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The research presented here is focused on photochemical studies of a supramolecular structural motif for photoinitiated electron collection. The complex studied, [{(bpy)2Ru(dpp)}2RhCl2](PF6)5, is of the form LA-BL-EC-BL-LA comprising a Ru(II) polyazine light absorber (LA) bearing two bpy (bpy = 2,2'-bipyridine) ligands, two dpp (dpp = 2,3'-bis(2-pyridyl)pyrazine) bridging ligands (BL), and a central rhodium(III) electron collector (EC). Ruthenium-polyazine light absorbers are commonly used in light to energy conversion systems due to the intense metal to ligand charge transfer (MLCT) absorptions observed in the visible spectrum. Electrochemical methods establish rhodium as the site of localization of the lowest lying unoccupied molecular orbital, while phosphorescence measurements are used to study electron transfer within the supramolecular assembly. Electrochemical and photochemical experiments show that the absorption of light in the rhodium centered supramolecular complex, [{(bpy)2Ru(dpp)}2RhCl2](PF6)5, can initiate the sequential transfer of multiple electrons to the rhodium metal center, i.e. photoinitiated electron collection. A mechanistic study of photoinitiated electron collection, involving a Stern-Volmer analysis of emission quenching and product formation, is also presented, to determine the rate constants of the possible excited state and ground state reactions. One application of a molecular device for photoinitiated electron collection is fuel production. It has been shown that the complex studied, [{(bpy)2Ru(dpp)}2RhCl2](PF6)5, can collect reducing equivalents and use them to catalyze the reduction of water to hydrogen. Photocatalytic hydrogen generation experiments will also be presented including initial quantum yield optimization experiments. / Ph. D.

PhD. (Chemistry) / Pre-synthesised gadolinium oxide decorated multiwalled carbon nanotubes (MWCNT-Gd) were coupled with titania to form nanocomposite photocatalysts (MWCNT-Gd/TiO2) using a sol-gel method. Rare earth metal ions (Eu, Nd and Gd), nitrogen and sulphur tridoped titania were decorated on MWCNT-Gd to yield composite photocatalysts (MWCNT-Gd/Eu/Nd/Gd/N,S-TiO2) by a similar method, using thiourea as nitrogen and sulphur source. Different carbon nanomaterials were incorporated into tridoped titania to form various composite photocatalysts (MWCNT/Gd,N,S-TiO2, MWCNT/Nd,N,S-TiO2, SWCNT (single walled carbon nanotube)/Nd,N,S-TiO2 and rGO (reduced graphene oxide)/Nd,N,S-TiO2) via the sol-gel method. Likewise, gadolinium doped graphitic carbon nitride (g-C3N4-Gd3+) was obtained by heating a mixture of gadolinium nitrate hexahydrate and cyanoguanidine and subsequently hybridised with MWCNT/TiO2 using the sol-gel method to yield composite photocatalysts with varying g-C3N4-Gd3+ loadings. All the prepared photocatalysts were characterised by microscopic tools (FE/FIB-SEM-EDX, TEM), crystallographic technique (XRD), spectroscopic tools (UV-Vis, Raman and FT-IR) and nitrogen sorption technique (BET).

Thesis (Masters of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, [2018]. / Enhancing the efficiency of large scale photocatalytic systems has been a concern for decades. Engineering design and modelling for the successful application of laboratory-scale techniques to large scale is obligatory. Among the many fields of research in heterogeneous photocatalysis, photocatalytic reaction engineering can initiate improvement and application of conservative equations for the design and scale-up of photocatalytic reactors. Various reactor configurations were considered, and the geometry of choice was the annular shape. Theory supports the view that annular geometry, in the presence of constant transport flow properties, monochromatic light, and an incompressible flow, will allow a system to respect the law of conservation of mass. The degradation of a simulated dye, methyl orange (MO), by titanium dioxide (TiO2) with a simulated solar light (halogen lamp) in a continuous recirculating batch photoreactor (CRBPR) was studied. A response surface methodology (RSM) based on central composite design (CCD) was applied to study interaction terms and individual terms and the role they play in the photocatalytic degradation of MO. The studied terms were volume (L), TiO2 (g), 2 (mL), and initial dye concentration (mg/L), to optimize these parameters and to obtain their mutual interaction during a photocatalytic process, a 24 full-factorial CCD and RSM with an alpha set to 1.5 were employed. The polynomial models obtained for the chosen responses (% degradation and reaction rate constant, k) were shown to have a good externally studentized vs normal percentage probability fit with R2 values of 0.69 and 0.77 respectively. The two responses had a common significant interaction term which was the H2O2 initial dye concentration term. The optimum degradation that was obtained in this study was a volume of 20 L, TiO2 of 10 g, H2O2 of 200 mL and the initial dye concentration of 5 mg/L which yielded 64.6% and a reaction rate constant of 0.0020 min-1. The model of percentage degradation was validated on a yield of 50% and 80% over a series of set volumes and the model validation was successful.

