Graphene@microalgae-based nanohybrid structures as adsorbents for removal of Cr(VI) ions in aqueous solutions
- Authors: Mulovhedzi, Rolivhuwa
- Date: 2024-12
- Subjects: Nanoscience , Nanotechnology , Nonaqueous solvents
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69404 , vital:77252
- Description: iv ABSTRACT The efficient removal of heavy metals using carbon-based nanoadsorbents poses a substantial challenge in the domain of water purification. Graphene-based materials have been extensively utilised in the treatment of water and wastewater due to their tremendous surface areas, porosity, turntable nature to different functional groups, and photo-catalytic properties. In this project, graphene oxide (GO) was synthesised via the modified Hummers method. A similar method was used to produce nitrogen-doped graphene oxide (NGO), with urea as the nitrogen precursor. Utilising biomass materials to dope graphene-based nanocomposites can effectively enhance their application in water treatment. In this work, graphene oxide-microalgae (GO@Algae) and N-doped graphene oxide-microalgae (NGO@Algae) nanocomposites were synthesised by combining GO or NGO with green Scenedesmus microalgae. This was done through a solution self-assembly mixing method using ultrasonication. The resulting nanocomposites were used to remove Cr(VI) from water solutions. The influence of microalgae content deposited on GO and NGO nanosheets at different weight ratios (1:1, 3:1, and 1:3) on the chemical, structural, morphological, and thermal characteristics of nanoadsorbents was evaluated using various techniques such as Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The flat nanosheet-like morphology of GO@Algae and NGO@Algae nanostructured materials was observed through SEM, confirming microalgae's incorporation within the GO and NGO matrices. The thermal stability and surface area properties of GO and NGO nanocomposite materials decreased with the incorporation of microalgae content. The incorporation of microalgae into GO nanosheets showed enhancements in chemical and structural properties due to the presence of the strong covalent interaction (oxygen and nitrogen-containing groups) between the interfaces of nanocomposites. XPS and FT-IR analyses revealed the existence of amides, carboxylic acids, and phosphates, which exhibited positive charges below the pH 2.03 point-of-zero charge. The second phase of the study involved assessing the adsorption capabilities of the GO, NGO nanosheets, and GO@Algae and NGO@Algae nanocomposites in removing Cr(VI)from the water solution. Adsorption parameters such as the effect of solution pH, contact time, adsorbent dosage and metal ion concentrations were evaluated for Cr(VI) removal. When comparing GO, NGO, GO@Algae, and NGO@Algae, it was found that GO@Algae and NGO@Algae exhibited superior adsorption performance due to the available functional groups and well-developed pores. Additionally, a mixed ratio of GO or NGO and algae at a ratio of 1:3 was found to be the most suitable for GO@Algae and NGO@Algae. The adsorption efficiency of nanostructured materials for Cr(VI) is significantly influenced by their surface charge, porosity and specific surface area. The results revealed that the adsorption capabilities of GO@Algae (1:3) and NGO@Algae (1:3) were 2.24 and 2.01 times higher than GO and NGO which were 1.64 and 1.89, respectively, at a solution of pH 2 where HCrO4− species are predominant compared to a solution of pH 5 which predominate a mix of Cr2O72− and CrO42- species. The enhanced performance of the GO@Algae and NGO@Algae nanocomposites is attributed due to their increased surface functionalities and porosity. The adsorption of Cr(VI) ions by the GO/NGO@Algae nanocomposites declined with increasing initial concentration of Cr(VI) species in the water medium. The adsorption kinetics data for GO, NGO, GO@Algae (1:3), and NGO@Algae (1:3) exhibited a good fit with the pseudo-second-order model (R2 > 0.995) suggesting that chemisorption governed the adsorption process. Similarly, the isotherm adsorption findings showed a good fit with the Freundlich model (R2 > 0.961). The findings indicated that the adsorption mechanism process was characterised by monolayer adsorption onto a heterogeneous adsorbent surface. Furthermore, the GO@Algae (1:3) was found to have the maximum adsorption capacity of 10.85 mg/g surpassing the capacities of both unmodified and NGO@Algae counterparts. The application of GO@Algae and NGO@Algae has the potential to promote the green reuse of graphene-based nanomaterials. In summary, GO@Algae and NGO@Algae show great potential as eco-friendly adsorbents for the feasible treatment of heavy metal-contaminated water. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
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- Date Issued: 2024-12
Development of TiO2 nanostructures with a modified energy band gap for hydrogen extraction
- Authors: Mutubuki, Arnold
- Date: 2024-04
