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Synthesis and Characterization of Zn-Al Layered Double Hydroxides Intercalated With 1- to 19-Carbon Carboxylic Acid Anions

Published online by Cambridge University Press:  01 January 2024

Thomas Kuehn  and
Herbert Poellmann
Thomas Kuehn*
Affiliation:
Soil Science, Martin Luther University Halle-Wittenberg, Weidenplan 14, 06108 Halle, Germany
Herbert Poellmann
Affiliation:
Soil Science, Martin Luther University Halle-Wittenberg, Weidenplan 14, 06108 Halle, Germany
*
* E-mail address of corresponding author: [email protected]
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Abstract

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Layered double hydroxides (LDHs) are layered ion exchangers, with a large surface-charge density, which react easily with organic anions. Various types of organics are rapidly substituted in the interlayer space of inorganic precursor LDHs. ZnAl-LDHs were intercalated with 1- to 19-carbon monocarboxylic acid anions by anion exchange of NO3-saturated LDH precursor phases in order to study the dependence of exchange reactions on synthesis parameters (temperature, pH, and interlayer anion). The carboxylic acid anion-LDHs synthesized were characterized using X-ray diffraction, infrared spectroscopy, thermal analysis, scanning electron microscopy, chemical analysis, and N2 adsorption. Carboxylic anion quantities in excess of the LDH anion exchange capacity easily replaced exchangeable nitrate anions at moderate pH. The intercalated LDH interlayer space depended on the alkyl chain length and orientation (inclination angle) of thecarboxylic-acid anion. Thelatticeparameter c0 ranged from 3.4 to 13.5 nm, but the a0 lattice parameter remained constant at 0.31 nm. Crystallographic analyses indicated a monomolecular arrangement of intercalated short-chain fatty-acid anions. At pH < 7, intercalated long-chain carboxylates showed a preferred bimolecular interlayer orientation. Carboxylic-acid anion exchange with LDHs at pH 7 resulted in the formation of two different sets of basal spacings, which indicated the coexistence of LDHs intercalated with monomolecular and bimolecular arrangements of interlayer carboxylic compounds.

Thermal treatment of the carboxylic acid anion-intercalated LDHs indicated stability up to ~140ºC. The release of interlayer water led to distortion of the crystallographic units and resulted in smaller basal spacings without collapse of the layered structure. Heat treatment re-oriented alkyl-chain carbon carboxylates (with >10 carbons) to a more upright interlayer position.

Keywords

Anion ExchangeCarboxylic Acid AnionHydrotalciteLDH
Type
Article
Information
Clays and Clay Minerals , Volume 58 , Issue 5 , October 2010 , pp. 596 - 605
Copyright
Copyright © Clay Minerals Society 2010

