Citation: LI Yan-Feng, ZHU Ji-Qin, LIU Hui, HE Peng, WANG Peng, TIAN Hui-Ping. Theoretical Study of the Double-Bond Isomerization of 1-Hexene to cis-2-Hexene over ZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2011, 27(05): 1081-1088. doi: 10.3866/PKU.WHXB20110516 shu

Theoretical Study of the Double-Bond Isomerization of 1-Hexene to cis-2-Hexene over ZSM-5 Zeolite

LI Yan-Feng ¹ ,
ZHU Ji-Qin ¹ ,
LIU Hui ^1, ,
HE Peng ¹ ,
WANG Peng ² ,
TIAN Hui-Ping ²

1.
1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China;
2. Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, P. R. China

Received Date: 6 January 2011
Available Online: 1 April 2011
Fund Project: 国家重点基础研究发展计划项目(973) (2010CB732301)资助 (973) (2010CB732301)

We investigated the double-bond isomerization reaction of 1-hexene to cis-2-hexene on the surface of ZSM-5 zeolite using density functional theory with a 54T cluster model simulating the local structures of zeolite materials. We found that the double-bond isomerization proceeded by a mechanism that did not involve the bifunctional (acid-base) nature of the zeolite active sites but exclusively involved the Brønsted acid sites. According to this mechanism, 1-hexene is the first physically adsorbed onto the zeolite acid site resulting in the formation of a π-complex, and then the acidic proton of the zeolite transfers to a carbon atom of the double bond of the physisorbed 1-hexene. The other carbon atom of the double bond of the physisorbed 1-hexene bonds with the Brønsted host oxygen and yields a stable alkoxy intermediate. Thereafter, the Brønsted host oxygen abstracts a hydrogen atom from the C₆H₁₃ fragment and the C―O bond of the alkoxy intermediate is broken, which restores the zeolite active site and yields physisorbed cis-2-hexene. The proposed reaction pathway competes with the bifunctional pathway. The rate- determining step is the decomposition of the alkoxy intermediate with an activation energy of 134. 64 kJ·mol^-1. The calculated apparent activation energy for the isomerization reaction is 59. 37 kJ·mol^-1, which is in od agreement with the reported experimental value. These results well explain the energetic aspects during the double-bond isomerization and extend the understanding of the nature of zeolite active sites.
- ZSM-5,
- Active site,
- Hexene,
- Density functional theory,
- Double-bond isomerization
1. [1]
  
