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Item Trimetallic nanoparticles immobilised on polymeric membranes for the degradation of organic pollutants in water(2021) Kgatle, Masako; Moloto, Nosipho; Sikhwivhilu, Keneiloe; Ndlovu, GebhuWater is one of the most essential resources in the world, but its scarcity has become an issue of global concern. The scarcity of water is largely the result of climate change, water pollution and increasing population growth which limits the availability of water resources. Moreover, South Africa has been making headlines since 20 IO due to water shortages experienced. It is, therefore crucial to find cost-effective ways to expand the water supply and address the issue of water pollution. This study seeks to tackle the problem of water pollution emanating from textile industries. Over the last few years, nanotechnology and membrane technology have appeared as some of the most widely used methods for the mitigation of water pollution problems. Particularly, nanoscale zerovalent iron (nZVI) has emerged as one of the most broadly used nanoparticles in wastewater treatment and remediation owing to its low-cost and high effectiveness. However, because of its ease of aggregation and consequent loss of reactivity, nZVI is coupled with one or more transition metals to produce multimetallic systems. Nanoparticles alone quickly agglomerate and form large micro-scale particles owing to the magnetic forces thus losing their mobility and chemical reactivity. To avoid these issues, the nanoparticles are stabilized on polymeric membranes. In this study, two trimetallic nanoparticle systems were synthesized, characterized and tested for catalytic activity. The polyvinylpyrrolidone (PVP)-stabilized Fe/Cu/Ag nanoparticles were synthesized by the sodium borohydride chemical reduction method. These nanoparticles were characterized using XRD, XPS, EDX and TEM. The XRD, EDX and XPS techniques showed the presence of all three metals, including iron oxides due to the oxidation of iron in air. The obtained TEM images showed the characteristic core-shell morphology of the nZVI-based nanoparticles. The evaluation of the catalytic activity of the nanoparticles was conducted using methyl orange (MO) dye as the model pollutant and this showed a remarkable degradation efficiency within few minutes. The effect of parameters such as MO solution pH, initial MO dye concentration and nanoparticle dosage in MO degradation was investigated. The nanoparticles were found to have performed better at lower pH, lower initial MO dye concentration and higher nanoparticle dosage. The degradation of MO dye was monitored using UV-Vis analysis and occurred within 1 min. The degradation was found to follow a pseudo first-order kinetic model and was vastly influenced by the studied parameters. The analysis of by-products and reaction pathway were done using LC-MS and this further confirmed that the degradation of MO was indeed rapid. The Fe/Cu/Ag trimetallic nanoparticles were demonstrated as suitable and effectual alternative for the remediation of textile dye wastewater. For the second trimetallic system, three different trimetallic nanoparticles (Fe/(Zn/Ag), Fe/Zn/Ag and Fe/ Ag/Zn) with different metal addition sequences were synthesized. The prepared nanoparticles were characterized using XRD, EDX and TEM analyses. The techniques proved successful synthesis of the nanoparticles and XRD and EDX showed the presence of the three metals together with the oxides. The evaluation of the catalytic reactivity of the nanoparticles was conducted in a series of batch experiments using MO dye as the model pollutant. About 100% of the MO dye was degraded by Fe/ Ag/Zn trimetallic nanoparticles within 1 min and the second-order rate constant obtained was 0.0744 ppm- 1min-\ the rate of reaction was higher than that of the other trimetallic systems. Using Fe/ Ag/Zn trimetallic nanoparticles, parametric tests were conducted at different MO solution pH, initial MO concentration and nanoparticle dosage. The results showed that the reactivity of the Fe/Ag/Zn trimetallic nanoparticles was highly dependent on the aforementioned parameters. Like the Fe/Cu/Ag system, the Fe/Ag/Zn performed better at lower pH, lower initial MO dye concentration and higher nanoparticle dosage. The overall kinetic study showed the removal of MO using Fe/Ag/Zn system to follow a second-order kinetic model. The elucidation of the degradation pathway and MO by-products identification were done using LC-MS and the mechanism of degradation displayed the degradation of methyl orange to proceed via azo-bond cleavage. Moreover, the Fe/ Ag/Zn nanoparticles proved to be effective at degrading methyl orange dye and can be used to treat azo-dye wastewater from textile industries. The Fe/Cu/ Ag trimetallic nanoparticle system was immobilized on a polymethacrylic acid grafted polyethersulfone (PMAA-g-PES) membrane to minimize the issue of recoverability and nanoparticle agglomeration. The nanocomposite membranes