Citation: WANG Li-Geng, YUAN Ting, LI Yuan, SHI Wei, NI Zhe-Ming. Interlayer Reaction of Thiosulfate in a Confined Region of Layered Double Hydroxides[J]. Acta Physico-Chimica Sinica, ;2012, 28(02): 273-282. doi: 10.3866/PKU.WHXB201111243 shu

Interlayer Reaction of Thiosulfate in a Confined Region of Layered Double Hydroxides

1.
College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China

Received Date: 1 August 2011
Available Online: 24 November 2011

The thiosulfate anion (S₂O₃^2-) was intercalated into a ZnAl layered double hydroxide (LDH), and its oxidation reaction with hexacyanoferrate(III) (Fe(CN)₆^3-) in the confined region between the layers of LDH has been discussed. Based measurements of the intermediate state and final product using X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, the oxidation product tetrathionate (S4O₆^2-) dissolved in solution, while the reduction product hexacyanoferrate (II) existed in the interlayer of the LDH. Furthermore, the kinetics of this reaction were investigated in batch mode. The influences of the initial Fe(CN)₆^3- concentration, ZnAl-S₂O₃LDH quantity, and reaction temperature on the oxidation reaction were studied. The reaction follows a diffusion-controlled process represented by Crank-Ginstling and Brounstein model with the apparent activation energy of 24.6 kJ·mol^-1, which was about 13.7 kJ·mol^-1 less than that of the solution reaction under the same conditions. The influence of water content on interlayer spacing was simulated by molecular dynamics. The simulation result shows that the size of this microreactor can be regulated in a certain orientation in the solution environment. From the experimental results and theoretical calculation, we propose a mechanism for the interlayer reaction. This layered material can be used as a novel nano-reactor to regulate the rate of chemical reactions.
- Kinetics,
- Thiosulfate,
- Hexacyanoferrate(III),
- Interlayer reaction,
- Reaction mechanism
1. [1]
  (1) Newman, S. P.; Jones,W. New J. Chem. 1998, 22, 105.
2. [2]
  (2) Yuan Q.;Wei, M.; Evan, D.; Duan, X. J. Phys. Chem. B 2004, 108, 12381.
3. [3]
  (3) Miyata, S. Clays Clay Miner. 1983, 31, 305.
4. [4]
  (4) Yan, D.; Lu, J.;Wei, M.; Li, H.; Ma, J.; Li, F.; Evans, D. G.; Duan, X. J. Phys. Chem. A 2008, 33, 7671.
5. [5]
  (5) Yang,W. S.; Kim, Y.; Liu, P. K. T.; Sahimi, M.; Tsotsis, T. T. Chem. Eng. Sci. 2002, 57, 2954
6. [6]
  (6) Hou, X.Q.; Kalinichev, A. G.; Krikpatrick, R. J. Chem. Mater. 2002, 14, 2078.
7. [7]
  (7) Xu, Q.; Ni, Z. M.; Yao, P.; Li Y. J. Mol. Struct. 2010, 977, 165.
8. [8]
  (8) Li, Y.; Ni, Z. M.; Xu ,Q.; Yao, P.; Liu, X. M.;Wang, Q. Q. J. Chin. Ceramic Soc. 2011, 39, 63. [李远, 倪哲明, 胥倩, 姚萍, 刘晓明, 王巧巧. 硅酸盐学报, 2011, 39, 63.]
9. [9]
  (9) Das, D. P.; Das, J.; Parida, K. J. Colloid Interface Sci. 2003, 261, 213.
