Structural identification of DClO4 clathrate hydrates: Neutron powder diffraction analysis

Kyuchul Shin; Minjun Cha; Wonhee Lee; Huen Lee

Korean Journal of Chemical Engineering, Vol.33, No.5, 1728-1735, May, 2016

DOI10.1007/s11814-016-0010-0 Export Citation

Structural identification of DClO4 clathrate hydrates: Neutron powder diffraction analysis

Kyuchul Shin^†, Minjun Cha¹, Wonhee Lee², and Huen Lee^{3, †}

School of Applied Chemical Engineering, Major in Applied Chemistry, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu 41566, Korea
¹Department of Energy and Resources Engineering, Kangwon National University, 1 Kangwondaehak-gil, Chuncheon-si, Gangwon-do 24341, Korea
²Climate Change Research Division, Korea Institute of Energy Research (KIER), Daejeon 34128, Korea
³Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34143, Korea

E-mail:,

Acid clathrate hydrates which do not contain hydrogen fluoride impurities are believed to include several vacancy sites in the host lattice for protonation of the framework. In this work, the crystal structures of a DClO4·5.5D2O solid at various temperatures were identified by the direct space method and Rietveld refinement of the neutron powder diffraction patterns. A position change of vacancy sites accompanying the shift of ClO4- guest ions in the 51262 cavity toward the center of the cavity from the edge of the hexagonal face was observed at about 180 K, and this phenomenon is expected to result in weakened host proton-guest anion interactions and to induce a phase transition related to the proton conduction behavior of the DClO4 clathrate. The present findings explain the proton dynamics of the hydrogen fluoride-free acid clathrate hydrates and provide a better understanding of the nature of guest-host interactions occurring on ion-doped hydrate materials.

Keywords:Clathrate;Hydrate;Neutron Powder Diffraction

[References]

Jeffrey GA, in Inclusion Compounds, Vol. 1, pp. 135-190; Atwood JL, Davies JED, MacNicol DD, Eds., Academic Press, London (1984).
Shin K, Cha JH, Seo Y, Lee H, Chem. Asian J., 5, 22 (2010)
Choi S, Shin K, Lee H, J. Phys. Chem. B, 111(34), 10224 (2007)
Cha JH, Shin K, Choi S, Lee S, Lee H, J. Phys. Chem. C, 112, 13332 (2008)
Cha JH, Lee W, Lee H, J. Mater. Chem., 19, 6542 (2009)
Lee W, Lim D, Lee H, Electrochim. Acta, 109, 852 (2013)
Cha JH, Lee W, Lee H, Angew. Chem.-Int. Edit., 48, 8687 (2009)
Lee W, Kown M, Park S, Lim D, Cha JH, Lee H, Chem. Asian J., 8, 1569 (2013)
Davidson DW, Garg SK, Can. J. Chem., 50, 3515 (1972)
Davidson DW, Calvert LD, Lee F, Ripmeester JA, Inorg. Chem., 20, 2013 (1981)
Mootz D, Oellers EJ, Wiebcke M, J. Am. Chem. Soc., 109, 1200 (1987)
Huang TH, Davis RA, Frese U, Stimming U, J. Phys. Chem., 92, 6874 (1988)
Desmedt A, Stallmach F, Lechner RE, Cavagnat D, Lassegues JC, Guillaume F, Grondin J, Gonzalez MA, J. Chem. Phys., 121(23), 11916 (2004)
Desmedt A, Lechner RE, Lassegues JC, Guillaume F, Cavagnat D, Grondin J, Solid State Ion., 252, 19 (2013)
Takeya S, Udachin KA, Moudrakovski IL, Susilo R, Ripmeester JA, J. Am. Chem. Soc., 132(2), 524 (2010)
Shin K, Lee W, Cha M, Koh DY, Choi YN, Lee H, Son BS, Lee S, Lee H, J. Phys. Chem. B, 115(5), 958 (2011)
Favre-Nicolin F, Cerny R, J. Appl. Crystallogr., 35, 734 (2002)
Cerny R, Favre-Nicolin F, Z. Kristrallogr-Cryst. Mater., 222, 105 (2007)
Rodriguez-Carvajal J, Phys. B, 192, 55 (1993)
Shin K, Udachin KA, Moudrakovski IL, Leek DM, Alavi S, Ratcliffe CI, Ripmeester JA, Proc. Natl. Acad. Sci. USA, 110, 8437 (2013)
Shin K, Cha M, Lee W, Seo Y, Lee H, J. Phys. Chem. C, 118, 15193 (2014)
Shin K, Kumar R, Udachin KA, Alavi S, Ripmeester JA, Proc. Natl. Acad. Sci. USA, 109, 14785 (2012)
Momma K, Izumi F, J. Appl. Crystallogr., 44, 1272 (2011)

