Electronic Theses and Dissertations (PhDs)

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Browsing Electronic Theses and Dissertations (PhDs) by SDG "SDG-17: Partnerships for the goals"

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    A study of the support effect of carbon dots-derived graphene-like sheets on the autoreduction of cobalt nanoparticles for Fischer–Tropsch synthesis
    (2022) Mokoloko, Lerato Lydia
    The aim of this study was to synthesize and characterize carbon dots (CDs) and to use them as a support material for cobalt (Co) based Fischer-Tropsch synthesis (FTS) reactions. The CDs were chosen for this study due to their small size (< 10 nm), easy surface functionalization and synthesis. The small size of the CDs was required for the study of inverse catalyst support effects. An inverse supported catalyst (in this case, the Co/CDs catalyst) refers to the dispersion of a support material that has a small size (d < 5 nm) onto the surface of a metal catalyst with a similar small size (d > 8 nm). The synthesis of this proposed catalyst was successful. FTS studies on the Co ‘supported’ CDs were attempted. Extremely poor FT activity was observed. Post analysis of the catalyst revealed that the CDs did not retain their quasi-spherical and small particle size morphology under the FTS reaction conditions (temperature 220 °C, 10 bar P; H2:CO ratio = 2:1). Instead, upon exposure to a heat treatment, the CDs were transformed into layered structures with a unique resemblance to graphene-based nanosheets (GNSs). This transformation impacted on the use of these catalysts in the FTS reaction. However, this result indicated an unusual transformation of the CDs into another carbon shape. In light of the fascinating transformation phenomenon, annealing studies were then conducted to investigate the effect of annealing temperatures on the CDs structural changes. The CDs (average d= ~ 2.5 nm) used in this study were obtained from the microwave-assisted carbonization of L-ascorbic acid and subjected to a heat treatment (i.e. annealing) at temperatures between 200 and 700 ℃ in a horizontal CVD apparatus under an inert nitrogen gas. It was observed that annealing transformed the CDs from 0-D qausi-spherical nanoparticles to 3- D multi-layered carbons (at 300-600 ℃) and finally 2-D layered materials (at 700 ℃). Furthermore, annealing at 700 ℃ yielded a 2-D single-layered material with comparable properties to traditionally reduced graphene oxide (rGO). A wide range of characterization techniques were used to gain an insight into the physicochemical properties of these novel CDs-derived allotropes as well as to rationalize their mechanism of formation. After evaluating the properties of these materials, it was clear that the surface oxygen functional groups, observed from XPS, 13C NMR and other studies, were responsible for the CDs to rGO transformation. It was proposed that the CDs are assembled to form rGO (and other CDs-rGO derivatives) by either the Ostwald ripening (in which the carbons agglomerated via a gas phase) or a solid phase reaction (involving reaction of CD edges). To further investigate the effect of annealing on the evolution of CDs to layered carbon structures, N-doped CDs (or NCDs) were also studied. The method used to make the pristine CDs was modified by incorporating urea as a nitrogen source to make the NCDs. Annealing the NCDs at temperatures between 200 and 700 ℃ also transformed the quasi-spherical NCDs (average d = ~ 4.1 nm) to multi-layered carbon sheets at temperature as low as 200 ℃. The CD transformation was also associated with the loss of surface functional groups, with % O and N contents of ca. 17 and 16 % (pristine NCDs) being reduced to ca. 8 and 7 % for NCDs annealed at 700 ℃. A similar mechanism for the formation of these N-doped layered carbon structures by annealing was also proposed here. For these samples, it was also observed that the N-bonds, especially the sp3 type nitrogen bonds found on the edges of the NCDs, also took part in the coalescence of the NCDs to give the layered materials. XPS data suggested that in the process, these sp3 type nitrogen bonds were transformed into sp2 pyrrolic-N, pyridinic-N and GraphiticN groups. The annealed CDs products were used to support Co (called Co3O4/T250, Co3O4/T400 and Co3O4/T700 where T is the temperature at which the CDs were annealed) for use in FT studies. Studies were conducted to evaluate the effect Co hydrogen reduction temperatures verses autoreduction temperature, catalyst thermal stability and performance in the FTS reaction at 220 °C (10 bar P; H2:CO ratio = 2:1). Upon investigation of the reduction behaviour of the Co/CDs derivative catalysts using in situ PXRD, it was found that these materials can successfully facilitate autoreduction of Co3O4 to Co face-centered-cubic (fcc) at temperatures > 400 ℃ by a reduction pathway similar to that observed using conventional H2 reduction conditions. As expected, the reduction under H2 took place at a lower activation temperature (> 250 ℃) than the autoreduction process. It was also noted that these novel carbon support derived from CDs gave reduced FTS performance compared to the unsupported Co, especially towards C5+ yields (< 30 % for all Co supported catalysts). These novel CDs-derived allotropes were found to have limited use as supports in Co-based FTS, due to Co agglomeration. These NCDs-derived allotropes (annealed at 200 ℃, 400 ℃ and 700 ℃) were incorporated as active layers in the fabrication of chemoresistive sensing device detection of volatile organic compounds (VOCs). These layered showed enhanced chemical vapour sensing properties, especially for methanol and ethanol detection at room temperature. Therefore, although there are great limitations for applications of these CDs-derived layered allotropes in FTS reaction, these materials show a much better potential for applications in facile and cost effective VOC sensors. Further studies on this will be conducted.
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    Fast oxide ion conductors for solid oxide fuel cells: average and local structure – property correlations in solid solutions of bi2o3
    (University of the Witwatersrand, Johannesburg, 2023) Masina,Sikhumbuzo Mfanawemphi; Billing, David Gordon
    In this thesis, substituted Bi2O3 systems were fabricated and characterized. W, Dy, Erand Nb were used as substituents in a goal to stabilise the highly conductive δ-Bi2O3like phases (hence forth referred to as the δ-phases) to ambient temperatures. Changes in both the average and local structures of the substituted Bi2O3 systems were correlated with the physical property conductivity. In the first part of the thesis, powder X-ray diffraction and Raman spectroscopy were used to show that WO3 on its own did not stabilise the δ-phase at ambient temperatures. The true equilibrium phase in the Bi2O3- WO3 system was a mixture of two tetragonal phases 7Bi2O3·2WO3 and 7Bi2O3·WO3. The co-doping strategy was used to fabricate the Bi2O3-Dy2O3-WO3 system (DWSB, where D =Dy, SB = stabilised Bi2O3). The δ-phase was stabilised with a minimum of 15 mol% total substituent concentration. Powder X-ray diffraction indicated that the δ- phases obtained in this system were metastable and degraded after isothermal annealing at ~ 500 °C for 100 hours. Addition of Er to the DWSB system to create the novel system Bi2O3-Dy2O3-Er2O3-WO3 (DEWSB, where E=Er) was found to significantly improve the stability of the δ-phase when annealed at virtually identical conditions as DWSB. The rest of the thesis is focused on the effect of each substituent cation on phase stability, local structure and the ageing phenomenon–the decrease in ionic conductivity upon isothermal annealing without any observable changes in average structure under powder X-ray diffraction. X-ray pair distribution function, X-ray absorption spectroscopy and photoluminescence were used to probe the local structure around the host Bi cations and some of the substituent cations (Dy, Er, W). The results indicated that some of the Bi cations are displaced away from the 4a site of the defect fluorite structure (Fm-3m) and that at the local level, the Bi cations assume an arrangement similar to that found in the monoclinic α-Bi2O3 phase. Dy and Er were also found to prefer local environments similar to those in their parent oxides. The resemblance increased as the material aged and might explain why the conductivity decreases upon ageing