Citation: LI Jing-Hong, ZHOU Dan-Hong, REN Jue. Theoretical Study of Ethylene Dimerization on the Ga/HZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2011, 27(06): 1393-1399. doi: 10.3866/PKU.WHXB20110631 shu

Theoretical Study of Ethylene Dimerization on the Ga/HZSM-5 Zeolite

1.
Institute of Chemistry for Functionalized Materials, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China

Received Date: 14 January 2011
Available Online: 10 May 2011
Fund Project: 国家自然科学基金(20073058)资助项目 (20073058)

We studied the reaction mechanisms of ethylene dimerization to 1-butene on Ga/HZSM-5 and Al/HZSM-5 zeolite catalysts by theoretical calculations and investigated the influence of zeolite acidity on the reaction energetics. The calculations were performed using the hybrid ONIOM2 (B3LYP/6-31G(d, p):UFF) method based on the two-layered 76T cluster model. Ethylene dimerization may proceed along two different pathways: either a stepwise or a concerted mechanism, and both produce a surface butoxide intermediate. Our results indicated that with respect to the reactions on Al/HZSM-5, the adsorption energy of ethylene on Ga/HZSM-5 was 20.62 kJ·mol^-1 lower, and the activation energy for the protonation process was only 1.26 kJ·mol^-1 higher. Additionally, the activation energy for a combination of ethoxide intermediate with ethylene was 62.55 kJ·mol^-1 higher because of the larger atomic radius of Ga, which led to an unstable six-member ring transition state. For the concerted mechanism, protonation and C―C bond formation proceeded in one step and the activation energy on Ga/HZSM-5 was 16.44 kJ·mol^-1 higher than that on Al/HZSM-5. Therefore, the ethylene dimerization reaction proceeded according to the concerted mechanism. The surface butoxide intermediate was transformed to 1-butene by deprotonation and adsorbed on the recovered Brönsted acid sites. The corresponding activation energy on Ga/HZSM-5 was similar to that on Al/HZSM-5 but it was obviously higher than that in the other steps. Therefore, it was the rate-determining step for this reaction.
- Ga/HZSM-5,
- Ethylene dimerization,
- Reaction mechanism,
- Density functional theory
1. [1]
  
  (1) Stocker, M. Microporous Mesoprous Mat. 1999, 29, 3.
2. [2]
  (2) Rozanska, X.; Saintigny, X.; van Santen, R. A.; Clemendot, S.; Hutschka. F. J. Catal. 2002, 208, 89.
3. [3]
  (3) Lukyanov, D. B.; Shtral, V. I.; Khadzhiev, S. N. J. Catal. 1994, 146, 87.
4. [4]
  (4) Artit, A.; Tawan, S. Appl. Catal. A-Gen. 2009, 361, 93.
5. [5]
  (5) Tielens, F.; Langenaeker,W.; Geerlings, P. J. Mol. Stuct. -Theochem 2000, 496, 153.
6. [6]
  (6) Yuan, S. P.;Wang, J. G.; Li, Y.W.; Peng, S. Y. J. Mol. Catal. AChem. 2002, 178, 267.
7. [7]
  (7) Schroder, K. P.; Sauer, J. J. Phys. Chem. 1993, 97, 6579.
8. [8]
  (8) Yang, G.;Wang, Y. J. Chem. Phys. 2003, 19, 18.
9. [9]
  (9) Deka, R. C.; Hirao, K. J. Mol. Catal. A- Chem. 2002, 181, 275.
10. [10]
  (10) Done, M.;Wang, J.; Sun, Y. Microporous Mesoprous Mat. 2001, 43, 237.
11. [11]
  (11) Wang, Y.; Zhou, D. H.; Yang, G.; Miao, S. J.; Liu, X. C.; Bao, X. H. J. Phys. Chem. A 2004, 108, 6730.
12. [12]
  (12) Yuan, S. P.;Wang, J. G.; Li, Y.W.; Peng, S. Y. J. Mol. Catal. A. Chem. 2001, 1.
13. [13]
  (13) Choudhary, V. R.; Devadas, P.; Banerjee, S.; Kinage, A. K. Microporous Mesopoous Mat. 2001, 47, 253.
14. [14]
  (14) Yuan, S. P.;Wang, J. G.; Li, Y.W.; Jiao, H. J. J. Phys.Chem. A 2002, 106, 8167.
15. [15]
  (15) Fricke, R.; Kooslick, H.; Lischke, G.; Richter, M. Chem. Rev. 2000, 100, 2303.
16. [16]
  (16) Chu, C. T.W.; Chang, C. D. J. Phys. Chem. 1985, 89, 1569.
17. [17]
  (17) Sauer, J. Chem. Rev. 1989, 89, 199.
18. [18]
  (18) Mikhailov, M. N.; Mishin, I. V.; Kustov, L. M.; Lapidus, A. L. Microporous Mesoprous Mater. 2007, 104, 145.
19. [19]
  (19) Zygmunt, S. A.; Muller, R. M.; Curtiss, L. A.; Iton, L. E. J. Mol. Strut. 1998, 430, 9.
20. [20]
  (20) Meitzner, G. D.; Iglesa, E.; Baumgarnter, J. E.; Huang, E. S. J. Catal. 1993, 140, 209.
21. [21]
  (21) Pereira, M. S.; Nascimento, M. A. C. Chem. Phys Lett. 2005, 406, 446.
22. [22]
  (22) Frash, M. V.; van Santen, R. A. J. Catal. 1997, 170, 1.
23. [23]
  (23) Derouane, E. G.; Fripiat, J. G. J. Phys. Chem. 1987, 91, 145.
24. [24]
  (24) Fripiat, J. G.; Berger-André, F.; André, J. M.; Derouane, E. G. Zeolites 1983, 3 (4), 306.
25. [25]
  (25) Chatterjee, A.; Vetrivel, R. Microporous Mesoprous Mat. 1994, 3 (3), 211.
26. [26]
  (26) Fisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03, Revision C.02; Gaussian Inc.:Wallingford, CT, 2004.
27. [27]
  (27) Zhang, J.; Zhou, D. H.; Ni, D. Chin. J. Catal. 2008, 29 (8), 715.
28. [28]
  [张佳, 周丹红, 倪丹. 催化学报, 2008, 29 (8), 715.]
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