The aim of this project was to investigate methods for purification and modification of Single Wall and Multi Wall Carbon Nanotubes. Covalent and noncovalent approaches to functionalization were studied. The dispersibility, structure and electronic properties of modified tubes were characterized by Raman, UV-vis-NIR and XPS. Fluorescence, NMR and TEM were further employed to characterize the interaction between nanotubes and non-covalent modifiers. The effects of five different purification methods on the dispersibility, and degree of carboxylic acid functionality of SWCNTs, along with the level of defects on the tube side walls, and the resulting electronic properties of SWCNTs have been investigated. It was found that all oxidation treatments successfully removed metallic oxides and amorphous carbon impurities, while different oxidation treatments introduced different levels of oxidized sites on the SWCNTs. Heat treatment after oxidation eliminated some of the carboxylic groups introduced by oxidation. SWCNTs covalently functionalized by aromatic diazonium salts containing nitro, carboxylate and fluoro groups on the aromatic ring were prepared. Heating of these tubes in vacuum at 350_C for 5 h partially reversed the effects of functionalization. However, due to the low degree of functionalization achieved in the preliminary studies, the dispersibility/solubility of functionalized tubes did not greatly improve. The interaction in stable suspensions of CNTs with positively or negatively charged pyrene derivatives via noncovalent functionalization, was extensively studied. 1-pyrene methylamine hydrochloride gave most stable dispersions. 1H and 2H NMR spectroscopy of MWCNTs/1-pyrene methylamine hydrochloride dispersion in DMF-d7 showed that the broadened signals are associated with weakly or unbound pyrene, while strongly bound pyrene is not observable in solution-state NMR. The strong pyrene attachment on MWCNTs by π-π stacking can be reversed by dialysis and/or extensive washing. Biological molecules such as polypeptides and amino acids also dispersed MWCNTs into solvents by noncovalent modification. It is found that polytryptophan demonstrated the greatest ability to disperse MWCNTs. Digestion with chymotrypsin enabled polytryptophan binding to be reversed. A combination of tube cutting and non-covalent functionalization by pyrenes or peptides enables tubes to be suspended/dissolved in solvents such as DMF and ethanol, and significantly allows tubes to be manipulated for practical device applications.

Philosophiae Doctor - PhD / The development of finely dispersed powders and superfine-grained materials intended for application in various areas of science and engineering is one of the challenges facing modern nanotechnology. Thus, specific fundamental and applied research was required in order to consolidate advancement made in preparing nano- and submicron crystalline composite materials. Useful templates for electrochemical deposition of nanowires include porous alumina films formed by anodic oxidation of aluminium, nuclear track-etched porous membranes, nanochannel array-glass and mesoporous channel hosts. The properties of the nanowires are directly related to the properties of the nanoporous templates such as, the relative pore orientations in the assembly, the pore size distribution, and the surface roughness of the pores. The template synthesis method, based on the use of porous polymeric and inorganic matrixes, is now actively used for synthesis of such composite materials. The method allows the chemical and/or electrochemical synthesis of nano- and microstructured tubes and wires consisting of conducting polymers, metals and semiconductors.In this study various technological challenges relating to template synthesis and development of nickel nano- and microstructures on adequately strong and durable substrates were investigated. The two methods used were the electrochemical and chemical deposition. “Hard nickel” bath solution was used for optimal nickel deposition. This optimization included investigating variables such as the template structure, type of electrolyte and form of electrolytic deposition. Scanning Electron Microscopy was used to investigate the structures of template matrixes and the resultant materials. The cyclic voltammetry method was applied for the analysis of electrochemical properties and hydrogen evaluation reaction of nano- and microstructured nickel based electrodes. The activity of composite nano- and microstructured materials in various configurations resulting from pore filling of template matrices by nickel was explored. Studies of the physical structure and chemical properties of the nanostructured materials included investigating the necessary parameters of template matrices. The optimum conditions of synthesis, which allowed development of materials with the highest catalytic activity, were determined.  The effect of the template structure on microcrystallinity of the catalyst particles was established using the XRD method. Different new types of non-commercial asymmetric ion track membranes has been tested for nanostructure preparation. The catalytic activity of the new developed nanomaterials is higher as compared to materials using commercial templates. The procedures to modify the newly developed nickel catalyst with Pt, Pd and Pt-Pd alloy have been developed. The Pt and Pt-Pd alloy containing catalyst showed the best performance in water electrolysis. In this work, the promising role for specific application of the new materials in hydrogen economy has been demonstrated. / South Africa

published_or_final_version / Physics / Doctoral / Doctor of Philosophy

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published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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