10. [10]
  (10) Pérez-Bemal, M. E.; Ruano-Casero, R.; Pinnavaia, T. J. Catal. Lett. 1991, 11, 55.
11. [11]
  (11) Choudary, B. M.; Kantam, M. L.; Kavita, B.; Reddy, C. V.; Figueras, F. Tetrahedron 2000, 56, 9357.
12. [12]
  (12) Zubitur, M.; Gómez, M. A.; Cortázar, M. Poly. Degrad. Stab. 2009, 5, 804.
13. [13]
  (13) Lee, K.; Nam, J.H.; Lee, J.H.; Lee, Y.; Cho, S.M.; Jung, C.H.; Choi, H.G.; Chang, Y.Y.; Kwon, Y. U.; Nam, J. D. Electrochem. Commun. 2005, 7, 113.
14. [14]
  (14) Ji, X. M.; Li, M. L.; Zhao, Y. X.;Wei, Y. B.; Xu, Q. H. Solid State Sci. 2009, 6, 1170.
15. [15]
  (15) Choi, G.; Lee, J.H.; Oh, Y. J.; Choy, Y. B.; Park, M. C.; Chang, H. C.; Choy, J. H. Int. J. Pharm. 2010, 402, 117.
16. [16]
  (16) Arulraj, J.; Rajamathi, J. T.; Prabhu, K. R.; Rajamathi, M. Solid State Sci. 2007, 9, 812..
17. [17]
  (17) Das, N.; Das, R. Appl. Clay Sci. 2008, 42, 90.
18. [18]
  (18) Freund, P. L.; Spiro, M. J. Phys. Chem. 1985, 7, 1074.
19. [19]
  (19) Freund, P. L.; Spiro, M. J. Chem. Soc. Faraday Trans. 1986, 82, 2277.
20. [20]
  (20) Li, Y.; Petroski, J.; El-Sayed, M. A. J. Phys. Chem. B 2000, 104, 10956.
21. [21]
  (21) Li, D.; Sun, C. Y.; Huang, Y. J.; Li, J. H.; Chen, S.W. Sci. China, Ser. B-Chem. 2005, 35, 33. [李迪, 孙春燕, 黄云杰, 李景虹, 陈少伟. 中国科学B辑: 化学, 2005, 35, 33.]
22. [22]
  (22) Bonnet, S.; Forano, C.; de Roy, A.; Besse, J. P.; Maillard, P. Maomenteau, M. Chem. Mater. 1996, 8, 1962.
23. [23]
  (23) Meng,W.; Li, F.; Evans, D. G.; Duan, X.; Mater. Res. Bull. 2004, 39, 1185.
24. [24]
  (24) Kloprogge, J. T.;Weier, M.; Crespo, I.; Ulibarri, M. A.; Barriga, C.; Rives, V.; Martens,W. N.; Frost, R. L. J. Solid State Chem. 2004, 177, 1382.
25. [25]
  (25) Thomas, N.; Rajamathi, M. Langmuir 2009, 25, 2212.
26. [26]
  (26) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordinatio Compound; Chemical Industry Press: Beijing, 1999; pp 187-188; translated by Huang, D. R.,Wang, R. Q. [Nakamoto, K. 无机和配位化合物红外和拉曼光谱.黄德如, 王仁庆译. 北京: 化学工业出版社, 1999: 187-188. ]
27. [27]
  (27) Fernández, J. M.; Ulibarri, M. A. ; Labajos, F.; Rives, V. J. Mater. Chem. 1998, 8, 2507.
28. [28]
  (28) Yao, K.; Tanaguchi, M.; Nakata, M.; Shimazu, K.; Takahashi, M.; Yamagishi, A. J. Electroanal. Chem. 1998, 457, 119.
29. [29]
  (29) Dickinson, C. F.; Heal, G. R. Thermochim. Acta 1999, 340, 89.
30. [30]
  (30) Markus, H.; Fugleberg, S.; Valtakari, D.; Salmi, T.; Murzin, D. Y.; Lahtinen, M. Chem. Eng. Sci. 2004, 59, 919.
31. [31]
  (31) Ho, Y. S.; Ng, J. C. Y.; McKay, G. S. Purif. Methods 2000, 29, 189.
32. [32]
  (32) Lazaridis, N. K.; Asouhidou, D. D. Water Res. 2003, 37, 2875.
33. [33]
  (33) Lv, L.; He, J.;Wei, M.; Evans, D. G. and Zhou, Z. L. Water Res. 2007, 7, 1534.
34. [34]
  (34) Howleit,W. E.;Wedzicha, B. L. Inorg. Chim. Acta 1976, 18, 133.
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沈阳化工大学材料科学与工程学院沈阳 110142