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The Inclusion of Hydrogen in Clathrate Hydrates of the Various Guests and Tuning of the tert-Butylamine Hydrate

Published online by Cambridge University Press:  01 February 2011

Huen Lee ,
Jong-won Lee ,
Do Youn Kim  and
Jeasung Park
Huen Lee
Affiliation:
[email protected], Korea Advanced Institute of Science and Technology (KAIST), Chemical and Biomolecular Engineering, 373-1 Guseong-dong, Yuseong-gu, Daejeon, N/A, 305-701, Korea, Republic of, +82-42-869-3917, +82-42-869-3910
Jong-won Lee
Affiliation:
[email protected], Korea Advanced Institute of Science and Technology, Department of Chemical and Biomolecular Engineering, 373-1 Guseong-dong, Yuseong-gu, Daejeon, N/A, 305-701, Korea, Republic of
Do Youn Kim
Affiliation:
[email protected], Korea Advanced Institute of Science and Technology, Department of Chemical and Biomolecular Engineering, 373-1 Guseong-dong, Yuseong-gu, Daejeon, N/A, 305-701, Korea, Republic of
Jeasung Park
Affiliation:
[email protected], Korea Advanced Institute of Science and Technology, Department of Chemical and Biomolecular Engineering, 373-1 Guseong-dong, Yuseong-gu, Daejeon, N/A, 305-701, Korea, Republic of
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Abstract

Clathrate hydrates of structure II with organic cyclic oxides were identified to have the ability to include molecular hydrogen into their empty small cages at near-ambient temperature and moderate pressure. Solid-state NMR and Raman spectroscopy of the included hydrogen molecules indicate that the small cavities are both singly and doubly occupied by hydrogen molecules in the mixed hydrates. The inclusion mechanism can be derived from the critical progression of the cage occupancies as determined from in-situ kinetic experiments on formation and decomposition. The inclusion ability of hydrogen molecules was observed for several organic clathrate hydrate formers such as THF (tetrahydrofuran) and 1,4-dioxane, suggesting this to be a general property. A structural transition of the simple amine hydrate was suggested to produce a novel double CH4 + t-BuNH2 hydrate as confirmed by using microscopic analytical methods. The corresponding hydrate compositions were determined by using NMR spectroscopy to describe a tuning mechanism to increase the storage capacity.

Keywords

nuclear magnetic resonance (NMR)Raman spectroscopyx-ray diffraction (XRD)
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 927: Symposium EE – Hydrogen Storage Materials , 2006 , 0927-EE06-01
Copyright
Copyright © Materials Research Society 2006

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References

1. Sloan, E.D., Clathrate Hydrates of Natural Gases, (Marcel Dekker Inc.: New York, 1998), 2nd ed.Google Scholar
2. Jeffrey, G. A., in Inclusion Compounds, Vol. 1 (Eds.: Atwood, J. L., Davies, J. E. D., MacNicol, D. D.), ACADEMIC PRESS, London, 135–190 (1984)Google Scholar
3. Mao, W. L.; Mao, H.-K.; Goncharov, A. F.; Struzhkin, V. V.; Guo, Q.; Hu, J.; Shu, J.; Hemley, R. J.; Somayazulu, M.; Zhao, Y. Science 297, 2247 (2002)Google Scholar
4. Patchkovskii, S. and Tse, J.S., Proc. Nat. Acad. Sci. U.S.A. 100, 14645 (2003)Google Scholar
5. Kuhs, W.F. et al., J. Inclusion Phenom. Mol. Recognit. Chem. 29, 65 (1997)Google Scholar
6. Klaveren, E. P. et al., J. Chem. Phys. 114, 5745 (2001)Google Scholar
7. Itoh, H., Tse, J.S., and Kawamura, K., J. Chem. Phys. 115, 9414 (2001)Google Scholar
8. Chazallon, B. and Kuhs, W.F., J. Chem. Phys. 117, 308 (2002)Google Scholar
9. Sasaki, S. et al., J. Chem. Phys. 118, 7892 (2003)Google Scholar
10. Udachin, K. A., Ratcliffe, C. I., Ripmeester, J. A., Angew. Chem. 113, 1343 (2001)Google Scholar
11. Gudmundsson, J. S., Mork, M., Graff, O. F., Proceedings of the 4th International Conference on Gas Hydrates Yokohama, 997 (2002)Google Scholar
12. Teng, H., Yamasaki, A., Chun, M. K., Lee, H., Energy 22, 1111 (1997)Google Scholar
13. Kang, S.-P., Lee, H., Environ. Sci. Technol. 34, 4397 (2000)Google Scholar
14. Takeya, S., Hori, A., Hondoh, T., Uchida, T., J. Phys. Chem. B 104, 4164 (2000)Google Scholar
15. Seo, Y.-T., Lee, H., J. Phys. Chem. B 105, 10084 (2001)Google Scholar
16. Subramanian, S., Sloan, E. D., J. Phys. Chem. B 106, 4348 (2002)Google Scholar
17. Seo, Y.-T., Lee, H., Moudrakovski, I., Ripmeester, J. A., ChemPhysChem 4, 379 (2003)Google Scholar
18. Seo, Y.-T., Lee, H., J. Phys. Chem. B 108, 530 (2004)Google Scholar
19. Lee, H., Lee, J.-W., Kim, D.-Y., Park, J.-S., Seo, Y.-T., Zeng, H., Moudrakovski, I. L., Ratcliffe, C. I., Ripmeester, J. A., Nature 434, 743 (2005)Google Scholar
20. Mak, T. C. W., McMullan, R. K., J. Chem. Phys. 42, 2732 (1965)Google Scholar
21. Lokshin, K.A., Zhao, Y., He, D., Mao, W.L., Mao, H.K., Hemley, R.J., Lobanov, M.V., and Greenblatt, M., Phys. Rev. Lett. 93, 125503 (2004)Google Scholar