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Substitution of Fe3+ for Al3+ Cations in Layered Double Hydroxide [LiAl2(OH)6]2CO3-nH2O

Published online by Cambridge University Press:  01 January 2024

Piotr Kuśtrowski ,
Agnieszka Węgrzyn ,
Alicja Rafalska-Łasocha ,
Agnieszka Pattek-Janczyk  and
Roman Dziembaj
Piotr Kuśtrowski*
Affiliation:
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
Agnieszka Węgrzyn
Affiliation:
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
Alicja Rafalska-Łasocha
Affiliation:
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
Agnieszka Pattek-Janczyk
Affiliation:
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
Roman Dziembaj
Affiliation:
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
*
*E-mail address of corresponding author: [email protected]
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Abstract

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Synthesis of the Li-Al-Fe layered double hydroxides was performed by the coprecipitation method at constant pH (11.0±0.2) and temperature (40±2°C). Structural features of the as-synthesized samples were investigated by X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy and Mössbauer spectroscopy. The samples consisted of well crystallized [LiFexAl2-x(OH)6]2CO3·nH2O phases with strict ordering of M+ and M3+ cations in the sheets. However, only a proportion of Al3+ could be substituted by Fe3+ ions. The excess Fe3+ cations formed a separate ferrihydrite phase. Incorporation of Fe into the hydrotalcite-like structure resulted in an increase in the a lattice parameter determined by XRD. In addition, a shift of IR absorption bands, ascribed to the stretching vibrations of interlayer CO32− anions as well as the transitional motions of oxygen in the layers, to lower frequencies was observed. The presence of Fe3+ in the octahedral sheets caused a splitting of the band assigned to the stretching vibrations of the layer OH groups. Mössbauer experiments revealed that Fe exists in the synthesized samples in two different chemical environments. A proportion of the Fe3+ cations is incorporated as isolated ions in the [LiFexAl2-x(OH)6]2CO3.nH2O crystal structure. However, Fe3+ ions forming the ferrihydrite phase are dominant in the Fe-rich materials.

Keywords

FTIRHydrotalcite-like CompoundsLi-Al-Fe Layered Double HydroxidesMössbauer SpectroscopySEMXRD
Type
Research Article
Information
Clays and Clay Minerals , Volume 53 , Issue 1 , February 2005 , pp. 18 - 27
Copyright
Copyright © Clay Minerals Society 2005

References

Cavani, F. Trifirò, F. and Vaccari, A., (1991) Hydrotalcite-type anionic clays: preparation, properties and application Catalysis Today 11 173–301 10.1016/0920-5861(91)80068-K.Google Scholar
Chisem, I.C. and Jones, W., (1994) Ion-exchange properties of lithium aluminum layered double hydroxides Journal of Materials Chemistry 4 1737–1744 10.1039/jm9940401737.Google Scholar
Dutta, P.K. and Robins, D.S., (1994) Interlayer dynamics of a fatty acid exchanged lithium aluminum layered double hydroxide monitored by infrared spectroscopy and pyrene fluorescence Langmuir 10 4681–4687 10.1021/la00024a048.Google Scholar
Hansen, H.C.B. and Koch, C.B., (1995) Synthesis and characterization of pyroaurite Applied Clay Science 10 5–19 10.1016/0169-1317(95)00014-U.Google Scholar
Hernandez-Moreno, M.J. Ulibarri, M.A. Rendon, J.L. and Serna, C.J., (1985) IR characteristics of hydrotalcite-like compounds Physics and Chemistry of Minerals 12 34–38.Google Scholar
Kannan, S. and Swamy, C.S., (1997) Effect of trivalent cation on the physicochemical properties of cobalt containing anionic clays Journal of Materials Science 32 1623–1630 10.1023/A:1018599211053.Google Scholar
Klug, H.P. and Alexander, L.E., (1974) X-ray Diffraction Procedures New York John Wiley and Sons Inc..Google Scholar
Koch, C.B., (1998) Structures and properties of anionic clay minerals Hyperfine Interactions 117 131–157 10.1023/A:1012603712578.Google Scholar
Kumbhar, P.S. Sanchez-Valente, J. Millet, J.M. and Figueras, F., (2000) Mg-Fe hydrotalcite as a catalyst for the reduction of aromatic nitro compounds with hydrazine hydrate Journal of Catalysis 191 467–473 10.1006/jcat.2000.2827.Google Scholar
Lasocha, W. and Lewinski, K., (1994) PROSZKI - a System of Programs for Powder Diffraction Data Analysis Journal of Applied Crystallography 27 437–438 10.1107/S002188989400066X.Google Scholar
Miyata, S., (1975) The syntheses of hydrotalcite-like compounds and their structures and physico-chemical properties - I: The systems Mg2+-Al3+-NO3−, Mg2+-Al3+-Cl−, Mg2+-Al3+-ClO4−, Ni2+-Al3+-Cl− and Zn2+-Al3+-Cl− Clays and Clay Minerals 23 369–375 10.1346/CCMN.1975.0230508.Google Scholar
Rajamathi, M. Thomas, G.S. and Kamath, P.V., (2001) The many ways of making anionic clays Proceedings of the Indian Academy of Sciences — Chemical Sciences 113 671–680 10.1007/BF02708799.Google Scholar
Ramos-Gallardo, A. and Vegas, A., (1996) The cation array in aluminum oxides, hydroxides and oxihydroxides Zeitschrift für Kristallographie 211 299–303.Google Scholar
Schwertmann, U. and Cornell, R.M., (1991) Iron Oxides in the Laboratory: Preparation and Characterization Weinheim, Germany Verlag Chemie.Google Scholar
Serna, C.J. Rendon, J.L. and Iglesias, J.E., (1982) Crystal-chemical study of layered [Al2Li(OH)6]X_-nH2O Clays and Clay Minerals 30 180–184 10.1346/CCMN.1982.0300303.Google Scholar
Sissoko, I. Iyagba, E.T. Sahai, R. and Biloen, P., (1985) Anion intercalation and exchange in Al(OH)3-derived compounds Journal of Solid State Chemistry 60 283–288 10.1016/0022-4596(85)90278-6.Google Scholar
Taylor, H.F.W., (1969) Segregation and cation-ordering in sjögrenite and pyroaurite Mineralogical Magazine 37 338–342 10.1180/minmag.1969.037.287.04.Google Scholar
Twu, J. and Dutta, P.K., (1989) Structure and reactivity of oxovanadate anions in layered lithium aluminate materials Journal of Physical Chemistry 93 7863–7868 10.1021/j100360a028.Google Scholar