  (1) Wang, W. L.; Liu, B. J.; Zeng, X. J. Acta Phys. -Chim. Sin. 2008, 24, 2102.
2. [2]
  [王文兰, 刘百军, 曾贤君. 物理化学学报, 2008, 24, 2102. ]
3. [3]
  (2) Vermeiren, W.; Gilson, J. P. Top. Catal. 2009, 52, 1131.
4. [4]
  (3) Kazansky, V. B. Acc. Chem. Res. 1991, 24, 379.
5. [5]
  (4) Perez-Luna, M.; Cosultchi, A.; Toledo-Antonio, J. A.; Diaz-Garcia, L. Catal. Lett. 2009, 128, 290.
6. [6]
  (5) Song, Y.; Bai, J.; Wu, Z. H.; Zhai, Y. C.; Xu, L. Y. Nat. Gas Chem. Ind. 2005, 30, 1.
7. [7]
  [宋毅, 白杰, 吴治华, 翟玉春, 徐龙伢. 天然气化工, 2005, 30, 1. ]
8. [8]
  (6) Zheng, A.; Wang, L.; Chen, L.; Yue, Y.; Ye, C.; Lu, X.; Deng, F. Chem. Phys. Chem. 2007, 8, 231.
9. [9]
  (7) Lechert, H.; Dimitrov, C.; Bezuhanova, C.; Nenova, V. J. Catal. 1983, 80, 457.
10. [10]
  (8) Bezouhanova, C.; Lechert, H.; Taralanska, G.; Meyer, A. React. Kinet. Catal. Lett. 1989, 40, 209.
11. [11]
  (9) Abbot, J.; Corma, A.; Wojciechowski, B. W. J. Catal. 1985, 92, 398.
12. [12]
  (10) Campbell, I. M. Catalysis at Surfaces, 1st ed.; Chapman and Hall: New York, 1988; pp 174-178.
13. [13]
  (11) Pines, H. The Chemistry of Catalytic Hydrocarbon Conversions, 1st ed.; Academic Press: New York, 1981; pp 29-33.
14. [14]
  (12) Burwell, R. L.; Shim, K. C.; Rowlinsox, H. C. J. Am. Chem. Soc. 1957, 79, 5142.
15. [15]
  (13) Brouwer, D. M. J. Catal. 1962, 1, 22.
16. [16]
  (14) Haw, J. F.; Richardson, B. R.; Oshiro, I. S.; Lazo, N. D.; Speed, J. A. J. Am. Chem. Soc. 1989, 111, 2052.
17. [17]
  (15) Kondo, J. N.; Wakabayashi, F.; Domen, K. Catal. Lett. 1998, 53, 215.
18. [18]
  (16) Pu, M.; Li, Z. H.; Zhai, S. R.; Wu, D.; Sun, Y. H. Stud. Surf. Sci. Catal. 2003, 146, 737.
19. [19]
  (17) Pu, M.; Li, Z. H.; ng, Y. J.; Wu, D.; Sun, Y. H. J. Mater. Sci. Lett. 2003, 22, 955.
20. [20]
  (18) Li, H. Y.; Pu, M.; Chen, B. H. Acta Phys. -Chim. Sin. 2005, 21, 898.
21. [21]
  [李会英, 蒲敏, 陈标华. 物理化学学报, 2005, 21, 898. ]
22. [22]
  (19) Benco, L.; Demuth, T.; Hafner, J.; Hutschka, F.; Toulhoat, H. J. Catal. 2002, 205, 147.
23. [23]
  (20) Bhan, A.; Joshi, Y. V.; Delgass, W. N.; Thomson, K. T. J. Phys. Chem. B 2003, 107, 10476.
24. [24]
  (21) Li, Y. F.; He, P.; Zhu, J. Q.; Liu, H.; Shao, Q.; Tian, H. P. J. Mol. Struc-theochem 2010, 940, 135.
25. [25]
  (22) Boronat, M.; Viruela, P. M.; Corma, A. J. Am. Chem. Soc. 2004, 126, 3300.
26. [26]
  (23) Namuangruk, S.; Khongpracha, P.; Pantu, P.; Limtrakul, J. J. Phys. Chem. B 2006, 110, 25950.
27. [27]
  (24) Zheng, A.; Chen, L.; Yang, J.; Zhang, M.; Su, Y.; Yue, Y.; Ye, C.; Deng, F. J. Phys. Chem. B 2005, 109, 24273.
28. [28]
  (25) Zheng, A.; Chen, L.; Yang, J.; Yue, Y.; Ye, C.; Lu, X.; Deng, F. Chem. Commun. 2005, 19, 2474.
29. [29]
  (26) Zheng, A.; Liu, S. B.; Deng, F. Microporous Mesoporous Mat. 2009, 121, 158.
30. [30]
  (27) Jacobs, P. A.; Martens, J. A.; Weitkamp, J.; Beyer, H. K. Faraday Discuss. Chem. Soc. 1981, 72, 353.
31. [31]
  (28) Mortier, W. J.; Sauer, J.; Lercher, J. A.; Noller, H. J. Phys. Chem. 1984, 88, 905.
32. [32]
  (29) Trombetta, M.; Armaroli, T.; Alejandre, A. G.; Solis, J. R.; Busca, G. Appl. Catal. A-Gen. 2000, 192, 125.
33. [33]
  (30) Lomratsiri, J.; Probst, M.; Limtrakul, J. J. Mol. Graphics Modell. 2006, 25, 219.
34. [34]
  (31) Lermer, H.; Draeger, M.; Steffen, J.; Unger, K. K. Zeolites 1985, 5, 131.
35. [35]
  (32) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
36. [36]
  (33) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
37. [37]
  (34) Pantu, P.; Pabchanda, S.; Limtrakul, J. Chem. Phys. Chem. 2004, 5, 1901.
38. [38]
  (35) Bobuatong, K.; Limtrakul, J. Appl. Catal. A-Gen. 2003, 253, 49.
39. [39]
  (36) Kasuriya, S.; Namuangruk, S.; Treesukol, P.; Tirtowidjojo, M.; Limtrakul, J. J. Catal. 2003, 219, 320.
40. [40]
  (37) Panjan, W.; Limtrakul, J. J. Mol. Struct. 2003, 654, 35.
41. [41]
  (38) Namuangruk, S.; Tantanak, D.; Limtrakul, J. J. Mol. Catal. A: Chem. 2006, 256, 113.
42. [42]
  (39) Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502.
43. [43]
  (40) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03, Revision D. 01; Gaussian Inc. : Wallingford, CT, 2004.
44. [44]
  (41) Föttinger, K.; Kinger, G.; Vinek, H. Appl. Catal. A: Gen. 2003, 249, 205.
45. [45]
  (42) Krossner, M.; Sauer, J. J. Phys. Chem. 1996, 100, 6199.
46. [46]
  (43) Viruela-Martin, P.; Zicovich-Wilson, C. M.; Corma, A. J. Phys. Chem. 1993, 97, 13713.
47. [47]
  (44) Clark, M. C.; Subramaniam, B. AIChE J. 1999, 45, 1559.
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