. [11] J. E. Schmidt, M. A, Deimund, D. Xie, M. E. Davis, Chem. Mater., 2015, 27, 3756-3762.
12. [12] H. Xu, Q. M. Wu, Y. Y. Chu, J. G. Jiang, L. Zhang, S. X. Pan, C. S. Zhang, L. F. Zhu, F. Deng, X. J. Meng, S. Maurer, R. McGuire, A. N. Parvulescu, U. Müller, F. S. Xiao, J. Mater. Chem. A, 2018, 6, 8705-8711.
13. [13] L. Van Tendeloo, E. Gobechiya, E. Breynaert, J. A. Martens, C. E. A. Krischhock, Chem. Commun., 2013, 49, 11737-11739.
14. [14] N. Funase, T. Tanigawa, Y. Yamasaki, N. Tsunoji, M. Sadakane, T. Sano, J. Mater. Chem. A, 2017, 5, 19245-19254.
15. [15] M. Itakura, K. Ota, S. Shibata, T. Inoue, Y. Ide, M. Sadakane, T. Sano, J. Cryst. Growth, 2011, 314, 274-278.
16. [16] C. Y. Hu, W. F. Yan, R. R. Xu, Acta Chim. Sin., 2017, 75, 679-685.
17. [17] Y. C. Shi, E. H. Xing, X. Z. Gao, D. Y. Liu, W. H. Xie, F. M. Zhang, X. H. Mu, X. T. Shu, Microporous Mesoporous Mater., 2014, 200, 269-278.
18. [18] W. Fan, M, Ogura, G. Sankar, T. Okubo, Chem. Mater., 2007, 19, 1906-1917.
19. [19] M. B. Park, Y. Lee, A. M. Zheng, F. S. Xiao, C. P. Nicholas, G. J. Lewis, S. B. Hong, J. Am. Chem. Soc., 2013, 135, 2248-2255.
20. [20] S. Prodinger, A. Vjunov, J. Z. Hu, J. L. Fulton, D. M. Canaioni, M. A. Derewinski, J. A. Lercher, Chem. Mater., 2018, 30, 888-897.
21. [21] S. A. Pelster, R. Kalamajka, W. Schrader, F. Schuth, Angew. Chem. Int. Ed., 2007, 46, 2299-2302.
22. [22] B. B. Schaack, W. Schrader, F. Schuth, Angew. Chem. Int. Ed., 2008, 47, 9092-9095.
23. [23] T. M. Davis, T. O. Drews, H. Ramanan, C. He, J. S. Dong, H. Schnablegger, M. A. Katsoulakis, E. Kokkoli, A. V. McCormick, R. L. Penn, M. Tsapatsis, Nat. Mater., 2006, 5, 400-408.
24. [24] A. I. Lupulescu, J. D. Rimer, Science, 2014, 344, 729-732.
25. [25] S. Mintova, N. H. Olson, V. Valthev, T. Bein, Science, 1999, 283, 958-960.
26. [26] Y. Zhao, H. B. Zhang, P. C. Wang, F. Q. Xue, Z. Q. Ye, Y. H. Zhang, Y. Tang, Chem. Mater., 2017, 29, 3387-3396.
27. [27] F. T. Fan, Z. C. Feng, C. Li, Chem. Soc. Rev., 2010, 39, 4794-4801.
28. [28] L. M. Ren, Q. Guo, H. Y. Zhang, L. F. Zhu, C. G. Yang, L, Wang, Z. C. Feng, C. Li, F. S. Xiao, J. Mater. Chem., 2012, 22, 6564-6567.
29. [29] N. Sheng, Y. Y. Chu, S. H. Xin, Q, Wang, X. F. Yi, Z. C. Feng, X. J. Meng, X. L. Liu, F. Deng, F. S. Xiao, J. Am. Chem. Soc., 2016, 138, 6171-6176.
30. [30] M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 09, Revision B, 01, 2010.
31. [31] Y. Yu, G. Xiong, C. Li, F. S. Xiao, Microporous Mesoporous Mater., 2001, 46, 23-34.
32. [32] P. Li, T. Ding, L. P. Liu, G. Xiong, Mater. Charact., 2013, 86, 221-231.
33. [33] P. K. Dutta, D. C. Shieh, M. Puri, J. Phys. Chem., 1987, 91, 2332-2336.
34. [34] F. T. Fan, Z. C. Feng, G. N. Li, K. J. Sun, P. L. Ying, C. Li, Chem. Eur. J., 2008, 14, 5125-5129.
35. [35] C. L. Angell, J. Phys. Chem., 1973, 77, 222-227.
36. [36] D. K. Arkhipenko, G. P. Valueva, T. N. Moroz, J. Struct. Chem., 1995, 36, 171-174.
37. [37] C. H. Sun, D. J. Srivastava, P. J. Grandinetti, P. K. Dutta, Microporous Mesoporous Mater., 2016, 230, 208-216.
38. [38] T. Ikuno, W. Chaikittisilp, Z. D. Liu, T. Iida, Y, Yanaba, T. Yoshikawa, S. Kohara, T. Wakihara, T. Okubo, J. Am. Chem. Soc., 2015, 137, 14533−14544.
39. [39] B. Mihailova, V. Valtchev, S. Mintova, A. C. Faust, N. Petkov, T. Bein, Phys. Chem. Chem. Phys., 2005, 7, 2756-2763.
40. [40] L. M. Ren, Q. Guo, H. Y. Zhang, L. F. Zhu, C. G. Yang, L. Wang, X. J. Meng, Z. C. Feng, C. Li, F. S. Xiao, J. Mater. Chem., 2012, 22, 6564-6567.
41. [41] Q. M. Wu, X. Wang, G. D. Qi, Q. Guo, S. X. Pan, X. J. Meng, F. Deng, F. T. Fan, Z. C. Feng, C. Li, S. Maurer, U. Muller, F. S. Xiao, J. Am. Chem. Soc., 2014, 136, 4019-4025.
42. [42] Y. Y. Chu, G. C. Li, L. Huang, X. F. Yi, H. Q. Xia, A. M. Zheng, F. Deng, Catal. Sci. Technol., 2017, 7, 2512-2523.
43. [43] Y. Y. Chu, B. Han, A. M. Zheng, X. F. Yi, F. Deng, J. Phys. Chem. C, 2013, 117, 2194−2202.

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紫外拉曼光谱研究FAU到CHA和MFI分子筛的转晶过程

English

Interzeolite transformation from FAU to CHA and MFI zeolites monitored by UV Raman spectroscopy

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

紫外拉曼光谱研究FAU到CHA和MFI分子筛的转晶过程

English

Interzeolite transformation from FAU to CHA and MFI zeolites monitored by UV Raman spectroscopy

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？

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