Development of Tio 2 nanostructure arrays for photonic extraction of hydrogen gas
- Authors: Suliali, Nyasha Joseph
- Date: 2020
- Subjects: Nanostructures , Nanostructured materials Hydrogen
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49314 , vital:41620
- Description: Amid the energy crisis of the 21st century, renewable energy is a thriving field of study, light harvesting materials being a central theme due to the abundance of solar energy. Nanostructured TiO2 is the most studied photocatalysis material, since the discovery of its energy harvesting properties by Fujishima and Honda in 1972. Environmentally friendly products such as hydrogen fuel, can be produced using TiO2 due to its non-toxicity, chemical stability and photocatalytic activity. The surprising aspect of this important material is that it can be prepared using cost-effective methods such as hydrothermal synthesis, solution gelation and anodic oxidation. This research focused on the three key elements required to develop TiO2 photoelectrodes i.e. the deposition of Ti films on transparent substrates, a thorough analysis of the chemistry of the anodic oxidation process and the development of the TiO2 thin films. Glass substrates that have Ti films are the base component for TiO2 photoelectrode production. Ti films with thicknesses up to 4 μm, were developed on commercial F-doped SnO2 (FTO) glass substrates using high-power impulse magnetron sputtering (HiPIMS). The sputter deposition experiments were performed in the 1 to 8 kW range at a substrate temperature of 500 °C and Ar pressure of 400 mPa. At higher powers, thicker films were deposited, resulting in increased intensity of Xray-diffraction peaks. However, on comparing the XRD patterns, the (001) peak outgrew the rest regardless of thickness of the film. The deposition process therefore favoured orientation of most of the α-Ti phase crystallites with the [001] axis perpendicular to the substrate surface. Surface roughness results were interesting, showing a non-linear dependence of the surface roughness on HiPIMS pulse energy in the 1 to 8 kW range. The surface roughness is highest at the starting deposition power of 1450 W and reduces to a minimum at 4500 W. From this minimum, it increases to its second highest value at 7900 W. From this data, the parameters required to produce Ti films of lowest surface roughness, for deposition on commercial Technistro® FTO glass, were deduced at the inflection point, where the deposition power was 4500 W. The surface roughness obtained is a critical result for the anodic production of quality TiO2 photoelectrodes, which if high, leads to uneven etching, thus irregular and inefficient photoelectrodes. Direct current magnetron sputtering was also carried out in the 1 to 5 kW range to obtain ratios of power-normalised growth rates of the Ti films. This investigation provided the Ti films on FTO glass, the transparent, conductive substrates which were used to develop TiO2 photoelectrodes. To elucidate the chemistry of anodic oxidation of Ti, a mathematical model of the anodic current density, which had not been reported at the time of its publication, was developed. The technique, a highlight of this research, is a predictive numerical computation of the instantaneous quantities of species that participate in the anodization process. From eleven chemical reactions, 14 first order ordinary differential equations were compiled using the principles of chemical reaction kinetics. The pattern, transient behaviour and response to anodization parameters of the current density signal, were successfully predicted. Strong agreement between the model and measurements was demonstrated in seven experiments. The results confirm that the current density signal is a numerical integral of the kinetics of redox reactions of water. The bulk of this research was on the development of TiO2 nanotubular arrays on Ti foil substrates and Ti films on FTO glass. TiO2 films with well-defined tubular structures were synthesised. The films were developed in anhydrous, polar organic hosts with water and etching agents in the range of 10 V to 70 V. The control of geometrical properties of the tubes such as the length, pore diameter, wall thickness, tube separation and number of nanotubes per unit area was demonstrated. Anatase only and mixed anatase-rutile phase compositions were obtained at different annealing temperatures. Nanotubes with diameters as small as 20 nm and thickness as high as 29 μm were produced. Apart from an increase in nanotube thickness, a decrease in distance between nanotubes grown in diethylene glycol was observed at longer anodization times. Studies of the effects of anodization parameters on the current density measured, morphological and crystallographic properties of the nanotube films were conducted in three main investigations. The first was the study of the effect of anodization parameters on current density. Besides the obvious increase of current density with anodic voltage, the first steady state of the growth process was found to depend on the NH4F concentration. The second investigation focused on the effect of accelerated growth of TiO2 nanotubular films. In the study, 9 μm-thick nanotube films were synthesised at twice the growth rate of a 9 μm-thick control sample. The array obtained by accelerated growth had distinguishable nanotubes, however, the morphological quality was reduced. The third investigation demonstrates the control of the number of nanotubes per unit area. By varying the etchant content, the anodic voltage and the viscosity of the electrolyte host, various distributions were obtained. The research ends with a photoelectrochemical application: measurement on photocurrents generated in a two-electrode setup. The photocurrent densities measured in the off and on conditions were 30 nA/cm2 and 2.57 μA/cm2, respectively, demonstrating photoactivity of the developed films.
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- Date Issued: 2020
Photocatalytic reduction of CO2 by cobalt doped TiO2 and ZnO micro/nanostructured materials
- Authors: Mgolombane, Mvano
- Date: 2020
- Subjects: Nanostructures , Catalysis , Nanotechnology , Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49171 , vital:41607
- Description: Large emissions of carbon dioxide (CO2) in the atmosphere have caused many harmful effects on humans and the environment. Carbon dioxide is a good source C and is used in a number of applications such as synthesis of fossil fuels. Redox reaction of CO2 and H2O with photocatalysts such as TiO2 and ZnO to produce solar fuels is a promising approach in reducing the environmental impacts of greenhouse gasses. This dissertation describes an in-depth synthesis of four photochemical catalysts and their photocatalytic conversion of CO2 to methanol, thereby addressing the above-mentioned problems by applying synthesised nano-based catalysts. Prior to photocatalytic reduction studies, catalysts such as TiO2, Co-doped TiO2, Co-doped TiO2/rGO, ZnO, Co-doped ZnO and Co-doped ZnO/rGO were synthesized and characterized using various spectroscopic and imaging techniques such as Powder X-Ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Transmission Electron Micrograph (TEM), X-ray Photoelectron Spectroscopy (XPS), Brunner- Emmet- Teller measurement (BET), Thermogravimetry Analysis (TGA) and UV-Vis Diffuse Reflectance Spectroscopy (UV-Vis-DRS). The conversion yield of CO2 to methanol on TiO2, Co-doped TiO2 and Co-doped TiO2/rGO reached 32.3 μmol/gcat, 730 μmol/gcat and 936 μmol/gcat, respectively, after 7 h of irradiation. Theoretical studies via Density functional theory (DFT) revealed that doping TiO2 with Co ions facilitated the formation of adsorbed carbonate or CO2•- species, as CO2 adsorbs onto Co-doped TiO2 surface with binding energy (BE) of -18.12 KJ/mol. The photocatalytic activities of ZnO-based nanomaterials found that Co-doped ZnO/rGO with high ratio of Co, reduced graphene (rGO) and large surface area (10.62 m2g-1) possessed higher CH3OH (30.1 μmol/g) in comparison with Co-doped ZnO (27.3 μmol/g) and ZnO (7.5 μmol/g). The research will deepen the understanding that TiO2 based photocatalyst show higher activity and the mole ratio (Ti/Zn:Co) influences nanocomposites performance and provide new ideas for designing efficient photocatalysts.
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- Date Issued: 2020