Naphthenic acids (NAs) are natural constituents of bitumen and crude oil, and predominantly obtained as the by-product of petroleum refining with variable composition and ingredients. Naphthenic acids are composed of alkyl-substituted cycloaliphatic carboxylic acids, with smaller amounts of acyclic aliphatic acids. Naphthenic acids become a significant part of the tailings pond water (TPW) after separation from oil sands material. NAs are soluble in water and are concentrated in TPW as a result of caustic oil sands extraction processes. Tailings ponds near the Athabasca oil sands region near Fort McMurray, Alberta, Canada are contaminated with a variety of toxic organic compounds released in industrial effluent from the oil extraction processes. NAs are among the major water contaminants in those regions because of their toxicity and environmental recalcitrance. They may enter surface water systems due to erosion of riverbank oil sands deposits and through groundwater mixing. Significant environmental and regulatory attention has been focused on the naphthenic acids fraction of oil sands material to address these challenges and potential hazards. Biological, chemical, and photolytic treatments of water contaminated with NAs have been studied, but are either time consuming or involve significant capital investment. There is a growing need to develop more efficient and cost-effective treatment methods. Based on existing literature, microwave and photocatalysis for degradation of naphthenic acids in water may be one solution. A knowledge gap exists in determining the effect of microwave energy and/or photocatalysis on the rate and extent of NAs degradation in contaminated water.<p> Part of this work included evaluation of the physical and chemical properties of NAs. Dielectric properties, important for designing a microwave system, were investigated. Effects of temperature, concentration, and frequency of microwaves on the dielectric properties of NA-water mixtures were studied and were used in designing the treatment systems for NAs. Three laboratory scale systems, (1) photocatalysis, (2) microwave, and (3) microwave assisted photocatalysis systems were designed and developed. Experiments were conducted to determine the NA degradation efficiency of these systems for both commercially available Fluka NAs and those extracted from oil sand process water (OSPW). Effects of water source (deionised and river water) and use of TiO2 catalyst in the degradation process, were also investigated. Degradation kinetics for total NAs as well as individual z-family were calculated.<p> Results show that the three developed treatment systems were able to degrade NAs at a faster rate than the methods reported to date. The concentration of higher molecular weight NAs (z = -4 to -12) decreased more significantly than the lower molecular weight NAs in all the three treatment systems. Toxicity assessments of the NAs samples before and after treatment indicated that photocatalysis and microwave assisted photocatalysis systems decreased the toxicity of Fluka and OSPW NAs completely (up to 5 min IC50 v/v > 90%). The microwave system reduced the toxicity of water containing Fluka NAs from high (5 min IC50 v/v = 15.85%) to moderate (5 min IC50 v/v = 36.45%) toxicity. However, a slight increase in toxicity was noted post-treatment in OSPW NAs.<p> Microwave-assisted photocatalysis was the most rapid degradation system for OSPW NA extracts in water with a half-life of 0.56 h in the presence of TiO2. The microwave system degraded OSPW NAs in water at a more moderate half-life of 3.32 h. The photocatalysis system was the slowest with a half-life of 3.99 h under similar conditions.<p> High and ultra high resolution analysis of NA sample, estimations of cost and further efficiency related research of the developed systems to treat water with microbial load along with chemical contaminants are recommended for future work to further validate these treatment systems.

