Synthesis and Characterization of Methanesulfonate and Ethanesulfonate Intercalated Lithium Aluminum LDHs

Abstract

LDH-phases become increasingly interesting due to their broad ability to be able to incorporate many different cations and anions. The intercalation of methanesulfonate and ethanesulfonate into a Li-LDH as well as the behavior of the interlayer structure as a function of the temperature is presented. A hexagonal P63/m [LiAl2(OH)6][Cl∙1.5H2O] (Li-Al-Cl) precursor LDH was synthesized by hydrothermal treating of a LiCl solution with γ-Al(OH)3. This precursor was used to intercalate methanesulfonate (CH3O3S−) and ethanesulfonate (C2H5O3S−) through anion exchange by stirring Li-Al-Cl in a solution of the respective organic Li-salt (90˚C, 12 h). X-ray diffraction pattern showed an increase of the interlayer space c' (d001) of Li-Al-methanesulfonate (Li-Al-MS) with 1.2886 nm and Li-Al-ethanesulfonate (Li-Al-ES) with 1.3816 nm compared to the precursor with 0.7630 nm. Further investigations with Fourier-transform infrared spectroscopy and scanning electron microscopy confirmed a complete anion exchange of the organic molecules with the precursor Cl−. Both synthesized LDH compounds [LiAl2(OH)6]CH3SO3∙nH2O (n = 2.24-3.72 (Li-Al-MS) and [LiAl2(OH)6]C2H5SO3}∙nH2O (n = 1.5) (Li-Al-ES) showed a monomolecular interlayer structure with additional interlayer water at room temperature. By increasing the temperature, the interlayer water was removed and the interlayer space c' of Li-Al-MS decreased to 0.87735 nm (at 55˚C). Calculations showed that a slight displacement of the organic molecules is necessary to achieve this interlayer space. Different behavior of Li-Al-ES could be observed during thermal treatment. Two phases coexisted at 75˚C - 85˚C, one with a reduced c' (0.9015 nm, 75˚C) and one with increased c' (1.5643 nm, 85˚C) compared to the LDH compound at room temperature. The increase of c' is due to the formation of a bimolecular interlayer structure.