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
- Full Text:
- Date Issued: 2024-04
- 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
- Full Text:
- Date Issued: 2024-04
Lipid nanocarriers : a novel approach to delivering ophthalmic clarithromycin
- Authors: Makoni, Pedzisai Anotida
- Date: 2021
- Subjects: Clarithromycin , Nanomedicine , Nanostructures , Antibiotics , Eye -- Diseases -- Treatment , Ocular pharmacology , Ophthalmic drugs , Karatitis -- Chemotherapy
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/171678 , vital:42109 , 10.21504/10962/171678
- Description: The feasibility of incorporating clarithromycin (CLA) into innovative solid lipid nanoparticles (SLN) and nanostructured lipi d carriers (NLC) using hot emulsification ultrasonication (HEUS) was investigated. This approach was investigated in an attempt to address the shortcomings associated with the use of lyophilized parenteral formulations administered via the ocular route suc h as toxic reactions, intolerance and patient discomfort due to frequent insti llation of topical solutions of CLA. In particular, sustained release approaches to delivery may enhance precorneal retention, increase ocular availability and permit dose reduction or use of a longer dosing frequency when treating ocular non - tuberculous m ycobacterial (NTM) keratitis infections. This approach may potentially improve the delivery of CLA to the eye, thereby addressing some or all of the unmet clinical needs described vide infra . Prior to initiating pre - formulation, formulation development a nd optimization studies of CLA - loaded SLN and/or NLC, Design of Experiments (DoE), specifically a Central Composite Design (CCD) was used in conjunction with Response Surface Methodology (RSM) to develop and optimize a suitable method for the quantitative determination of CLA in pharmaceutical formulations and for monitoring CLA release from SLN and/or NLC in vitro . A simple, accurate, precise, sensitive and stability - indicating reversed phase - high performance liquid chromatography (RP - HPLC) method with ele ctrochemical (EC) detection was developed, validated and optimized for the in vitro analysis of CLA loaded SLN and/or NLC formulations. Pre - formulation studies were undertaken to investigate the thermal stability of CLA and bulk lipids to facilitate the s election of lipid excipients for the manufacture of nanocarriers in addition to establishing compatibility of CLA with the excipients. It was established that CLA was thermostable up to a temperature of approximately 300 °C thereby indicating that HEUS cou ld be used for the manufacture of CLA - loaded SLN and/or NLC. Lipid screening revealed that CLA i s, in general, poorly soluble in solid and liquid lipids however a combination of stearic acid (SA) and Transcutol ® HP (THP) exhibited the best dissolution pote ntial for CLA of all lipids tested . Stearic acid appears to exist as polymorphic form B prior to exposure to heat however occurs as the form C polymorph following heating at 85 °C for one hour. The best ratio for the mixture of SA and THP for the manufactu re of CLA - NLC ii was an 80:20 ( w/w ) ratio of SA: THP as the two lipids are miscible in this ratio and exhibited the greatest dissolution potential for CLA. Furthermore, an investigation of binary mixtures of CLA/SA and SA/Transcutol ® HP, in addition to eutect ic mixtures of CLA, SA and Transcutol ® HP, revealed no obvious interaction between CLA and the lipids selected for the production of the nanocarriers. Due to the relatively high solubility of CLA in THP in comparison to SA, NLC are likely to exhibit a hig her loading capacity (LC) and encapsulation efficiency (EE) for CLA than SLN. Consequently the feasibility of incorporating CLA (10% w/w ) into NLC was investigated and evaluation of the production of SLN was not undertaken as the production of these might not result in the manufacture of a delivery technology with a high EE and LC for CLA. Tween ® 20 was used as the surfactant as it is readily available, exhibits little or no cytotoxicity and is relatively cheap. Polyethylene glycol (PEG) was used as a coati ng polymer to impart muco - adhesive properties the formulated CLA - NLC. Response surface methodology (RSM) in conjunction with DoE, specifically a Box - Behnken Design (BBD) used as a screening design was used to identify a formulation composition which would produce a product that would meet the pre - defined target critical quality attributes (CQA) for the nanoparticles viz. particle size (PS) in the nano - range, polydispersity index (PDI) < 0.5, Zeta Potential (ZP) ≥ ± 30 mV, and EE > 80%. The formulation composition identified was subsequently used for the optimization of the manufacturing parameters viz. sonication time and amplitude, using a Central Composite Design (CCD) . The LC and EE, in vitro CLA release, cytotoxicity, osmolarity, pH, degree of crystallinity and lipid modification, elemental analysis and surface morphology of the optimized batch was investigated and mon itored to ensure that CLA - loaded NLC, of the desirable quality, had been produced. On the day of manufacture the mean PS and PDI of the optimized CLA - loaded NLC formulation adjusted to physiological osmolarity (250 – 450 mOsm/kg) was 461.9 ± 40.16 nm and 0. 