published_or_final_version / abstract / Physics / Master / Master of Philosophy

published_or_final_version / abstract / Physics / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Mechanical Engineering / Doctoral / Doctor of Philosophy

Metal-organic frameworks (or coordination polymers) are a recently-identified class of porous polymeric materials, consisting of metal ions or clusters linked together by organic bridging ligands. The major advantage of MOFs over other traditional materials, such as zeolites or activated carbons, is that their synthesis methods have provided an extensive class of crystalline materials with high stability, tunable metrics, and organic functionality. The ability to modify the physical environment of the pores and cavities within MOFs allow tuning of the interactions with guest species, and serves as a route to tailor the chemical stability and/or reactivity of the frameworks for specific applications. The classical way to incorporate functional groups into a MOF is the modification of the organic precursor with specific substituents before synthesizing the MOF itself; we call this approach pre-functionalization method. Functionalization of organic precursors is the initial and necessary step to obtaining functionalized isostructural MOFs and also provides the possibility for the post-synthetic modification of MOFs. However, in some cases, the functional groups may interfere with MOF synthesis and alter the topology of desired MOF. The goal of this proposed research is to explore the possibilities of metal-organic frameworks (MOFs) as novel porous structures, to study the effect of functional groups on the topologies and adsorption behavior of MOFs, and to understand how the synthesis conditions affect the phase purity and the in-situ reaction of ligands.

Thesis (DTech (Chemistry))--Cape Peninsula University of Technology, 2015. / Researchers around the world are now focusing on inculcating green chemistry principles in all level of research especially in nanotechnology to make these processes environmental friendly. Nanoparticles synthesized using green chemistry principles has several advantages such as simplicity, cost effectiveness, compatibility for biomedical and pharmaceutical applications and large scale production for commercial purpose. Based on this background, this thesis present the design, synthesis, characterization and applications of various CdSe based core-shell and core-multi shell quantum dots (QDs), quantum dots-polymer nanocomposites, silver nanoparticles (Ag-NPs) and silver nanocomposites via completely green methods. Various QDs like CdSe/CdS/ZnS and CdSe/ZnS, and there polymer nanocomposites were successfully synthesized and characterized. The high quality of the as-synthesized nanoparticles was confirmed using absorption and photoluminescence (PL) spectroscopy, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM). Detailed optical and morphological characterization showed that the CdSe/CdS/ZnS core-multi shell QDs were small, monodispersed with high fluorescent intensity and narrow emission width. The CdSe/CdS/ZnS core multi-shell QDs were dispersed in epoxy polymer matrix to obtain fluorescent epoxy nanocomposite. The brillouin spectroscopy analysis revealed that the presence of QDs inside polymer composite reduces the acoustic frequency of the polymer. Highly fluorescent CdSe/ZnS core-shell QDs was also synthesized and dispersed in PMMA polymer matrix to prepare bright yellow emitting nanocomposite film. The as-synthesized QDs also undergone surface exchange to convert the organically soluble nanomaterial to water soluble. After the ligand exchange, the morphology and above all the fluorescence property of the quantum dots remained intact. In another approach, HDA-capped CdSe nanoparticles were synthesized in the absence of an inert gas followed by dispersion in polymer polycaprolactone to produce orange light emitting electrospun polymer nanocomposite nanofibre.

Department of Mechanical, Industrial and Aeronautical Engineering MSc (Mechanical Engineering) / Aramid fibre reinforced epoxy composites were hybridised by the addition of electrospun PAN (polyacrylonitrile) and ECNF (electrospun carbon nanofibre) doped PAN nanomats. One of the major concerns in polymer composites is the effect of the interlaminar properties on the overall mechanical properties of the composite. Electrospun carbon nanofibres were used as doping agents within PAN nanofibres, and coated in between aramid epoxy laminates to improve the interlaminar properties. PAN nanomats and ECNF doped PAN nanomats were created by the use electrospinning on the surface of aramid fibre sheets. Multiscale hybrid aramid reinforced composites were then fabricated. Mechanical characterization was carried out to determine the effect of PAN and CNF doped PAN nanofibre mats on aramid fibre reinforced epoxy. It was found that PAN reinforced nanomats had improved the mechanical properties and more specifically, when doped by ECNFs, the volume fraction of ECNFs played a vital role. An addition of 1% vol. CNF doped 0.1% vol. PAN reinforcement within a 30% vol. aramid fibre composite (control composite), improved the tensile strength and elastic modulus by 17.3% and 730% respectively. The 0.5% vol. PAN reinforced AFC (aramid fibre composite) specimens revealed a major increase in the flexural strength by 9.67% and 12.1%, when doped by both 0.5% vol. ECNFs and 1% vol. ECNFs respectively. The 0.5% vol. CNF doped reinforcement increased the impact energy by over 40%, for both the 0.1% vol. and 0.2 % vol. PAN reinforced aramid hybrid specimens. The 0.5% vol. CNF doped 0.5% vol. PAN had increased by 30% when compared to a non-doped sample. Morphological studies indicated interlaminar shearing between plies was affected by CNF agglomerations. This was discovered when determining the impact properties of the multiscale doped hybrid composites. Electrospun nanofibres however, assisted in improving the interlaminar regions within aramid epoxy by mechanical locking within the epoxy, and creating an adhesive bond using Van der Waals forces and electrostatic charges between nanofibre and macro fibre. Hybridising aramid epoxy with the use of nanofibres assisted in improving various mechanical properties. Impact degradation was one disadvantage of hybridising using CNF doped PAN nanofibre reinforcements. / MT2017

