ETD Collection
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Item Effect of fly ash composition on the synthesis of carbon nanomaterials(2016-05-10) Matshitse, Refilwe Manyama StephinaFly ash is a by-product generated during the combustion of coal for electricity gen- eration. Previous studies have shown that various waste fly-ashes (Japanese, Saudi Arabian, and Australian) contain trace quantities of transition metal elements which can be used in the synthesis of shaped carbon nanomaterials. A survey of the litera- ture has shown that no attempts to correlate the composition of a particular coal fly ash and the type or quantity of carbon nanomaterials (CNMs) that can be synthesized has been made. Neither has the effect of leached fly ash been tested for the synthesis of CNMs. Hence a study on the effect of the chemical composition of South African fly ash (collected from ESKOM’s Duvha power station in Mpumalanga) upon the chemical vapour deposition (CVD) synthesis of carbon nanostructures is justified. Untreated and chemically treated fly ash samples were used as catalysts in the CVD method to synthesize CNMs. In the latter case selective leaching experiments were conducted on the fly ash samples under acidic, basic and neutral conditions. Op- timal CNM synthetic conditions were achieved by initially flowing H2 gas to re- duce the metal oxides within the fly ash catalyst followed by the introduction of the carbon source (C2H2) at a temperature range of 600 - 800 ◦C. All samples were quantitatively and/or qualitatively characterized. Inductively coupled plasma optical emission spectrometry (ICP-OES) and X-ray fluorescence (XRF) techniques were used to quantify the metal ions which were removed from the fly ash samples. Fur- thermore, qualitative studies were conducted with (PXRD, and laser Raman spec- troscopy), morphological and surface area characterization techniques (SEM, TEM and BET) were used to investigate the synthesis of CNMs from the untreated and chemically treated fly ash samples. Results have shown that carbon nanofibers (CNFs) of different geometric morpholo- gies were synthesized at an optimal yield temperature of 700◦C. A combination of smooth, thin, wide, spiral platelet-like, stacked cup, and fishbone morphologies were reported when the untreated fly ash catalyst was used. Fly ash catalysts under acidic, basic and neutral treatments showed CNFs of varying sizes and specific morpholo- gies. Smooth graphitic platelet-like, stacked cup and platelet-like CNFs were re- ported when the fly ash catalyst was leached with neutral, basic and acidic solutions. Carbon nanofibre sizes with the IG ID ratios were reported as follows 115 nm (1.092), 52 nm (0.799), and 200 nm (0.960) under neutral, basic and acidic mediums respec- tively. Surface areas (41, 14 and 7) m2/g for the CNFs that were synthesised from the neutral, basic and acidic treated fly ash catalysts were related to the selective leaching of metals. The quality and quantity of CNFs obtained under acidic medium were associated with the leaching of iron (5.6%), cobalt (1.7%), calcium (20.4%), copper (12.5%), chromium (4.6%), magnesium (23.3%), manganese (15.2%) and nickel (2%) from the fly ash catalyst. Under a basic medium only chromium (0.2%), calcium (0.3%) and copper (7.4%) were removed. Significantly the best quality of CNFs was ob- tained when fly ash was treated under neutral conditions. Metal ions such as: cal- cium (3.7%), copper (3.8%), chromium (0.1%), and magnesium (1.3%) were mod- erately removed from the ash matrix. Therefore, composition and quantity of the fly ash catalyst had an effect on the synthesis of CNFs.Item Synthesis and characterisation of gold-rhodium nanocatalysts and their catalytic activity on carbon monoxide oxidation(2016-05-10) Rikhotso, Rirhandzu ShamaineGold nanoparticles are ideally suited as catalysts for selected low temperature reactions such as CO oxidation for catalytic convertors in the motor industry due to their high activity. But they are prone to sintering at high temperatures. Platinum-group-metal based catalysts are efficient at elevated temperatures and generally inactive at lower temperatures. This study explored the CO oxidation efficiency of gold nanoparticles and of a combination of gold and rhodium nanoparticles. Variables such as pH, loading concentration and type of support were varied to control the final properties of the Au based catalysts. Possible bimetallic systems of gold and rhodium were explored for wider temperature range activity than gold alone. All catalysts were characterised using Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDS) and X-Ray Diffraction (XRD). Activity was measured using a temperature controlled, custom-built reactor linked to a gas chromatograph. The conditions yielding the smallest gold nanoparticles were established by adding 5, 8 or 10 wt.