523 ± 0.104, respectively. The ZP for the optimized NLC generated on the day of manufacture using HPLC grade water as the dispersion medium was - 20.5 ± 4.82 mV. The pH and osmolarity of the optimized CLA - loaded NLC formulation was 7.76 ± 0.01 and 316 ± iii 2 m Osm/Kg, respectively and the EE was 88.62 ± 0.23 %. The optimized NLC exhibited a decreased crystallinity in comparison to the bulk lipid materials. DSC, WAXS and FT - IR revealed that CLA was molecularly dispersed in the nanocarriers. The optimized CLA - load ed NLC exhibited muco - adhesive properties, when tested under stationary conditions using laser doppler anemometry (LDA). The optimized formulation also exhibited sustained release of CLA over 24 hours during in vitro release testing and CLA release was bes t described using the Baker - Lonsdale model . The cumulative % CLA released over 24 hours was 56.13 ± 0.23% and mass balance analysis revealed 41.38 ± 0.02% CLA had been retained in the NLC. In vitro cytotoxicity testing revealed that the optimized CLA - NLC w ere less cytotoxic to HeLa cells when compared to CLA alone and further confirmed that the lipids and excipients used in these studies were of GRAS status . Stability studies revealed that the EE reduced over 28 days by 14.42% and 5.14% when stored at 4 °C and 22 °C , respectively. In addition, the particle size increased from the nm to μm range for samples stored at 22 °C. The findings are a good starting point but require further optimization to ensure prolongation of stability. In addition , the technology requires additional developmental studies and a powder for reconstitution for use as a single - dose considered as single dose packaging may be a solution to the compromised formulation stability observed in these studies. The CLA - NLC produced in these stu dies exhibit sound product attributes which serve as a useful foundation for the novel delivery of antibiotics to the eye. The results suggest that the optimized NLC have the potential to enhance precorneal retention and increase ocular availability of CLA , which in turn may be useful to reduce the required dose and dosing frequency when administering CLA as a reconstituted solution to treat susceptible organisms that infect ocular tissues.
- Full Text:
- Date Issued: 2021
- Authors: Makoni, Pedzisai Anotida
- Date: 2021
- Subjects: Clarithromycin , Nanomedicine , Nanostructures , Antibiotics , Eye -- Diseases -- Treatment , Ocular pharmacology , Ophthalmic drugs , Karatitis -- Chemotherapy
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/171678 , vital:42109 , 10.21504/10962/171678
- Description: The feasibility of incorporating clarithromycin (CLA) into innovative solid lipid nanoparticles (SLN) and nanostructured lipi d carriers (NLC) using hot emulsification ultrasonication (HEUS) was investigated. This approach was investigated in an attempt to address the shortcomings associated with the use of lyophilized parenteral formulations administered via the ocular route suc h as toxic reactions, intolerance and patient discomfort due to frequent insti llation of topical solutions of CLA. In particular, sustained release approaches to delivery may enhance precorneal retention, increase ocular availability and permit dose reduction or use of a longer dosing frequency when treating ocular non - tuberculous m ycobacterial (NTM) keratitis infections. This approach may potentially improve the delivery of CLA to the eye, thereby addressing some or all of the unmet clinical needs described vide infra . Prior to initiating pre - formulation, formulation development a nd optimization studies of CLA - loaded SLN and/or NLC, Design of Experiments (DoE), specifically a Central Composite Design (CCD) was used in conjunction with Response Surface Methodology (RSM) to develop and optimize a suitable method for the quantitative determination of CLA in pharmaceutical formulations and for monitoring CLA release from SLN and/or NLC in vitro . A simple, accurate, precise, sensitive and stability - indicating reversed phase - high performance liquid chromatography (RP - HPLC) method with ele ctrochemical (EC) detection was developed, validated and optimized for the in vitro analysis of CLA loaded SLN and/or NLC formulations. Pre - formulation studies were undertaken to investigate the thermal stability of CLA and bulk lipids to facilitate the s election of lipid excipients for the manufacture of nanocarriers in addition to establishing compatibility of CLA with the excipients. It was established that CLA was thermostable up to a temperature of approximately 300 °C thereby indicating that HEUS cou ld be used for the manufacture of CLA - loaded SLN and/or NLC. Lipid screening revealed that CLA i s, in general, poorly soluble in solid and liquid lipids however a combination of stearic acid (SA) and Transcutol ® HP (THP) exhibited the best dissolution