Naphthenic acids (NAs) are natural constituents of bitumen and crude oil, and predominantly obtained as the by-product of petroleum refining with variable composition and ingredients. Naphthenic acids are composed of alkyl-substituted cycloaliphatic carboxylic acids, with smaller amounts of acyclic aliphatic acids. Naphthenic acids become a significant part of the tailings pond water (TPW) after separation from oil sands material. NAs are soluble in water and are concentrated in TPW as a result of caustic oil sands extraction processes. Tailings ponds near the Athabasca oil sands region near Fort McMurray, Alberta, Canada are contaminated with a variety of toxic organic compounds released in industrial effluent from the oil extraction processes. NAs are among the major water contaminants in those regions because of their toxicity and environmental recalcitrance. They may enter surface water systems due to erosion of riverbank oil sands deposits and through groundwater mixing. Significant environmental and regulatory attention has been focused on the naphthenic acids fraction of oil sands material to address these challenges and potential hazards. Biological, chemical, and photolytic treatments of water contaminated with NAs have been studied, but are either time consuming or involve significant capital investment. There is a growing need to develop more efficient and cost-effective treatment methods. Based on existing literature, microwave and photocatalysis for degradation of naphthenic acids in water may be one solution. A knowledge gap exists in determining the effect of microwave energy and/or photocatalysis on the rate and extent of NAs degradation in contaminated water.<p> Part of this work included evaluation of the physical and chemical properties of NAs. Dielectric properties, important for designing a microwave system, were investigated. Effects of temperature, concentration, and frequency of microwaves on the dielectric properties of NA-water mixtures were studied and were used in designing the treatment systems for NAs. Three laboratory scale systems, (1) photocatalysis, (2) microwave, and (3) microwave assisted photocatalysis systems were designed and developed. Experiments were conducted to determine the NA degradation efficiency of these systems for both commercially available Fluka NAs and those extracted from oil sand process water (OSPW). Effects of water source (deionised and river water) and use of TiO2 catalyst in the degradation process, were also investigated. Degradation kinetics for total NAs as well as individual z-family were calculated.<p> Results show that the three developed treatment systems were able to degrade NAs at a faster rate than the methods reported to date. The concentration of higher molecular weight NAs (z = -4 to -12) decreased more significantly than the lower molecular weight NAs in all the three treatment systems. Toxicity assessments of the NAs samples before and after treatment indicated that photocatalysis and microwave assisted photocatalysis systems decreased the toxicity of Fluka and OSPW NAs completely (up to 5 min IC50 v/v > 90%). The microwave system reduced the toxicity of water containing Fluka NAs from high (5 min IC50 v/v = 15.85%) to moderate (5 min IC50 v/v = 36.45%) toxicity. However, a slight increase in toxicity was noted post-treatment in OSPW NAs.<p> Microwave-assisted photocatalysis was the most rapid degradation system for OSPW NA extracts in water with a half-life of 0.56 h in the presence of TiO2. The microwave system degraded OSPW NAs in water at a more moderate half-life of 3.32 h. The photocatalysis system was the slowest with a half-life of 3.99 h under similar conditions.<p> High and ultra high resolution analysis of NA sample, estimations of cost and further efficiency related research of the developed systems to treat water with microbial load along with chemical contaminants are recommended for future work to further validate these treatment systems.