References

Anbarasan, R., Lee, W.D. and Im, S.S., 2005 Adsorption and intercalation of anionic surfactants onto layered double hydroxides-XRD study Bulletin of Materials Science 28 145–149 10.1007/BF02704234.CrossRefGoogle Scholar
Bish, D.L., 1980 Anion-exchange in takovite: applications to the other hydroxide minerals Bulletin of Mineralogy 103 170–175.CrossRefGoogle Scholar
Carlino, S., 1997 Theintercalation of carboxylic acids into layered double hydroxides: a critical evaluation and review of the different methods Solid State Ionics 98 73–84 10.1016/S0167-2738(96)00619-4.CrossRefGoogle Scholar
Cavani, F., Trifiro, F. and Vaccari, A., 1991 Hydrotalcite-type anionic clays: Preparation, properties and applications Catalysis Today 11 173–301 10.1016/0920-5861(91)80068-K.CrossRefGoogle Scholar
Choudhary, V.R., Dumbre, D.K., Narkhede, V.S. and Jana, S.K., 2003 Solvent-free selective oxidation of benzyl alcohol and benzaldehyde by tert-butyl hydroperoxide using MnO4-exchanged Mg-Al-hydrotalcite catalysts Catalysis Letters 86 229–233 10.1023/A:1022620203071.CrossRefGoogle Scholar
Cooper, M.A. and Hawthorne, F.C., 1996 The crystal structureof shigaite, [AlMn22+ (OH)6]3(SO4)2 Na(H2O)6(H2O)6, a hydrotalcite-group mineral The Canadian Mineralogist 34 91–97.Google Scholar
Hansen, B., Curtius, H. and Odoj, R., 2009 Synthesis of a Mg-Cd-Al layered double hydroxide and sorption of selenium Clays and Clay Minerals 57 330–337 10.1346/CCMN.2009.0570305.CrossRefGoogle Scholar
Itoh, T., Ohta, N., Shichi, T., Yui, T. and Takagi, K., 2003 The self-assembling properties of stearate ions in hydro-talciteclay composites Langmuir 19 9120–9126 10.1021/la0302448.CrossRefGoogle Scholar
Khan, A.I. and O’Hare, D., 2002 Intercalation chemistry of layered double hydroxides: recent developments and applications Journal of Materials Chemistry 12 3191–3198 10.1039/B204076J.CrossRefGoogle Scholar
Kloprogge, J.T., Wharton, D., Hickey, L. and Frost, R.L., 2002 Infrared and Raman study of interlayer anions CO3−2, NO3, SO42 and ClO4− in Mg/Al-hydrotalcite American Mineralogist 87 623–629 10.2138/am-2002-5-604.CrossRefGoogle Scholar
Kopka, H., Beneke, K. and Lagaly, G., 1988 Anionic surfactants between double metal hydroxide layers Journal of Colloid and Interface Science 123 427–436 10.1016/0021-9797(88)90263-9.CrossRefGoogle Scholar
Lagaly, G., 1981 Inorganic layer compounds Naturwissenschaften 68 82–88 10.1007/BF01047226.CrossRefGoogle Scholar
Meyn, M., Beneke, K. and Lagaly, G., 1990 Anion-exchange reactions of layered double hydroxides Inorganic Chemistry 29 5201–5207 10.1021/ic00351a013.CrossRefGoogle Scholar
Nhlapo, N., Motumi, T., Landman, E., Verryn, A.M.C. and Focke, W.W., 2008 Surfactant-assisted fatty intercalation of layered double hydroxides Journal of Materials Science 43 1033–1043 10.1007/s10853-007-2251-0.CrossRefGoogle Scholar
Ogawa, M. and Kaiho, H., 2002 Homogeneous precipitation of uniform hydrotalciteparticles Langmuir 18 4240–4242 10.1021/la0117045.CrossRefGoogle Scholar
Poellmann, H., 2007 Immobilisierung von Schadstoffen durch Speichermineralbildung Achen, Germany Shaker-Verlag 130–150.Google Scholar
Prasanna, S.V., Radha, A.V., Kamath, P.V. and Kannan, S., 2009 Bromide-ion distribution in the interlayer of the layered double hydroxides of Zn and Al: Observation of positional Disorder Clays and Clay Minerals 57 82–92 10.1346/CCMN.2009.0570108.CrossRefGoogle Scholar
Reichle, W.T., 1986 Synthesis of anionic clay minerals (mixed metal hydroxides, hydrotalcite) Solid State Ionics 22 135–141 10.1016/0167-2738(86)90067-6.CrossRefGoogle Scholar
Reinholdt, M.X. and Kirkpatrick, R.J., 2006 Experimental investigations of amino acid-layered double hydroxide complexes: glutamate-hydrotalcite Chemistry of Materials 18 2567–2576 10.1021/cm052107x.CrossRefGoogle Scholar
Roy, A., Forano, C., Besse, J.P. and Rives, V., 2001 Layered double hydroxides: Synthesis and postsynthesis modifications Layered Double Hydroxides: Present and Future New York Nova Science Publishers, Inc. 1–38.Google Scholar
Wypych, F., Arı´zaga, G.G.C. and da Costa Gardolinski, J.E.F., 2005 Intercalation and functionalization of zinc hydroxide nitratewith mono- and dicarboxylic acids Journal of Colloid and Interface Science 283 130–138 10.1016/j.jcis.2004.08.125.CrossRefGoogle ScholarPubMed
Xu, Z.P. and Bratermann, P.S., 2007 Competitive Intercalation of Sulfonates into Layered Double Hydroxides (LDHs): the Key Roleof Hydrophobic Interactions Journal of Physical Chemistry C 111 4021–4026 10.1021/jp0683723.CrossRefGoogle Scholar
Yang, L., Sharivari, Z., Liu, P.K.T., Sahimi, M. and Tsotsis, T.T., 2005 Removal of trace levels of arsenic and selenium from aqueous solutions by calcined and uncalcined layered doublehydroxides (LDH) Industrial & Engineering Chemical Research 44 6804–6815 10.1021/ie049060u.CrossRefGoogle Scholar
Zhao, H. and Vance, G.F., 1998 Selectivity and molecular sieving effects of organic compounds by a ß-cyclodextrin-pillared layered double hydroxide Clays and Clay Minerals 46 712–718 10.1346/CCMN.1998.0460612.Google Scholar
Zhu, J., Yuan, P., He, H., Frost, R., Tao, Q., Shen, W. and Bostrom, T., 2008 In situ synthesis of surfactant/silane-modified hydrotalcites Journal of Colloid and Interface Science 319 498–504 10.1016/j.jcis.2007.11.037.CrossRefGoogle ScholarPubMed