Effect of Hydration on Polytypism and Disorder in the Sulfate-Intercalated Layered Double Hydroxides of Li and Al

  • Latha Pachayappan
  • P. Vishnu KamathEmail author


The double hydroxide of Li+ and Al3+ is an anionic clay comprising positively charged metal hydroxide layers and intercalated anions. While the structure of the iono-covalently bonded metal hydroxide layer is well known, relatively less knowledge is available regarding the manner in which the anions and water molecules are packed in the interlayer region. The sulfate ion is of special interest as it can potentially intercalate in a multiplicity of orientations and grow an extended hydration sphere. The sulfate-intercalated double hydroxide was synthesized by the imbibition of Li2SO4 into both the gibbsite and bayerite forms of Al(OH)3 to obtain layered double hydroxides with the nominal formula Li2Al4(OH)12SO4·nH2O (n = 4–8). The as-prepared compounds were poorly ordered and did not yield any structural information. Temperature-induced partial dehydration yielded ordered phases of different structures in the two systems. Simulation of the powder patterns of different model structures, followed by structure refinement in both direct and reciprocal spaces, showed that the gibbsite-derived phase yielded a two-layer polytype of hexagonal symmetry (space group P63/m). The local symmetry of the sulfate ion was close to D2d with one of the C2 axes of the SO42− being nearly parallel to the c axis of the crystal. The bayerite-derived phase yielded a one-layer polytype of monoclinic symmetry (space group C2/m). The sulfate ion was oriented with its C3 axes tilted away from the stacking direction. Cooling and rehydration (relative humidity ~70%) resulted in a reversible expansion of the basal spacing due to the ingress of water molecules from the ambient humidity into the interlayer region. Hydration in both cases resulted in turbostratic disorder. The disorder in the bayerite-derived phase was a result of random intergrowth of motifs with rhombohedral and monoclinic symmetries.


Layered Double Hydroxide Rietveld Method Sulfate XRPD 



The authors are grateful to the Department of Science and Technology (DST), Government of India, for financial support. L.P. is a recipient of support under the Women Scientists (WOS-A) Scheme of the DST.

Supplementary material

42860_2019_11_MOESM1_ESM.doc (2.3 mb)
ESM 1 (DOC 2.26 mb)


