The effects of various catalyst synthesis parameters on the photocatalytic degradation kinetics of aqueous methyl orange dye are presented. The four factors investigated were: i) InVO4 concentration, ii) nickel concentration, iii) InVO4 calcination temperature, and iv) ballmilling time. Three levels were used for each factor. Due to the large number of possible experiments in a full factorial experiment, an orthogonal-array experimental design was used. UV-vis spectrophotometry was used to measure the dye concentration. The results show that nickel concentration was a significant parameter, with 90% confidence. The relative ranking of importance of the parameters was nickel concentration > InVO4 concentration > InVO4 calcination temperature > milling time. The results of the orthogonal array testing were used to make samples of theoretically slowest and fastest catalysts. Curiously, the predicted-slowest catalyst was the fastest overall, though both samples were faster than the previous set. The only difference between the slowest and fastest catalysts was the milling time, with the longer-milled catalyst being more reactive. From this result, we hypothesize that there is an interaction effect between nickel concentration and milling time. The slowest and fastest catalysts were characterized using energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM), x-ray powder diffractometry (XRD), BET surface area analysis, and diffuse-reflectance spectroscopy (DRS). The characterization results show that the fastest catalyst had a lower band gap than the slowest one, as well as a slightly greater pore volume and average pore diameter. The results indicate that fast kinetics are achieved with low amounts of nickel and a long ball milling time. Under the levels tested, InVO4 concentration and the calcination temperature of the InVO4 precursor were not significant.

Magister Scientiae - MSc (Chemistry) / Drinking water with high concentrations of inorganic and organic contaminants can cause adverse health defects. Specifically methyl orange dye is an organic water contaminant that has been known (along with others like methyl blue etc.) to have an increase in our water systems over the past few years due to increasing demand in industrial processes. It is therefore of utmost importance to remediate organic contaminants and ultimately enable prevention. The contaminants can be removed by photocatalysis. Anatase TiO2 is known for its photocatalytic degradation of environmental pollutants and photoelectro-chemical conversion of solar energy. However its application is limited since it is a wide band gap semiconductor, (Eg = 3.2 eV). The following study deals with the enhancement of the photocatalytic properties of TiO2 for remediation of organic water contaminants.

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Heterogeneous photocatalysis is an advanced oxidation technology widely applied in environmental remediation processes. It is a relatively safe and affordable technology with a low impact on the environment and has found applications in a number of fields from chemical engineering, construction and microbiology to medicine. It is not catalysis in the real sense of the word as the photons which initiate the desired photocatalytic reaction are consumed in the process. The cost of these photons is by far the limiting economic factor in its application. From a technical standpoint, the inefficient use of the aforementioned photons during the photocatalytic reaction is responsible for the limited adoption of its application in industry. This inefficiency is characterised by low quantum yields or photonic efficiencies during its application. The mechanism of the technique of controlled periodic illumination which was previously proposed as a way of enhancing the low photonic efficiency of TiO2 photocatalysis has been investigated using a novel controlled experimental approach; the results showed no advantage of periodic illumination over continuous illumination at equivalent photon flux. When the technique of controlled periodic illumination is applied in a photocatalytic reaction where attraction between substrate molecules and catalyst surface is maximum and photo-oxidation by surface-trapped holes, {TiIVOH•}+ ads is predominant, photonic efficiency is significantly improved. For immobilized reactors which usually have a lower illuminated surface area per unit volume compared to suspended catalyst and mass transfer limitations, the photonic efficiency is even lower. A novel photocatalytic impeller reactor was designed to investigate photonic efficiency in gas–solid photocatalysis of aromatic volatile organic compounds. The results indicate photonic efficiency is a function of mass transfer and catalyst deactivation rate. The development of future reactors which can optimise the use of photons and maximize photonic efficiency is important for the widespread adoption of heterogeneous photocatalysis by industry.

