A new lyotropic liquid crystalline system: Oligo (ethylene oxide) surfactants with transition metal complexes and the synthesis of mesoporous metal sulfides

Abstract

In this study a new templating method, which can be used to synthesise mesporous materials, has been developed. The main objective of this work is to form organic mesophase in the presence of inorganic salts. This is an organic-inorganic hybrid mesophase, which can be used to template the growth of inorganic materials. Here for the first time, a new lyotropic liquid crystalline (LLC) system has been presented from oligo (ethylene oxide) type surfactant and transition metal aqua complexes. The temperature and the metal aqua complex concentration range of the complex/surfactant mixtures have been determined, where the mixtures have a liquid crystalline (LC) phase. Here, the complex refers to Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Zn(NO3)2·6H2O, Cd(NO3)2·4H2O, and CoCl2·6H2O and the surfactant is C12H25(CH2CH2O)10OH, (C12EO10). The addition of the metal aqua complexes directly to the surfactant produces a LC phase. The LC phase obtained from the mixture of these two is more stable than the LC phase obtained from a mixture of free water and surfactant. The FT-IR and UV-Vis absorption, Polarised Optical Microscopy (POM) and Powder X-ray Diffraction measurements show that the coordinated water molecules mediate the formation of the LC phase. Our observations also show that the coordinated water molecules make a stronger interaction with ethylene oxide (EO) chains than free water molecules. The LC templating approach, which is demonstrated as a new system has been used for synthesis of meso-structured metal oxides, metal sulphides and even metal mesh. From all these studies, it is well known that in order to maintain LC phase the metal ion concentration should correspond to metal ion to surfactant mole ratio below 0.8. However, this work shows that the amount of metal aqua complex concentration can be increased up to a 6.5 complex to surfactant mole ratio by maintaining the integrity of the hexagonal and/or cubic structure of the LC phase. This may open a new area for the realisation of new mesostructured materials with better qualities and much higher yields. In the first part of the thesis, the thermal and structural properties of the new LLC phase has been established by using polarized optical microscopy (POM) with an attached hot plate, PXRD, FT-IR and UV-Vis absorption methods. In the second part, the new phase has been used as a template to synthesise mesoporus metal sulfides. The second part of the thesis deals mainly with the structure and synthesis of mesostructured CdS and ZnS. It has been demonstrated that the LC phase of Zn(NO3)2·6H2O, and Cd(NO3)2·4H2O in oligo(ethylene oxide) surfactant survive partially during the reaction with H2S to produce the corresponding metal sulfides.