published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

D.Phil. (Chemistry) / Please refer to full text to view abstract

Cette thèse porte sur l’élaboration et l’étude des performances de membranes d’ultrafiltration PVDF-TiO2 possédant des propriétés anti-colmatantes et photo-induites. La membrane est obtenue par application de la méthode de séparation de phases induite par un non-solvant sur un collodion de polyfuorure de vinylidène au sein duquel ont été incorporées des nanoparticules de TiO2. Il est montré : i) que la presence des nanoparticules de TiO2 les propriétés membranaires, et notamment le flux de perméat, par rapport à la membrane PVDF ; ii) que l’augmentation de la température de préparation de la membrane permettait de modifier la structure membranaire, en passant d’une morphologie constituée principalement de macrovides (dite en “doigts de gants”) à des températures basses à une morphologie spongieuse, contenant des pores de plus petite taille, à température élevée. Au-delà de la structure membranaire, des propriétés telles que la perméabilité, la porosité, la résistance mécanique, la cristallinité et les propriétés thermiques sont également influences par les changements de température de formation. Lorsque les membranes PVDF-TiO2 sont mises en oeuvre en mode photo-filtration (c.-à-d. filtration avec irradiation ultraviolette (UV) continue sur la membrane), le flux à l’eau pure de la membrane PVDF-TiO2 est encore augmenté, du fait du phénomène d’hydrophilicité photo-induite des nanoparticules de TiO2. Des premières estimations suggèrent que la photo-filtration par les membranes PVDF-TiO2 serait une économiquement rentable, car le gain en termes de filtration et qualité d’eau l’emporterait sur le cout énergétique induit par l’irradiation UV. En outre, l’efficacité de la photo-filtration a été évaluée avec des solutions d’alimentation synthétiques contenant des composés inorganiques et organiques représentatifs des eaux de surface. Il a été montré que si la plupart des ions inorganiques communément rencontrés dans l’eau potable n’ont aucun effet sur l’efficacité de la photo-filtration, la coexistence de Cu2+ et HCO3- dans l’eau d’alimentation entraîne un colmatage inorganique sévère qui inhibe le phénomène hydrophilicité photoinduite. En outre, la membrane PVDF-TiO2 présente également des flux plus élevés et une activité photocatalytique lors de la photo-filtration de solutions contenant des matières colmatantes organiques comme les acides humiques ou l’alginate de sodium. En conclusion, la membrane composite PVDF-TiO2 a démontré des propriétés et des performances significativement améliorées par rapport à la membrane PVDF, a fortioti lorsqu’elle est mise en oeuvre dans un système de photo-filtration sous irradiation UV. Ainsi, ce sont des matériaux prometteurs pour des applications membranaires en traitement de l’eau. / This thesis deals with the elaboration and performance of a specific type of ultrafiltration membrane with anti-fouling and photo-induced properties, the PVDF-TiO2 composite membrane. The membrane was fabricated via the nonsolvent-induced phase separation method by incorporating titanium dioxide (TiO2) nanoparticles into the polyvinylidene fluoride (PVDF) polymer matrix. The TiO2 nanoparticles played a significant role in facilitating the membrane formation process and improving the composite membrane properties compared to the neat PVDF membrane. It was demonstrated that, by changing the membrane preparation temperature, the membrane structure could be affected dramatically, notably the morphological dominance of finger-like macrovoids at lower temperatures and their diminution in both size and number when temperature increased. Other membrane properties also saw systematic transitions with changes in formation temperature, as characterized by permeability, porosity, mechanical strength, crystallinity, and thermal properties. In terms of performance, the PVDF-TiO2 membrane exhibited superior permeate flux compared to the neat PVDF membrane. More importantly, when being operated in photo-filtration mode (i.e. filtration with continuous ultraviolet (UV) irradiation on the membrane), the pure water flux of PVDF-TiO2 membrane could be further increased, thanks to the enhanced hydrophilicity of the membrane, which comes from the photo-induced hydrophilicity phenomenon of TiO2. Preliminary estimations suggest that photo-filtration is a cost-effective method, as the benefit from enhanced water output outweighs the extra energy demand for UV irradiation. Furthermore, the efficiency of photo-filtration was evaluated with synthetic feed solutions containing inorganic and organic contents representative in surface water. It was identified that, while most of the common inorganic ions in drinking water had no effects on photo-filtration efficiency, the coexistence of Cu2+ and HCO3- in the feed led to severe inorganic fouling and inhibited the photo-induced hydrophilicity phenomenon. Besides, the PVDF-TiO2 membrane also showed its stronger flux performance and photocatalytic activity during photo-filtration of solutions containing organic foulants like humic acids or sodium alginate. In conclusion, the PVDF-TiO2 composite membrane exhibited much improved properties and performance compared to the neat PVDF membrane, and even stronger performance when operated in photo-filtration mode. Thus, it is a promising candidate to be used in membrane-based applications for water treatment.

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