Esta tese está voltada ao estudo da síntese e caracterização de hidro-esponjas de polímeros condutores estruturados sob a ação do agente molde de alaranjado de metila. A síntese destas hidro-esponjas foi realizada tanto quimicamente quanto eletroquimicamente. Na síntese química, destacam-se as hidro-esponjas de polipirrol, onde os estudos de eletrointumescimento realizados em meio aquoso, tanto a nível macroscópico (via variação de volume) quanto a nível molecular (via FTIR-ATR), mostraram que o material se comporta como um hidrogel apresentando alta capacidade de sofrer uma expansão de volume (um aumento de até 40%) e absorver grandes quantidades de água. No que se refere à síntese eletroquímica, destacam-se os filmes finos de hidro-esponja de polipirrol e de polianilina na forma tubular. Diferenças morfológicas foram analisadas de acordo com a mudança de parâmetros de síntese. Para os filmes de polipirrol, foi realizado um estudo sobre o crescimento da estrutura tridimensional de hidro-esponja via imagens AFM, onde foi observado um aumento significativo nas propriedades eletroquímicas com o aumento da estrutura esponjosa do polipirrol, mostrando grande atividade para aplicação em um sistema supercapacitivo (1200 F.g-1). Para os filmes de polianilina, foi realizado um estudo morfológico, eletroquímico e espectroscópico identificando as mudanças de propriedades provocadas pela nanoestruturação do material. Foi observado que a forma tubular da polianilina provoca uma mudança conformacional na cadeia polimérica refletindo nas propriedades eletroquímicas, principalmente devido ao aumento na população de transportadores de cargas. / The present work is focused on the study of the synthesis and characterization of conducting polymeric hydro-sponges structured by using methyl orange template. The syntheses of the hydro-sponges were performed by both chemical and electrochemical methods. Electro-swelling studies performed were with Polypyrrole hydro-sponges chemically synthezised, at macroscopic level (by volume change) and molecular level (by FTIR-ATR analysis) showing that the material behaves as a hydrogel presenting high ability to undergo large volume changes (until 40%) and to absorb high amounts of water. Regarding the electrochemical synthesis, the hydro-sponges thin films of polypyrrole and polyaniline of nanotubular shape were prepared. Morphological differences were analyzed according to the change in the synthesis parameters. For the polypyrrole films, a study of the growth of the three-dimensional structure was performed by using AFM analysis. A significant increase in the electrochemical properties with the increase of the spongy structure of polypyrrole was observed, leading to high electroactivity opening the possibility to be applied in supercapacitors (1220 F g-1). For the polyaniline films, a morphological, electrochemical and spectroscopic study was performed identifying the change of properties caused by the nanostructuring of the material. It was noted that the tubular shape of the polyaniline causes a conformational change in the polymer chain which reflects in the electrochemical properties, mainly due to the increase in the population of the charge carriers.

Esta tese está voltada ao estudo da síntese e caracterização de hidro-esponjas de polímeros condutores estruturados sob a ação do agente molde de alaranjado de metila. A síntese destas hidro-esponjas foi realizada tanto quimicamente quanto eletroquimicamente. Na síntese química, destacam-se as hidro-esponjas de polipirrol, onde os estudos de eletrointumescimento realizados em meio aquoso, tanto a nível macroscópico (via variação de volume) quanto a nível molecular (via FTIR-ATR), mostraram que o material se comporta como um hidrogel apresentando alta capacidade de sofrer uma expansão de volume (um aumento de até 40%) e absorver grandes quantidades de água. No que se refere à síntese eletroquímica, destacam-se os filmes finos de hidro-esponja de polipirrol e de polianilina na forma tubular. Diferenças morfológicas foram analisadas de acordo com a mudança de parâmetros de síntese. Para os filmes de polipirrol, foi realizado um estudo sobre o crescimento da estrutura tridimensional de hidro-esponja via imagens AFM, onde foi observado um aumento significativo nas propriedades eletroquímicas com o aumento da estrutura esponjosa do polipirrol, mostrando grande atividade para aplicação em um sistema supercapacitivo (1200 F.g-1). Para os filmes de polianilina, foi realizado um estudo morfológico, eletroquímico e espectroscópico identificando as mudanças de propriedades provocadas pela nanoestruturação do material. Foi observado que a forma tubular da polianilina provoca uma mudança conformacional na cadeia polimérica refletindo nas propriedades eletroquímicas, principalmente devido ao aumento na população de transportadores de cargas. / The present work is focused on the study of the synthesis and characterization of conducting polymeric hydro-sponges structured by using methyl orange template. The syntheses of the hydro-sponges were performed by both chemical and electrochemical methods. Electro-swelling studies performed were with Polypyrrole hydro-sponges chemically synthezised, at macroscopic level (by volume change) and molecular level (by FTIR-ATR analysis) showing that the material behaves as a hydrogel presenting high ability to undergo large volume changes (until 40%) and to absorb high amounts of water. Regarding the electrochemical synthesis, the hydro-sponges thin films of polypyrrole and polyaniline of nanotubular shape were prepared. Morphological differences were analyzed according to the change in the synthesis parameters. For the polypyrrole films, a study of the growth of the three-dimensional structure was performed by using AFM analysis. A significant increase in the electrochemical properties with the increase of the spongy structure of polypyrrole was observed, leading to high electroactivity opening the possibility to be applied in supercapacitors (1220 F g-1). For the polyaniline films, a morphological, electrochemical and spectroscopic study was performed identifying the change of properties caused by the nanostructuring of the material. It was noted that the tubular shape of the polyaniline causes a conformational change in the polymer chain which reflects in the electrochemical properties, mainly due to the increase in the population of the charge carriers.

