Citation: WANG Zhi-Qiang, SUN Wen-Jing, CHU Wei, YU Liang-Jun. Reaction Mechanism and Solvent Effects of Styrene Epoxidation with Hydrogen Peroxide[J]. Acta Physico-Chimica Sinica, ;2011, 27(02): 322-328. doi: 10.3866/PKU.WHXB20110218 shu

Reaction Mechanism and Solvent Effects of Styrene Epoxidation with Hydrogen Peroxide

1.
School of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China

Received Date: 25 August 2010
Available Online: 29 December 2010
Fund Project: 国家重点基础研究发展计划项目(973) (2011CB201202)资助 (973) (2011CB201202)

In this paper, styrene epoxidation with hydrogen peroxide was used as a model reaction. The Dmol³ implementation in the Materials Studio Software was used to simulate the mechanism of the model reaction. Solvent effects in the reaction were also studied using the conductor-like screening model (COSMO) as a part of the continuum model in three solvents: water, ethanol, and tert-butyl alcohol. To investigate the micro-process wherein the solvent molecules react with the solute molecules directly, the discrete model was employed to simulate the impact of a single molecule of water, ethanol and tert-butyl alcohol on the reaction. Consistent results were obtained for the two different solvent models. Reaction activity was most favorable for the tert-butyl alcohol followed by ethanol. Protic solvent molecules promote the heterolytic cleavage of hydrogen peroxide and form active oxygen species, which can reduce the reaction barrier.
- Density functional theory,
- Styrene,
- Hydrogen peroxide,
- Epoxidation reaction,
- Solvent effect
1. [1]
  