- Subjects: Nanostructures , Nanoscience , Nanochemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64226 , vital:73666
- Description: A rise in fossil fuel depletion has motivated the research towards alternative, cost effective and clean processes for energy production through renewable sources. The scientific community is currently engaged in extensive research to exploit viable, sustainable methods for generating green hydrogen. Titania (TiO2) is historically the most studied photoactive semiconductor material with great potential in photoelectrochemical water splitting (PECWS), following the discovery by Fujishima and Honda in 1972. TiO2 possesses superior physicochemical characteristics and band gap edges, which enables the semiconductor to effectively facilitate the PECWS process. Efforts are still ongoing to explore alternatives for narrowing the optical band gap energy of TiO2, for an efficient photoelectrode. In this research work, open-ended and well-ordered TiO2 nanotubular arrays were synthesised by a three-step anodization process. The third anodization was crucial to detach the TiO2 thin film from an opaque Ti metal substrate. The free-standing thin films were transferred and pasted onto conductive FTO-coated glass substrates transparent to visible light and annealed at 400 ℃ for crystallisation. The multi-step anodization has shown an improved top tube morphology by eliminating an initiation TiO2 mesh formed when a conventional single-step anodization process is used under similar conditions. To widen the absorption range of the samples, CuO nanosheets were deposited onto nanotubular TiO2/FTO films through successive ionic layer adsorption (SILAR), a wet chemical method. The formation of a CuO/TiO2 nanostructure enhances the transfer of photogenerated carriers, suppressing charge recombination. This research focused on investigating the influence of selected SILAR parameters on the formation of CuO nanostructures. The first was the effect of precursor concentration on the structural, morphological and optical properties of the CuO/TiO2/FTO nanostructured photoelectrode. The effect of the precursor concentration on the structure and morphology was evident in the X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) micrographs. Crystallite sizes of deposited CuO increased from 10.6 nm to 15.7 nm when precursor concentration was varied from 0.02 M to 0.10 M. The UV-visible absorbance results show that an increase in precursor concentration leads to a red shift of both the peak absorbance and edge wavelength of the CuO/TiO2/FTO absorbance spectra. This phenomenon is believed to be caused by the presence of CuO, which exhibits active absorption in the visible spectrum. As evidenced by the study, the continued increase in precursor concentration does not result in a further widening of the absorption band. This is demonstrated by the example of a CuO/TiO2/FTO sample decorated with a 0.2 M precursor. The second was the effect of SILAR immersion cycles on the properties of the CuO/TiO2/FTO nanostructure developed. The increase in the number of immersion cycles led to a notable progression in the adsorption cupric oxide on the TiO2/FTO samples. A redshift in the absorbance peak and edge wavelength is observed in the UV-visible spectra of CuO/TiO2/FTO photoelectrode. The efficacy of the SILAR technique in modifying the absorption band of nanotubular TiO2 thin films has been conclusively demonstrated through comprehensive analysis and correlation of the relationships between the structure and optical properties, as evidenced by the XRD patterns, Raman spectra, SEM, TEM micrographs, and UV-visible absorbance spectra. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
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- Date Issued: 2024-04
Of science and small things: recollections of the past twenty(-)odd years
- Authors: Botha, J. R
- Subjects: Nanoscience , Nanotechnology , f-sa
- Language: English
- Type: text , Lectures
- Identifier: http://hdl.handle.net/10948/20867 , vital:29409
- Description: I will start, therefore, with an overview of achievements in a “new” field of endeavour, a science of small things, popularly called nanoscience, and its spin-off called nanotechnology. I will present a brief history, look at the approaches that have been followed by scientists and engineers to develop and understand small things, and summarise some of the benefits to society in terms of new materials and processes, energy storage and generation, electronics, environmental applications, medicine and transportation. Since our own research focuses on the development on semiconductors, I will conclude the scientific part of the presentation by considering the contribution of semiconductors to the development of nanotechnology and highlight a few examples from our own research during the past two decades on the development of nano-scale semiconductor structures, like nanorods, quantum wells and superlattices.
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