% loadings of chloroauric acid to aqueous suspensions of either TiO2 or SiO2 at pH 5, 7 or 9 and at 70-75 °C over 60 minutes. Each preparation was sealed in parafilm, aged in the dark at room temperature for 3 days, vacuum-filtered and subsequently calcined at 300 °C. Gold nanoparticles were smallest when deposited onto TiO2 instead of SiO2, at pH 7 and at a loading of 5 wt. %. A combination of gold and rhodium catalysts were subsequently prepared using these conditions, with the simultaneous addition of rhodium at 1, 3, 5 or 10 wt. % loading. Hydrolysis of gold is highly dependent upon pH, resulting in the synthesis of smaller particles under alkaline conditions. Catalytic activity of samples analysed at 70 and 150 °C was highest for gold nanoparticles below 5 nm, in agreement with previous studies. In the proposed bimetallic catalysts, it was difficult to distinguish gold and rhodium nanoparticles in TEM images, although EDS confirmed their combined presence on the TiO2 support. Particle sizes remained below 5 nm, appearing monodispersed on the TiO2 support except at 10 % rhodium loading where some nanoparticle aggregation was observed. CO oxidation activity showed an apparent temperaturedependent shift in the optimal rhodium loading. Au-TiO2 catalysts with a 5% loading showed the highest activity up to 350 °C for a period of 10 hours and the catalyst deactivated due to sintering. At 150 and 200 °C the Au/Rh-TiO2 catalyst remained active for more than 12 hours. It was concluded that the inclusion of rhodium is a potentially-favourable method for stabilising the activity of gold catalysts.Item Dynamic electrical transport in carbon nanotubes and nanodiamond films(2014) Chimowa, GeorgeA comprehensive experimental study on alternating current (AC) electrical transport in the three forms of carbon nanotubes (CNTs) and nanodiamond films is presented. It is termed dynamic electrical transport to differentiate it from direct current measurements, which may be referred as static transport. The results and analysis are based on the scattering parameter measurements of a few horizontally aligned single, double, multi-walled carbon nanotubes and nanodiamond films. Which were measured in the frequency range 10 MHz to 65 GHz, at room and cryogenic temperatures using a vector network analyser. The work is motivated by the fact that AC transport in 1D systems has not been fully studied and is not well understood. From direct current measurements, it is known that one dimensional (1D) electrical transport is very different from its two or three dimensional counterpart. This is because adding an electron to a 1D system tends to affect the whole system in ways which to date cannot be fully explained theoretically. CNTs present an ideal platform to study the AC or dynamic transport behaviour of 1D systems because of the high mobility and electrical conductivity at nano-scale. Therefore from the AC complex impedance and conductance, this work demonstrates quantum effects of collectively excited strongly interacting electrons (Luttinger Liquid), which had been predicted theoretically but not observed experimentally using this technique. Ballistic transport at room temperature is also demonstrated by setting the stimulus frequency higher than the scattering rate in the CNTs. A crossover from capacitive to inductive behaviour in the imaginary component of impedance has been shown by improving the CNT-electrode coupling. Furthermore the effect of metal contacts on microwave/ radio frequency transmission is also demonstrated. The results are consolidated by RF simulations, as strong conclusions are drawn. Studies on the dynamic transport in nanodiamond films revealed a crossover from the insulating to semi-metallic regime by nitrogen incorporation. The crossover is explained by considering the changes of the grain boundary morphology. This work shows that AC transport in polycrystalline nanodiamond films is similar to DC transport.Item Synthesis and characterization of bimetallic platinum nanoparticles for use in catalysis(2015) Mathe, Ntombizodwa RuthBimetallic platinum nanoparticles were synthesized for application as anode catalysts for low temperature fuel cells such as direct methanol fuel cells (DMFCs). Two distinct synthesis procedures were used; namely conventional synthesis with post-synthesis heat treatment, and secondly polyol microwave-irradiation without further heat-treatment. The aim was to synthesize interesting and novel bimetallic nanostructures and relate their shape and morphologies to their methanol oxidation reaction (MOR) activities and their CO tolerance. Due to the high cost of the conventional synthesis processes as well as their use of harmful solvents, microwave-irradiation was explored as a possible synthesis procedure. It is a greener and more environmentally friendly approach with possibilities of mass production of the nanoparticles. For