Reversible hydration of the perchlorate-intercalated layered double hydroxides of Li and Al: structure models for the dehydrated phases


Imbibition of lithium sulphate into aluminium hydroxide is known to result in a sulphate-intercalated layered double hydroxide (LDH) of Li and Al. The perchlorate ion has the same size and molecular symmetry as the sulphate ion, but only half its charge. Consequently, twice the number of \(\hbox {ClO}_{4}^{-}\) ions is needed to balance LDHs the charge on the metal hydroxide layer, compared to the \(\hbox {SO}_{4}^{2-}\) ions. In this work, the \(\hbox {ClO}_{4}^{-}\)-intercalated LDHs were obtained from both the bayerite and gibbsite precursors. Inclusion of the hydration sphere along with the \(\hbox {ClO}_{4}^{-}\) anion, induced turbostratic disorder in the stacking of the metal hydroxide layers. Temperature-induced dehydration (\(T \sim 100\)\(140{^{\circ }}\hbox {C}\)) brought about a partial ordering in the interlayer region and the \(\hbox {ClO}_{{4}}^{{-}}\) ion oriented itself with one of its \(C_{{2}}\)-axes parallel to the metal hydroxide layer. The close packing of \(\hbox {ClO}_{4}^{-}\) ions could be realized by the complete dehydration of LDH and the distribution of the \(\hbox {ClO}_{4}^{-}\) ions in all the available interlayer sites. In contrast, within the crystal of the sulphate analogue, the sulphate ions occupy only half the number of interlayer sites. The other half is occupied by the residual water molecules, as the sulphate analogue does not fully dehydrate even at elevated temperatures. This difference in the behaviour of the two LDHs has its origin in the large difference in the hydration enthalpies of the two anions.

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  1. 1.

    Megaw H D 1934 Z. Kristallogr. 87 185

    CAS  Google Scholar 

  2. 2.

    Rothbauer R, Zigan F and O’Daniel H 1967 Z. Kristallogr. 125 317

    CAS  Article  Google Scholar 

  3. 3.

    Lipin V A 2001 Russ. J. Appl. Chem. 74 184

    CAS  Article  Google Scholar 

  4. 4.

    Clark G R, Rodgers K A and Henderson G S 1998 Z. Kristallogr. 213 96

    CAS  Google Scholar 

  5. 5.

    Williams G R, Norquist A J and O’Hare D 2004 Chem. Mater. 16 975

    CAS  Article  Google Scholar 

  6. 6.

    Fogg A M and O’Hare D 1999 Chem. Mater. 11 1771

    CAS  Article  Google Scholar 

  7. 7.

    Besserguenev A V, Fogg A M, Francis R J, Price S J, O’Hare D, Isupov V P et al 1997 Chem. Mater. 9 241

    CAS  Article  Google Scholar 

  8. 8.

    Serna C J, Rendon J L and Iglesias J E 1982 Clays Clay Miner. 30 180

    CAS  Article  Google Scholar 

  9. 9.

    Britto S and Kamath P V 2009 Inorg. Chem. 48 11646

    CAS  Article  Google Scholar 

  10. 10.

    Nagendran S, Periyasamy G and Kamath P V 2016 Dalton Trans. 45 18324

    CAS  Article  Google Scholar 

  11. 11.

    Nagendran S and Kamath P V 2017 Inorg. Chem. 56 5026

    CAS  Article  Google Scholar 

  12. 12.

    Nagendran S, Periyasamy G and Kamath P V 2018 J. Solid State Chem. 266 226

    CAS  Article  Google Scholar 

  13. 13.

    Pachayappan L and Kamath P V 2019 Clays Clay Miner. 67 154

    CAS  Article  Google Scholar 

  14. 14.

    Britto S and Kamath P V 2011 Inorg. Chem. 50 5619

    CAS  Article  Google Scholar 

  15. 15.

    Hou X, Bish D L, Wang S L, Johnston C T and Kirkpatrick R J 2003 Am. Miner. 88 167

    CAS  Article  Google Scholar 

  16. 16.

    Poeppelmeier K R and Hwu S J 1987 Inorg. Chem. 26 3297

    CAS  Article  Google Scholar 

  17. 17.

    Hou X and Kirkpatrick R J 2002 Chem. Mater. 14 1195

    CAS  Article  Google Scholar 

  18. 18.

    Treacy M M J, Newsam J M and Deem M W 1991 Proc. Math. Phys. Eng. Sci. p 499

  19. 19.

    Treacy M M J, Deem M W and Newsam J M 2005 DIFFaX version 1.812.

  20. 20.

    Nagendran S and Kamath P V 2013 Eur. J. Inorg. Chem. 2013 4686

    CAS  Article  Google Scholar 

  21. 21.

    Favre-Nicolin V and Černý R 2002 J. Appl. Crystallogr. 35 734

    CAS  Article  Google Scholar 

  22. 22.

    Marcus Y 1988 J. Solution Chem. 88 1475

    CAS  Google Scholar 

  23. 23.

    Smith D W 1977 J. Chem. Educ. 54 540

    CAS  Article  Google Scholar 

  24. 24.

    Eklund L 2014 Hydration of oxo anions. A combined computational and experimental structure and dynamics study in aqueous solutions, Swedish University of Agricultural Sciences: Uppsala

    Google Scholar 

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We thank the Department of Science and Technology (DST), Government of India (GOI), for financial support. LP is a recipient of support under the Women Scientists (WOS-A) Scheme of the DST.

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Correspondence to P Vishnu Kamath.

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Pachayappan, L., Kamath, P.V. Reversible hydration of the perchlorate-intercalated layered double hydroxides of Li and Al: structure models for the dehydrated phases. Bull Mater Sci 43, 141 (2020).

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  • Layered double hydroxide
  • aluminium hydroxide
  • perchlorate
  • sulphate