Philosophiae Doctor - PhD / The overall aim of this thesis was to prepare nanostructured more processable heteronuclear sulphonated polyanyline nanocomposites with electroconductive properties suitable for applications in biosensors. The sulphonated self-assembled polyaniline and derivatised polyaniline nanocomposites (SPAHs) were prepared by chemical oxidative polymerisation or electrical decomposition. The SPAHs prepared include those of polyaniline (PANi), poly-o-methoxyaniline (POMA) and poly-2.5 dimethoxyaniline (PDMA). Two types of sulphonic acids of heteronuclear aromatic hydrocarbons were used in the production of sulphonated SPAH composites. These were anthracene sulphonic acid (ASA) and naphthalene sulphonic acids (NSA) wich played both doping and surfactant roles. / South Africa

The present thesis is focused on the synthesis and environmental applications of polyaniline and its nanocomposites. It is organized in six chapters and brief discussions of the contents of the individual chapters are given below. Chapter 1 reviews two important water purification methods: adsorption and photocatalysis, which are widely discussed in literature. A general introduction to conducting polymers has been given and their photocatalytic activity has been described. Chapter 2 reports the application of polyaniline emeraldine salt for the removal of anionic dyes from aqueous solutions by adsorption. A possible mechanism for the anionic dye adsorption by PANI emeraldine salt has been proposed. The electrostatic interaction between the positively charged PANI backbone and dye anions is responsible for significant dye adsorption. The kinetic parameters for the adsorption of anionic dyes on PANI have also been determined. In Chapter 3, we investigate the adsorption and desorption of anionic dyes from aqueous solution by PANI doped with different protonic acids. PANI with three dopants, namely p-toluene sulfonic acid (PTSA), camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA) were used to adsorb various dyes. The adsorbed dyes were desorbed from the polymer by using a basic aqueous solution. It was found that the adsorption of dye is dependent on the size and nature of the dopant acids. The influence of different dopants on the adsorption and desorption kinetic parameters was also examined. In chapter 4, the inherent property of PANI to adsorb dyes has been explored for the detection of dyes by electrochemical method. The changes in the CV of PANI film coated on Pt electrodes on addition of dye have been employed for detection of dye in aqueous solution. Furthermore, PANI coated stainless steel (SS) electrodes show a change in current intensity of Fe2+/Fe3+ redox peaks due to addition of dye in the electrolyte solution. Chapter 5 describes the synthesis and characterization of polyaniline-grafted-chitosan (CPANI) with different grafting ratios. The mechanical properties and the crystallinity of CPANI were investigated by means of nanoindentation and X-ray diffraction experiments, respectively. CPANI has been further self-assembled into multilayer thin film via versatile and simple layer-by-layer (LbL) approach. Negatively charged hyaluronic acid (HUA) was used as complementary polyelectrolyte for the self-assembly. LbL growth of the multilayer thin films has been monitored with UV-vis spectral analysis as well as by AFM. The formation of thin film has been further characterized by SEM. The pH responsive behavior of CPANI/HUA multilayer thin film has been investigated. Reusability of this thin film has been investigated by repeating the pH responsive experiments for 10 cycles. Chapter 6 is focused on the preparation of nanocomposite thin films of CPANI/PSS/TiO2 via LbL approach. LbL growth of this self-assembly was monitored by UV-vis spectral analysis and porous nature was observed from SEM images. Poly (styrene sulfonate) (PSS) was used as bridging layer between TiO2 nanoparticles and CPANI for the multilayer self-assembly. Incorporation of CPANI within this LbL self-assembly enhanced the dye degradation ability of the thin film by increasing the availability of dye molecules around the TiO2 nanoparticles. Furthermore, CPANI may act as a sensitizer to enhance the photocatalytic activity of TiO2. The effects of surface area of the multilayer thin film and amount of catalysts (TiO2 nanoparticles) incorporated in the self-assembly were described based on the kinetics of the dye degradation reactions. The same multilayer thin film can be efficiently used for dye degradation several times. The work presented in this thesis utilizes unique dye adsorption properties of PANI and its copolymers. The change in conductivity of PANI after dye adsorption and the electrochemical dye detection in aqueous medium promise the potential of PANI as a dye sensing material in waste water at very low concentration. The nanocomposites of CPANI/PSS/TiO2 present a novel material for photocatalysis.