  1. Besserguenev, A. V., Fogg, A.M., Francis, R.J., Price, S.J., O’Hare, D., Isupov, V.P., & Tolochko, B.P. (1997) Synthesis and structure of the gibbsite intercalation compounds [LiAl2(OH)6]X {X = Cl, Br, NO3} and [LiAl2(OH)6]Cl·H2O using synchrotron X-ray and neutron powder diffraction. Chemistry of Materials, 9, 241–247.CrossRefGoogle Scholar
  2. Britto, S. & Kamath, P.V. (2009) Structure of bayerite-based lithium - aluminum layered double hydroxides (LDHs): Observation of monoclinic symmetry. Inorganic Chemistry, 48, 11646–11654.CrossRefGoogle Scholar
  3. Britto, S. & Kamath, P.V. (2011) Polytypism in the lithium - aluminum layered double hydroxides : The [LiAl2(OH)6]+ layer as a structural synthon. Inorganic Chemistry, 50, 5619–5627.CrossRefGoogle Scholar
  4. Britto, S. & Kamath, P.V. (2012) Structural synthon approach to the study of stacking faults in the layered double hydroxides of lithium and aluminum. Zeitschrift fur Anorganische und Allgemeine Chemie, 638, 362–365.CrossRefGoogle Scholar
  5. Britto, S., Thomas, G.S., Kamath, P.V., & Kannan, S. (2008) Polymorphism and structural disorder in the carbonate containing layered double hydroxide of Li with Al. Journal of Physical Chemistry C, 112, 9510–9515.CrossRefGoogle Scholar
  6. Cavani, F., Trifirò, F., & Vaccari, A. (1991) Hydrotalcite-type anionic clays: Preparation, properties and applications. Catalysis Today, 11, 173–301.CrossRefGoogle Scholar
  7. Chen, M., Zhu, R., Lu, X., Zhu, J., & He, H. (2018) Influences of cation ratio, anion type, and water content on polytypism of layered double hydroxides. Inorganic Chemistry, 57, 7299–7313.Google Scholar
  8. Fawell, J.K., Ohanian, E., Giddings, M., Toft, P., Magara, Y., & Jackson, P. (2004). Sulfate in drinking-water Background document for development of WHO Guidelines for drinking-water quality. World Health Organization, 8.Google Scholar
  9. Fogg, A.M., Green, V.M., Harvey, H.G., & O’Hare, D. (1999) New separation science using shape-selective ion exchange intercalation chemistry. Advanced Materials, 11, 1466–1469.CrossRefGoogle Scholar
  10. Fogg, A.M., Freij, A.J., & Parkinson, G.M. (2002) Synthesis and anion exchange chemistry of rhombohedral Li/Al layered double hydroxides. Chemistry of Materials, 14, 232–234.CrossRefGoogle Scholar
  11. Larson, A.C. & Von Dreele, R.B. (2004). General Structure Analysis System (GSAS). Los Alamos National Laboratory Report LAUR, 748, 86–748.Google Scholar
  12. Łasocha, W. & Lewinski, K. (1994) PROSZKI – a system of programs for powder diffraction data analysis. Journal of Applied Crystallography, 27, 437–438.Google Scholar
  13. Megaw, H.D. (1934) The crystal structure of hydrargillite, Αl(OH) . Zeitschrift für Kristallographie – Crystalline Materials, 87, 185–205.Google Scholar
  14. Moosa, S., Nemati, M., & Harrison, S.T.L. (2005) A kinetic study on anaerobic reduction of sulphate, part II: Incorporation of temperature effects in the kinetic model. Chemical Engineering Science, 60, 3517–3524.CrossRefGoogle Scholar
  15. Nagendran, S. & Kamath, P.V. (2013) Structure of the chloride- and bromide-intercalated layered double hydroxides of Li and Al - Interplay of coulombic and hydrogen-bonding interactions in the interlayer gallery. European Journal of Inorganic Chemistry, 2013, 4686–4693.CrossRefGoogle Scholar
  16. Nagendran, S. & Kamath, P.V. (2017) Synthon approach to structure models for the bayerite-derived layered double hydroxides of Li and Al. Inorganic Chemistry, 56, 5026–5033.CrossRefGoogle Scholar
  17. Nagendran, S., Periyasamy, G., & Kamath, P.V. (2016) Structure models for the hydrated and dehydrated nitrate-intercalated layered double hydroxide of Li. Dalton Transactions, 45, 18324–18332.Google Scholar
  18. Nagendran, S., Periyasamy, G., & Kamath, P.V. (2018) Hydration-induced interpolytype transformations in the bayerite-derived nitrate-intercalated layered double hydroxide of Li and Al. Journal of Solid State Chemistry, 266, 226–232.CrossRefGoogle Scholar
  19. Poeppelmeier, K.R. & Hwu, S.J. (1987) Synthesis of lithium dialuminate by salt imbibition. Inorganic Chemistry, 26, 3297–3302.CrossRefGoogle Scholar
  20. Pol, L.W.H., Lens, P.N.L., Stams, A.J.M., & Lettinga, G. (1998) Anaerobic treatment of sulphate-rich wastewaters. Biodegradation, 9, 213–224.CrossRefGoogle Scholar
  21. Prasanna, S. V. & Kamath, P.V. (2008) Chromate uptake characteristics of the pristine layered double hydroxides of Mg with Al. Solid State Sciences, 10, 260–266.CrossRefGoogle Scholar
  22. Prasanna, S. V., Rao, R.A.P., & Kamath, P.V. (2006) Layered double hydroxides as potential chromate scavengers. Journal of Colloid and Interface Science, 304, 292–299.CrossRefGoogle Scholar
  23. Rhee, S.W., Kang, M.J., Kim, H., & Moon, C.H. (1997) Removal of aquatic chromate ion involving rehydration reaction of calcined layered double hydroxide (Mg-Al-CO3). Environmental Technology, 18, 231–236.Google Scholar
  24. Rothbauer, R., Zlgan, F., & O’daniel, H. (1967) Refinement of the structure of the bayerite, Al(OH)3 including a proposal for the h-position. Zeitschrift fur Kristallographie - New Crystal Structures, 125, 317–331.Google Scholar
  25. Saalfeld, H. & Wedde, M. (1974) Refinement of the crystal structure of gibbsite, Al(OH)3. Zeitschrift fur Kristallographie, 139, 120–135.CrossRefGoogle Scholar
  26. Serna, C.J., Rendon, J.L., & Iglesias, J.E. (1982) Crystal-chemical study of layered [A12Li(OH)6]+X-" n H2O. Clays and Clay Minerals, 30, 180–184.Google Scholar
  27. Smith, D.W. (1977) Ionic hydration enthalpies. Journal of Chemical Education, 54, 540.CrossRefGoogle Scholar
  28. Soediono, B. (1989) General structure analysis system. Journal of Chemical Information and Modeling, 53, 160.Google Scholar
  29. Thiel, J.P., Chiang, C.K., & Poeppelmeier, K.R. (1993) Structure of LiAl2(OH)7·2H2O. Chemistry of Materials, 12, 297–304.CrossRefGoogle Scholar
  30. Treacy, M.M.J., Newsam, J.M., & Deem, M.W. (1991). A general recursion method for calculating diffracted intensities from crystals containing planar faults. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences.Google Scholar
  31. Treacy, M.M.J., Deem, M.W., & Newsam, J.M. (2005). DIFFaX version 1.812; 1–71 pp.
  32. Warren, B.E. & Bodenstein, P. (1966) The shape of two-dimensional carbon black reflections. Acta Crystallographica, 20, 602–605.CrossRefGoogle Scholar
  33. Yang, L., Shahrivari, Z., Liu, P.K.T., Sahimi, M., & Tsotsis, T.T. (2005) Removal of trace levels of arsenic and selenium from aqueous solutions by calcined and uncalcined layered double hydroxides (LDH). Industrial and Engineering Chemistry Research, 44, 6804–6815.CrossRefGoogle Scholar
  34. You, Y.W., Zhao, H.T., & Vance, G.F. (2001) Environmental technology removal of arsenite from aqueous solutions by anionic clays. Environmental Technology, 2212, 37–41.Google Scholar

Copyright information

© The Clay Minerals Society 2019
AE: Runliang Zhu

Authors and Affiliations

  1. 1.Department of Chemistry, Central CollegeBangalore UniversityBangaloreIndia

Personalised recommendations