  (1) Jinka, K. M.; Bajaj, H. C.; Jasra, R. V.; Prasetyanto, E. A.; Park, S. E. Top Catal. 2010, 53, 238.
2. [2]
  (2) Xu, J. Q.; Chu,W.; Chen, M. H. Chinese Industry and Engineering Progress 2005, 24, 981.
3. [3]
  [许俊强, 储伟, 陈慕华. 化工进展, 2005, 24, 981.]
4. [4]
  (3) Xu, J. Q.; Chu,W.; Luo, S. Z. J. Mol. Catal. A: Chem. 2006, 256, 48.
5. [5]
  (4) Jiang, Y.; Chu,W.; Jiang, C. F.;Wang, Y. H. Acta Phys. -Chim. Sin. 2007, 23, 1723.
6. [6]
  [姜勇, 储伟, 江成发, 王耀红. 物理化学学报, 2007, 23, 1723.]
7. [7]
  (5) Zhang, X.; Chu,W.; Chen, J. J.; Dai, X. Y. Acta Phys. -Chim. Sin. 2009, 25, 451.
8. [8]
  [张旭, 储伟, 陈建钧, 戴晓雁. 物理化学学报, 2009, 25, 451.]
9. [9]
  (6) Sun,W. J.; Chu,W.; Yu, L. J.; Jiang, C. F. Chin. J. Chem. Phys. 2010, 23, 175.
10. [10]
  (7) Lane, B. S.; Burgess, K. Chem. Rev. 2003, 103, 2457.
11. [11]
  (8) Chen, Y. Y.; Han, X.W. Prog. Chem. 2006, 18, 399.
12. [12]
  [陈杨英, 韩秀文. 化学进展, 2006, 18, 399.]
13. [13]
  (9) Wang, X. L.;Wu, G. D.;Wei,W.; Sun, Y. H. Catal. Lett. 2010, 136, 96.
14. [14]
  (10) Choudhary, V. R.; Patil, N. S.; Chaudhari, N. K.; Bhargava, S. K. J. Mol. Catal. A: Chem. 2005, 227, 217.
15. [15]
  (11) Jinka, K. M.; Pai, S. M.; Newalkar, B. L.; Choudary, N. V.; Jasra, R. V. Catal. Commun. 2010, 11, 638.
16. [16]
  (12) Ren, T.; Yan, L.; Zhang, H. P.; Suo, J. S. J. Mol. Catal. (China.) 2003, 17, 310.
17. [17]
  [任通, 阎亮, 张汉鹏, 索继栓. 分子催化, 2003, 17, 310.]
18. [18]
  (13) Patil, N. S.; Uphade, B. S.; McCulloh, D. G.; Bhargava, S. K.; Choudhary, V. R. Catal. Commun. 2004, 5, 681.
19. [19]
  (14) Patil, N. S.; Uphade, B. S.; Jana, P.; Uphade, B. S.; Choudhary, V. R. J. Catal. 2004, 223, 236.
20. [20]
  (15) Choudhary, V. R.; Patil, N. S.; Chaudhari, N. K.; Bhargava, S. K. Catal. Commun. 2004, 5, 205.
21. [21]
  (16) Patil, N. S.; Jha, R.; Uphade, B. S.; Bhargava, S. K.; Choudhary, V. R. Appl. Catal. A: Gen. 2004, 275, 87.
22. [22]
  (17) Liu, J. H.;Wang, F.; Xu, T.; Gu, Z. G. Catal. Lett. 2010, 134, 51.
23. [23]
  (18) Liu, X.W.;Wang, X. S.; Guo, X.W.; Li, G. Catal. Today 2004, 93-95, 505.
24. [24]
  (19) Liu, J. H.;Wang, F.; Liu, Y. X.; Xu, X. L. Chin. J. Catal. 2007, 28, 1003.
25. [25]
  [刘俊华, 王芳, 刘艳侠, 徐贤伦. 催化学报, 2007, 28, 1003.]
26. [26]
  (20) Xiong, Y.; Zhang, Y.; Liu, Y.; Du, Z. X. Chinese Industry and Engineering Progress, 2006, 25, 675.
27. [27]
  [熊勇, 张宇, 刘易, 杜泽学. 化工进展, 2006, 25, 675.]
28. [28]
  (21) Wu, Y. L.; Liu, Q. S.; Su, X. L.; Mi, Z. T. Journal of Tsinghua University (Science & Technology), 2007, 47(9), 1511.
29. [29]
  [吴玉龙, 刘青山, 苏雪丽, 米镇涛. 清华大学学报(自然科学版), 2007, 47(9), 1511.]
30. [30]
  (22) Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2002, 105, 2999.
31. [31]
  (23) Kongsted, J.; Mennucci, B.; Coutinho, K.; Canuto, S. Chem. Phys. Lett. 2010, 484, 185.
32. [32]
  (24) Perdew, J. P.;Wang, Y. Phys. Rev. B 1992, 45, 13244.
33. [33]
  (25) Henkelman, G.; Jonsson, H. J. Chem. Phys. 2000, 113, 9978.
34. [34]
  (26) Klamt, A.; Schuurmann, G. J. Chem. Soc. Perkin Trans. 2, 1993, No.5, 799.
35. [35]
  (27) Cao, Z. Q. Studies and Applications of a Combined Discretecontinuum Solvation Model. Ph.D. Dissertation, Xiamen University, Xiamen, 2004.
36. [36]
  [曹志霁. 离散-连续组合溶剂化模型的应用研究
37. [37]
  [D]. 厦门: 厦门大学, 2004.]
38. [38]
  (28) Li, Y. Preparation, Characterization and Catalytic Performance of Supported Heteropoly Compounds Catalysts for Rin pening Polymerization of Tetrahydrofuran. Ph.D. Dissertation, Sichuan University, Chengdu, 2008.
39. [39]
  [李洋. 四氢呋喃开环聚合用担载型杂多化合物催化剂的研制、表征与性能研究
40. [40]
  [D]. 成都: 四川大学, 2008.]
41. [41]
  (29) Reichardt, C. Solvent Effect in Organic Chemistry; Chemical Industry Press: Beijing, 1987; pp 278-319; translated by Tang, K., Xie, Z., Chen, Z. J., Lin, J.W.
42. [42]
  [Reichardt, C. 有机化学中的溶剂效应. 唐培堃, 谢周, 陈之基, 林吉文, 译. 北京: 化学工业出版社, 1987: 278-319.]
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