were prepared by loading different quantities of Fe/Cu/Ag trimetallic nanoparticles onto the PMAA-g-PES membrane for optimization purposes. Characterization was performed using FTIR, NMR, XPS, SEM/EDS and AFM analyses. The PMAA g-PES and nanocomposite membranes were found to have a porous top layer and a rough surface. Moreover, the addition of nanoparticles did not cause any significant changes in the membrane structure, however, further addition of nano particles led to the blockage of pores. The performance of the synthesized membranes was tested using pure water flux and MO (anionic dye) and methylene blue (MB) (cationic dye) dye removal capacity. The negatively charged membranes were found to have more affinity for MB dye than the MO dye and this was ascribed to the charge interaction between the membrane surface and the dyes. The nanocomposite with 5% Fe/Cu/Ag trimetallic nanoparticle loading on PMAA-g-PES membrane (M4-5% membrane) was found to have the best adsorption capacity with about 60% MB dye removal efficiency. Furthermore, the effect of process parameters such as pH, temperature and H2O2 concentration on the removal of MB was studied. The removal efficiency was found to be higher at higher pH and lower temperature. About 100% removal efficiency was obtained when the process was performed at pH 9 in the presence of H2O2 via adsorption and Fenton degradation. This showed that a hybrid of processes was convenient for the removal of MB dye by adsorption (primarily) and degradation using the nanocomposite membrane. Adsorption equilibrium data were assessed using the Langmuir, Freundlich and Temkin models; the Temkin model was the most convenient to explain the adsorption of MB onto M4-5% membrane. Moreover, lcinetic studies were performed on four kinetic models: pseudo first-order, pseudo second order, intraparticle diffusion and elovich models. The pseudo second-order was found to be the best suitable to explain the adsorption of MB onto M4-5% membrane. Thus, the adsorption of MB onto the nanocomposite membrane is an exothermic chemical process that occurs on a heterogeneous surface. Therefore, the nanocomposite membrane has the prospective to be applied in the removal of cationic textile dyes in the presence of an oxidiser.Item 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 LydiaThe 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.Item Colloidal synthesis and characterization of molybdenum and tungsten-based phosphide electrocatalysts for hydrogen evolution reaction(2022) Nkabinde, Siyabonga Sipho; Moloto , NosiphoThe production of hydrogen gas via hydrogen evolution reaction (HER) in acidic media has become an important area of research in light of the increasing demand for sustainable and environmentally friendly sources of energy. However, its large-scale production is currently being hindered by the lack of inexpensive and highly efficient non-noble electrocatalysts. Transition metal phosphides (TMPs) have transpired as favourable catalysts that can be prepared from cheap and readily available sources. Up to now, TMPs have been commonly prepared using solid-state and solid-gas reactions, which rely on the use of high temperatures and hence generate inhomogeneity in the prepared materials. Inhomogeneous materials are unattractive as catalysts because the correlation between a catalyst and its structural features cannot be systematically studied. For this reason, colloidal synthesis has emerged as a powerful method in the synthesis of TMPs as it allows for control over the resulting physical features (i.e. size, morphology, crystal phase, crystallinity etc.). The ability to tailor these physical properties provides room for improving the catalytic activity. By using the colloidal synthesis method, we have successfully prepared molybdenum and tungsten-based phosphide nanoparticles and studied the effect of their physical features on HER activity. In chapter 3, we report a facile colloidal synthesis method to produce an amorphous phase of molybdenum phosphide (MoP) by using trioctylphosphine (TOP) as a phosphorus source, molybdenum pentachloride (MoCl5) as a metal source and 1-octadecene (1-ODE) as a solvent/reducing agent. The use of the forementioned precursors promoted the formation of very small, shape controlled and well dispersed amorphous molybdenum phosphide (MoP) nanoparticles. Annealing (800 °C) of the amorphous MoP nanoparticles resulted in the formation of a crystalline MoP phase with a slightly bigger size but retained its dispersity and morphology upon exposure to high temperature. The amorphous and crystalline MoP phases were compared as HER electrocatalysts. HER results indicated that the amorphous MoP phase exhibited enhanced catalytic activity in hydrogen evolution reaction compared to the crystalline MoP phase. The high activity displayed by the amorphous MoP was attributed to the small sizes and the high density of unsaturated active sites characteristic of nanoparticles lacking long range crystalline order.