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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*
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.

Type
Research Article
Copyright
Copyright © Clay Minerals Society 2005

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