The photocatalytic wastewater treatment facility presented in this thesis is a promising economic green technology that can degrade wastewater’s organic and ammonia pollutants, which produce environmentally sensitive products like CO2, H2O, Nitrates, etc. that can be captured and used in many biological and engineering ways. Previous advances used for this research was determining the importance of cleaning the photocatalytic nanocrystals, Fe-TiO2, as one of the revolutionary improvements that expose and maximizes the active surface of the photocatalytic nanocrystals to the pollutants enabling the strong oxidants produced by the absorption of a photon, excitation of an electron and positive hole to produce oxidants on the surface of the nanocrystals. The oxidants indiscriminately produce CO2 and H2O from living and non-living organic matter to obtain near ~100% clean water. This research focused on taking the next steps in the development of a wastewater cleaning facility tested in our laboratory. An important step involved coating Fe-TiO2 crystals onto flexible, strong, fiber-glass cloth using a sol-gel processing method. Success was found in this research by applying the coated fiberglass cloth into a photoreactor aimed to clean a large amount of water rather than the laboratory scale. / Graduate

Composite materials formed from two or more functionally different materials offer a versatile avenue to create a tailored material with well defined traits. Within this dissertation research, multi-functional composites were synthesized based on organic and inorganic materials. The functionally of these composites was experimentally tested and a semi-empirical model describing the sedimentation behavior of these particles was developed. This first objective involved the fabrication of microcomposites consisting of titanium dioxide (TiO2) nanoparticles confined within porous, microgels of a thermo-responsive polymer for use in the photocatalytic treatment of wastewater. TiO2 has been shown to be an excellent photocatalyst with potential applications in advanced oxidative processes such as wastewater remediation. Upon UV irradiation, short-lived electron-hole pairs are generated, which produce oxidative species that degrade simple organic contaminants. The rapid sedimentation of these microcomposites provided an easy gravimetric separation after remediation. Methyl orange was used as a model organic contaminant to investigate the kinetics of photodegradation under a range of concentrations and pH conditions. Although after prolonged periods of UV irradiation (~8-13 hrs), the titania-microgels also degrade, regeneration of the microcomposites was straightforward via the addition of polymer microgels with no loss in photocatalytic activity of the reformed microcomposites. The second objective within this dissertation involved the systematic development of abrasive microcomposite particles containing well dispersed nanoparticles of ceria in an organic/inorganic hybrid polymeric particle for use in chemical mechanical polishing/planarization (CMP). A challenge in IC fabrication involves the defect-free planarization of silicon oxide films for successful multi-layer deposition. Planarization studies conducted with the microcomposites prepared in this research, yield very smooth, planar surfaces with removal rates that rival those of inorganic oxides slurries typically used in industry. The density and size of these ceria-microgel particles could be controlled by varying the temperature or composition during synthesis, leading to softer or harder polishing when desired.

In the past 30 years zero-valent iron (ZVI) has become an increasingly popular reducing agent technology for remediating environmental contaminants prone to chemical degradation. Azo dyes and chlorinated organic compounds (COCs) are two classes of such contaminants, both of which include toxic compounds with known carcinogenic potential. ZVI has been successfully applied to the surfaces of permeable reactive barriers, as well as grown into nanoscale particles (nZVI) and applied in-situ to chemically reduce these contaminants into more environmentally benign compounds. However, the reactivity of ZVI and nZVI in these technologies is limited by their finite supply of electrons for facilitating chemical reduction, and the tendency of nZVI particles to homo-aggregate in solution and form colloids with reduced surface area to volume ratio, and thus reduced reactivity. The goal of this project was to combine reactive nanoparticle and membrane technologies to create an electro-catalytic permeable reactive barrier that overcomes the weaknesses of nZVI for the enhanced electrochemical filtration of azo dyes in solution. Specifically, nZVI was successfully grown and stabilized in a network of functionalized carbon nanotubes (CNTs) and deposited into an electrically conductive thin film on the surface of a polymeric microfiltration support membrane. Under a cathodic applied voltage, this thin film facilitated the direct reduction of the methyl orange (MO) azo dye in solution, and regenerated nZVI reactivity for enhanced electro-catalytic operation. The electro-catalytic performance of these nZVI-CNT membrane surface composites to remove MO was validated, modelled, and optimized in a batch system, as well as tested in a dead-end continuous flow cell system. In the batch experiments, systems with nZVI and a -2 V applied potential demonstrated synergistic enhancement of MO removal, which indicated the regeneration of nZVI reactivity and allowed for the complete removal of 0.25 mM MO batches within 2-3 hours. Partial least squares regression (PLSR) modelling was used to determine the impact of each experimental parameter in the batch system and provided the means for an optimization leading to maximized MO removal. Finally, tests in a continuous system yielded rates of MO removal 1.6 times greater than those of the batch system in a single pass, and demonstrated ~87% molar removal of MO at fluxes of approximately 422 lmh. The work herein lays the foundation for a promising technology that, if further developed, could be applied to remediate azo dyes and COCs in textile industry effluents and groundwater sites respectively. / Thesis / Master of Applied Science (MASc)