Probing the local environment of hybrid materials designed from ionic liquids and synthetic clay by Raman spectroscopy

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 122; pp. 469 - 475
• Main Authors: Siqueira, Leonardo J.A., Constantino, Vera R.L., Camilo, Fernanda F., Torresi, Roberto M., Temperini, Marcia L.A., Ribeiro, Mauro C.C., Izumi, Celly M.S.
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 25.03.2014
• Subjects: Aluminum Silicates - chemistry; Cations - chemistry; Clay; Hybrid material; Imidazoles - chemistry; Ionic liquid; Ionic Liquids - chemistry; Models, Molecular; Piperidines - chemistry; Raman spectroscopy; Spectrum Analysis, Raman; X-Ray Diffraction; Clay; Raman spectroscopy; Hybrid material; Ionic liquid
• ISSN: 1386-1425; 1873-3557
• DOI: 10.1016/j.saa.2013.11.084

In this work, FT-Raman spectroscopy was employed to investigate the local environment probed by ionic-liquid-forming cations in a confined interlayer space of synthetic Laponite clay. Comparison of Raman spectra of pure ionic liquids and the hybrid materials and quantum chemistry calculations was performed to probe the local environment experienced by the confined cations. [Display omitted] •Laponite and ionic liquids forming cations nanomaterials have been prepared and characterized.•FT-Raman was employed to investigate the environment of confined organic cations.•Organic cations are located parallel to the clay slab with a relatively disordered structure.•The environment probed by these intercalated cations is similar to ionic liquids with TFSI anion. Hybrid organic–inorganic material containing Laponite clay and ionic liquids forming cations have been prepared and characterized by FT-Raman spectroscopy, X-ray diffraction, and thermal analysis. The effect of varying the length of the alkyl side chain and conformations of cations has been investigated by using different ionic liquids based on piperidinium and imidazolium cations. The structure of the N,N-butyl-methyl-piperidinium cation and the assignment of its vibrational spectrum have been further elucidated by quantum chemistry calculations. The X-ray data indicate that the organic cations are intercalated parallel to the layers of the clay. Comparison of Raman spectra of pure ionic liquids with different anions and the resulting solid hybrid materials in which the organic cations have been intercalated into the clay characterizes the local environment experienced by the cations in the hybrid materials. The Raman spectra of hybrid materials suggest that the local environment of all confined cations, in spite of this diversity in properties, resembles the liquid state of ionic liquids with a relatively disordered structure.