Clays and Clay Minerals

, Volume 45, Issue 6, pp 842–853 | Cite as

Formation of Spinel from a Hydrotalcite-Like Compound at Low Temperature: Reaction between Edges of Crystallites

  • Toshiyuki Hibino
  • Atsumu Tsunashima


The thermal decomposition behavior of hydrotalcite-like compounds (HTlcs) prepared by reconstruction of calcined HTlcs is described. From the results of X-ray diffraction (XRD), it seems that dicarboxylate intercalates of HTlc calcined at 500 °C are completely reconstructed to Mg-Al-CO3 HTlc by exposure to aqueous Na2CO3. However, the Mg-Al-CO3 HTlc reconstructed under particular conditions yields spinel (MgAl2O4) at 400 °C. This temperature is very low, because Mg-Al-CO3 HTlc that has been reported yields spinel at 900 °C after forming a Mg-Al double oxide. The reconstructed Mg-Al-CO3 HTlc that yields spinel at 400 °C is obtained when the following conditions are fulfilled: the crystallites of the starting dicarboxylate intercalates are coagulated tightly and the calcined HTlcs and reconstructed materials are not ground. The Mg-Al-CO3 HTlc reconstructed under these conditions contains only 55–70% of carbonate anions required by stoichiometry. Therefore, we conclude that the transformation of reconstructed Mg-Al-CO3 HTlc to spinel at 400 °C is the result of a reaction occurring between edges of crystallites.

Key Words

Double Hydroxide Grinding Hydrotalcite Reconstruction Spinel Thermal Decomposition 