pote ntial for CLA of all lipids tested . Stearic acid appears to exist as polymorphic form B prior to exposure to heat however occurs as the form C polymorph following heating at 85 °C for one hour. The best ratio for the mixture of SA and THP for the manufactu re of CLA - NLC ii was an 80:20 ( w/w ) ratio of SA: THP as the two lipids are miscible in this ratio and exhibited the greatest dissolution potential for CLA. Furthermore, an investigation of binary mixtures of CLA/SA and SA/Transcutol ® HP, in addition to eutect ic mixtures of CLA, SA and Transcutol ® HP, revealed no obvious interaction between CLA and the lipids selected for the production of the nanocarriers. Due to the relatively high solubility of CLA in THP in comparison to SA, NLC are likely to exhibit a hig her loading capacity (LC) and encapsulation efficiency (EE) for CLA than SLN. Consequently the feasibility of incorporating CLA (10% w/w ) into NLC was investigated and evaluation of the production of SLN was not undertaken as the production of these might not result in the manufacture of a delivery technology with a high EE and LC for CLA. Tween ® 20 was used as the surfactant as it is readily available, exhibits little or no cytotoxicity and is relatively cheap. Polyethylene glycol (PEG) was used as a coati ng polymer to impart muco - adhesive properties the formulated CLA - NLC. Response surface methodology (RSM) in conjunction with DoE, specifically a Box - Behnken Design (BBD) used as a screening design was used to identify a formulation composition which would produce a product that would meet the pre - defined target critical quality attributes (CQA) for the nanoparticles viz. particle size (PS) in the nano - range, polydispersity index (PDI) < 0.5, Zeta Potential (ZP) ≥ ± 30 mV, and EE > 80%. The formulation composition identified was subsequently used for the optimization of the manufacturing parameters viz. sonication time and amplitude, using a Central Composite Design (CCD) . The LC and EE, in vitro CLA release, cytotoxicity, osmolarity, pH, degree of crystallinity and lipid modification, elemental analysis and surface morphology of the optimized batch was investigated and mon itored to ensure that CLA - loaded NLC, of the desirable quality, had been produced. On the day of manufacture the mean PS and PDI of the optimized CLA - loaded NLC formulation adjusted to physiological osmolarity (250 – 450 mOsm/kg) was 461.9 ± 40.16 nm and 0. 523 ± 0.104, respectively. The ZP for the optimized NLC generated on the day of manufacture using HPLC grade water as the dispersion medium was - 20.5 ± 4.82 mV. The pH and osmolarity of the optimized CLA - loaded NLC formulation was 7.76 ± 0.01 and 316 ± iii 2 m Osm/Kg, respectively and the EE was 88.62 ± 0.23 %. The optimized NLC exhibited a decreased crystallinity in comparison to the bulk lipid materials. DSC, WAXS and FT - IR revealed that CLA was molecularly dispersed in the nanocarriers. The optimized CLA - load ed NLC exhibited muco - adhesive properties, when tested under stationary conditions using laser doppler anemometry (LDA). The optimized formulation also exhibited sustained release of CLA over 24 hours during in vitro release testing and CLA release was bes t described using the Baker - Lonsdale model . The cumulative % CLA released over 24 hours was 56.13 ± 0.23% and mass balance analysis revealed 41.38 ± 0.02% CLA had been retained in the NLC. In vitro cytotoxicity testing revealed that the optimized CLA - NLC w ere less cytotoxic to HeLa cells when compared to CLA alone and further confirmed that the lipids and excipients used in these studies were of GRAS status . Stability studies revealed that the EE reduced over 28 days by 14.42% and 5.14% when stored at 4 °C and 22 °C , respectively. In addition, the particle size increased from the nm to μm range for samples stored at 22 °C. The findings are a good starting point but require further optimization to ensure prolongation of stability. In addition , the technology requires additional developmental studies and a powder for reconstitution for use as a single - dose considered as single dose packaging may be a solution to the compromised formulation stability observed in these studies. The CLA - NLC produced in these stu dies exhibit sound product attributes which serve as a useful foundation for the novel delivery of antibiotics to the eye. The results suggest that the optimized NLC have the potential to enhance precorneal retention and increase ocular availability of CLA , which in turn may be useful to reduce the required dose and dosing frequency when administering CLA as a reconstituted solution to treat susceptible organisms that infect ocular tissues.
- Full Text:
- Date Issued: 2021
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.
- Full Text:
- Date Issued: 2020
- 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.
- Full Text:
- 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.
- Full Text:
- Date Issued: 2020
- 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
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