both the synthesis procedures, the reducing agent, the precursor salts, surfactants, pH of the solution and molar ratios were varied to determine the effect on the shape, size and ultimately the electrocatalytic activities of the Pt-Co and Pt-Ni nanoparticles. For the conventional synthesis procedure, the main parameter of comparison was the strength of the reducing agents, where NaBH4 and N2H4 were used under the same reaction conditions. In this study, the strength of the reducing agent affected the properties of the Pt-Co and Pt-Ni nanoparticles, such that, the stronger the reducing agent, the higher the degree of alloying and the more electrocatalytically active the materials. The drawback in the conventional synthesis was however low current outputs, in the microamps range, which necessitates a need to explore other synthesis procedures. Microwave-irradiation was thus used as an alternative synthesis procedure in an attempt to produce more active bimetallic platinum nanoparticles. Different reaction parameters were changed in this process to optimize the synthesis process, namely the pH of the solution, the amount of surfactant and the Pt-Ni molar ratio. In changing the reaction parameters, there was an observed change in the structure of the nanoparticles, with an average size in the order of 5 nm and different MOR activities. Furthermore, it was found that the activity was highest for the optimum amount of PVP and NaOH concentration of 500 mg and 1.0 M NaOH. In general, the MW synthesized nanoparticles achieved current values in the microamps to amps range, making it a more attractive synthesis procedure compared to the conventional method. The CO tolerance of the materials is an important aspect, as one of the main drawbacks of the commercial application of fuel cells is the propensity of Pt to get poisoned by CO during the methanol dissociation process. Therefore CO stripping measurements were performed on the MW-irradiated catalysts. The catalysts produced in this work showed good resistance towards CO. In general, the behaviours of the catalysts were dependent on the amount of surfactant and the molar ratio of the starting solution. The mechanism of CO tolerance in this case was determined as the bifunctional model, where the Ni-oxide and Ni-hydroxide species donate O to the electrooxidation of CO to CO2. In conclusion, the study of microwave-irradiated bimetallic nanoparticles performed here, resulted in highly active catalysts, which are even more active than commercial Pt/C nanoparticles.Item A comparative study of micro & nanocarbon reinforced synthetic rubber composites(2014-09-01) Maifadi, JamesThis study concentrated on two main thrusts: 1) the optimal synthesis and characterisation of various micro- and nanosized carbon materials and 2) a comparative investigation of the capabilities of these carbonaceous materials to reinforce a locally available styrene butadiene rubber (SBR), which was commonly used to make car tyres. In the former case, a range of carbon materials including nitrogen doped/undoped carbon nanotubes as well as carbon microspheres (CMSs) were successfully synthesized by two different techniques (i.e. chemical vapour deposition (CVD) and hydrothermal synthesis). These were then fully characterised by numerous techniques which included: TEM, TGA, FTIR, PXRD, laser Raman spectroscopy, Zeta potential measurements and BET surface area analysis. In the latter case, these micro and nanocarbon materials were systematically added to SBR at various loadings (ranging from 0.125–0.500% (m/m)). Here the tensile strengths of the resultant composites, loaded with these various micro and nanocarbon materials, were measured for comparison to establish which (if any) was the best reinforcement material for SBR. Results obtained from the tensile strength measurements of the variously loaded SBR composites, showed that irrespective of the method of synthesis (i.e. CVD or hydrothermal synthesis) carbon microspheres (undoped, doped, functionalised or unfuntionalised) performed more poorly as fillers than carbon nanotubes. Furthermore the results obtained, from the various characterisation techniques mentioned previously, indicated that the lower performance of these microspheres as fillers may have been due to their: size, shape and low surface areas. By contrast when the tensile strengths of SBR reinforced with either CNTs or NCNTs were measured, the former outperformed the latter as fillers. It was speculated, based upon the data obtained, that NCNTs were poorer fillers than CNTs due to their higher negative surface charges, larger diameters and lower crystallinity. Hence this study has shown that low loadings (i.e. 0.250 % (m/m)) of the correctly matched type of carbonaceous material can significantly enhance the tensile strength and Young’s modulus of a locally available styrene butadiene rubber.