Ph.D., Faculty of Science, University of the Witwatersrand, 2011 / ABSTRACT Page | iiAbstract i The deposition of carbon during catalytic reactions has a long history, with major efforts initially focused towards their prevention rather than synthesis. However the discovery of fullerenes and later that of carbon nanotubes by Iijima, shifted scientific focus towards the synthesis, characterization and application of carbon deposits. This renewed interest in carbon based materials, has revealed a universe of extraordinarily shaped carbon materials (SCMs) in the nano and micro range, from tubes and helices to horns and most recently graphene. It has been noted that there exists a relationship between the morphology of the carbon material and its inherent properties, making them highly prized for numerous technological applications. However before these carbon materials can be effectively exploited control over their selective synthesis is necessary, a problem that has been solved with only limited success. As such, there still exists a need to develop synthetic strategies that would yield shaped carbon materials selectively. More importantly, it is essential that a better understanding of the growth factors that lead to differently SCMs is obtained. In this study we have highlighted the parametric conditions for optimum growth of carbon helices, as well as that of carbon fibers with unique structure. We have found that catalyst morphology and the carbon source are key aspects, which control carbon material growth and morphology. The synthesis of carbon materials using bi and tri-metallic supported catalyst systems revealed that Cu was an effective promoter for obtaining helices, particularly at low temperatures (≤ 550 ˚C). On further investigation, Cu was shown to exhibit incredible carbon deposition capabilities at temperatures as low as 200 ˚C. Adjustments of the catalyst preparation conditions (support, metal counter ion, solvent and reduction temperature) and synthesis temperature, revealed that the yield and morphology of the carbon deposit could be altered to selectively produce both straight and helical carbon fibers. A TEM tomography study revealed that the copper particles that gave distorted decahedra formed helical fibers, while trigonal bi-pyramidal particles gave linear fibers. Various plate-like particles revealed that as the number of sides of a catalyst particle varied (3, 4, 5 or 6) there was a corresponding change in the Abstract Page | iv carbon fiber helicity. A relationship between catalyst particle morphology and fiber morphology was thus established. TEM analysis also revealed that catalyst particles underwent rapid reconstruction during carbon fiber synthesis, and that the carbon source (gas environment) was influential in this reconstruction event. A NiOx (unsupported) catalyst was prepared and reactions with various substituted alkyne hydrocarbons were undertaken. Analysis revealed that different alkynes produced carbon fibers with varying morphologies. Using different alkynes in a sequential manner led to the formation of ‘co-block’ carbon fibers with an A-B-A-B... or A-B-C... morphology. Using different alkynes followed by acetylene led to the selective synthesis of straight, Y-junction or irregular carbon fibers. Accompanying these results was the observation that in each case the catalyst particle morphology was unique. Reaction of NiOx with trichloroethylene, in which trichloroethylene acted as a source of carbon for fiber growth, also restructured the Ni catalyst into a tetrahedral shape that gave tripod-like carbon growth. It was found that, substituted alkynes (and alkenes) provided a means for controlling catalyst particle morphology and hence carbon fiber morphology. The study has highlighted the relationship that exists between catalyst and SCM morphology, as well as the effect of hydrocarbons, not only as a source of carbon for SCM growth but also as a means of controlling catalyst morphology and SCM structures.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the Degree of Doctor of Philosophy. Johannesburg, 2015 / Bimetallic 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.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment for the degree of Master of Science in Chemistry, 2017 / The aim of this study was to synthesize helical carbon nanofibers with controlled diameter by using copper nanoparticles contained inside hollow carbon sphere. In this work, different methods have been explored to synthesize copper nanoparticles contained inside mesoporous hollow carbon spheres in order to minimize the sintering effect of the copper nanoparticles. Mesoporous hollow carbon spheres were used not only as a support for the copper nanoparticles but to stabilize and disperse these nanoparticles to prevent the formation of aggregates. Mesoporous hollow carbon spheres were synthesized using a hard templating method, in which mesoporous silica spheres or polystyrene spheres were used as a sacrificial template. Carbon nanofibers with different morphologies, including straight and helical fibers were obtained by a chemical vapor deposition method where acetylene was decomposed over copper nanoparticles contained inside mesoporous hollow carbon spheres catalyst at 350 °C. The synthesized carbon nanofibers were grown on the surface of the mesoporous hollow carbon spheres as the methods used to synthesize the catalyst failed to incorporate copper nanoparticles inside the spheres. Differences in the diameter of the straight and helical carbon nanofibers were observed from both catalysts. This supports the important effect of particle size on influencing the shape of the synthesized carbon nanofibers. / XL2018