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  1. Allmann R. 1968. The crystal structure of pyroaurite. Acta Crystallogr B24:972–977.CrossRefGoogle Scholar
  2. Bratton RJ. 1969. Coprecipitates yielding MgAl2O4 spinel powders. Am Ceram Soc Bull 48:759–762.Google Scholar
  3. Brindley GW, Kikkawa S. 1979. A crystal-chemical study of Mg,Al and Ni,Al hydroxy-perchlorates and hydroxy-car-bonates. Am Mineral 64:836–843.Google Scholar
  4. Cavani F, Trifirò F, Vaccari A. 1991. Hydrotalcite-type anionic clays: Preparation, roperties and applications. Catal Today 11:173–301.CrossRefGoogle Scholar
  5. Chibwe K, Jones W. 1989a. Synthesis of polyoxometalate-pillared layered double hydroxides via calcined precursors. Chem Mater 1:489–490.CrossRefGoogle Scholar
  6. Chibwe K, Jones W. 1989b. Intercalation of organic and inorganic anions into layered double hydroxides. J Chem Soc, Chem Commun 926–927.Google Scholar
  7. Constantino VRL, Pinnavaia TJ. 1995. Basic properties of Mg2+,1-xAl3+x layered double hydroxides intercalated by carbonate, hydroxide, chloride and sulfate anions. Inorg Chem 34:883–892.CrossRefGoogle Scholar
  8. Dimotakis ED, Pinnavaia TJ. 1990. New route to layered double hydroxides intercalated by organic anions: Precursors to polyoxometalate-pillared derivatives. Inorg Chem 13:2393–2394.CrossRefGoogle Scholar
  9. Drezdzon MA. 1988. Synthesis of isopolymetalate-pillared hydrotalcite via organic-anion-pillared precursors. Inorg Chem 27:4628–4632.CrossRefGoogle Scholar
  10. Giannelis EP, Nocera DG, Pinnavaia TJ. 1987. Anionic pho-tocatalysts supported in layered double hydroxides: Intercalation and photophysical properties of a ruthenium complex anion in synthetic hydrotalcite. Inorg Chem 26:203–205.CrossRefGoogle Scholar
  11. Gusmano G, Nunziante P, Traversa E, Chiozzini G. 1991. The mechanism of MgAl2O4 spinel formation from the thermal decomposition of coprecipitated hydroxides. J Eur Ceram Soc 7:31–39.CrossRefGoogle Scholar
  12. Hibino T, Yamashita Y, Kosuge K, Tsunashima A. 1995. De-carbonation behavior of Mg-Al-CO3 hydrotalcite-like compounds during heat treatment. Clays Clay Miner 43:427–432.CrossRefGoogle Scholar
  13. Hibino T, Kosuge K, and Tsunashima A. 1996. Synthesis of carbon-hydrotalcite complex and its thermal degradation behavior. Clays Clay Miner 44:151–154.CrossRefGoogle Scholar
  14. Hokazono S, Nagai H, Kato A. 1991. Synthesis of spinel powder by the homogeneous precipitation method. Nippon Kagaku Kaishi 275–280.Google Scholar
  15. Hudson MJ, Carlino S, Apperley DC. 1995. Thermal conversion of a layered (Mg/Al) double hydroxide to the oxide. J Mater Chem 5:323–329.CrossRefGoogle Scholar
  16. Ingram L, Taylor HFW. 1967. The crystal structures of sjögrenite and pyroaurite. Mineral Mag 36:465–479.Google Scholar
  17. Itaya K, Chang H-C, Uchida I. 1987. Anion-exchanged hy-drotalcite-like-clay-modified electrodes. Inorg Chem 26: 624–626.CrossRefGoogle Scholar
  18. Kodama H, Kotlyar LS, Ripmeester JA. 1989. Quantification of crystalline and noncrystalline material in ground kaolin-ite by X-ray powder diffraction, infrared, solid-state nuclear magnetic resonance, and chemical-dissolution analyses. Clays Clay Miner 37:364–370.CrossRefGoogle Scholar
  19. Kristof É, Juhász AZ, Vassányi I. 1993. The effect of mechanical treatment on the crystal structure and thermal behavior of kaolinite. Clays Clay Miner 41:608–612.CrossRefGoogle Scholar
  20. MacKenzie KJD, Meinhold RH, Sherriff BL, Xu Z. 1993. 27Al and 25Mg solid-state magic-angle spinning nuclear magnetic resonance study of hydrotalcite and its thermal decomposition sequence. J Mater Chem 3:1263–1269.CrossRefGoogle Scholar
  21. Miyata S, Kumura T. 1973. Synthesis of new hydrotalcite-like compounds and their physico-chemical properties. Chem Lett 843–848.Google Scholar
  22. Miyata S. 1975. The syntheses of hydrotalcite-like compounds and their structures and physico-chemical properties—I: The systems Mg2+-Al3+-NCV, Mg2+-Al3+-CL, Mg2+-Al3+-C1O4-, Ni2+-Al3+-CL and Zn2+-Al3+-CL. Clays Clay Miner 23:369–375.CrossRefGoogle Scholar
  23. Miyata S. 1980. Physico-chemical properties of synthetic hy-drotalcites in relation to composition. Clays Clay Miner 28: 50–56.CrossRefGoogle Scholar
  24. Narita E, Kaviratna P, Pinnavaia TJ. 1991. Synthesis of het-eropolyoxometalate pillared layered double hydroxides via calcined zinc-aluminium oxide precursors. Chem Lett 805–808.Google Scholar
  25. Pesic L., Salipurovic S, Markovic V, Vucelic D, Kagunya W, Jones W. 1992. Thermal characteristics of a synthetic hydrotalcite-like material. J Mater Chem 2:1069–1073.CrossRefGoogle Scholar
  26. Rey F, Fornés V, Rojo JM. 1992. Thermal decomposition of hydrotalcites: An infrared and nuclear magnetic resonance spectroscopic study. J Chem Soc, Faraday Trans 88:2233–2238.CrossRefGoogle Scholar
  27. Rouxhet PG, Taylor HFW. 1969. Thermal decomposition of sjögrenite and pyroaurite. Chimia 23:480–485.Google Scholar
  28. Yun SK, Constantino VRL, Pinnavaia TJ. 1995. New polyol route to keggin ion-pillared layered double hydroxides. Microporous Mater 4:21–29.CrossRefGoogle Scholar

Copyright information

© The Clay Minerals Society1997 1997

Authors and Affiliations

  • Toshiyuki Hibino
    • 1
  • Atsumu Tsunashima
    • 1
  1. 1.Materials Processing DepartmentNational Institute for Resources and EnvironmentTsukubaJapan

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