[Referenced By]

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[1] Jeffrey GA, in Inclusion Compounds, Vol. 1, pp. 135-190; Atwood JL, Davies JED, MacNicol DD, Eds., Academic Press, London (1984).

[2] Shin K, Cha JH, Seo Y, Lee H, Chem. Asian J., 5, 22 (2010)

[3] Choi S, Shin K, Lee H, J. Phys. Chem. B, 111(34), 10224 (2007)

[4] Cha JH, Shin K, Choi S, Lee S, Lee H, J. Phys. Chem. C, 112, 13332 (2008)

[5] Cha JH, Lee W, Lee H, J. Mater. Chem., 19, 6542 (2009)

[6] Lee W, Lim D, Lee H, Electrochim. Acta, 109, 852 (2013)

[7] Cha JH, Lee W, Lee H, Angew. Chem.-Int. Edit., 48, 8687 (2009)

[8] Lee W, Kown M, Park S, Lim D, Cha JH, Lee H, Chem. Asian J., 8, 1569 (2013)

[9] Davidson DW, Garg SK, Can. J. Chem., 50, 3515 (1972)

[10] Davidson DW, Calvert LD, Lee F, Ripmeester JA, Inorg. Chem., 20, 2013 (1981)

[11] Mootz D, Oellers EJ, Wiebcke M, J. Am. Chem. Soc., 109, 1200 (1987)

[12] Huang TH, Davis RA, Frese U, Stimming U, J. Phys. Chem., 92, 6874 (1988)

[13] Desmedt A, Stallmach F, Lechner RE, Cavagnat D, Lassegues JC, Guillaume F, Grondin J, Gonzalez MA, J. Chem. Phys., 121(23), 11916 (2004)

[14] Desmedt A, Lechner RE, Lassegues JC, Guillaume F, Cavagnat D, Grondin J, Solid State Ion., 252, 19 (2013)

[15] Takeya S, Udachin KA, Moudrakovski IL, Susilo R, Ripmeester JA, J. Am. Chem. Soc., 132(2), 524 (2010)

[16] Shin K, Lee W, Cha M, Koh DY, Choi YN, Lee H, Son BS, Lee S, Lee H, J. Phys. Chem. B, 115(5), 958 (2011)

[17] Favre-Nicolin F, Cerny R, J. Appl. Crystallogr., 35, 734 (2002)

[18] Cerny R, Favre-Nicolin F, Z. Kristrallogr-Cryst. Mater., 222, 105 (2007)

[19] Rodriguez-Carvajal J, Phys. B, 192, 55 (1993)

[20] Shin K, Udachin KA, Moudrakovski IL, Leek DM, Alavi S, Ratcliffe CI, Ripmeester JA, Proc. Natl. Acad. Sci. USA, 110, 8437 (2013)

[21] Shin K, Cha M, Lee W, Seo Y, Lee H, J. Phys. Chem. C, 118, 15193 (2014)

[22] Shin K, Kumar R, Udachin KA, Alavi S, Ripmeester JA, Proc. Natl. Acad. Sci. USA, 109, 14785 (2012)

[23] Momma K, Izumi F, J. Appl. Crystallogr., 44, 1272 (2011)