EPR spectra of Fe³⁺ in a natural crystal of brookite have been investigated at X- and Q-band frequencies at room temperature and 573°K. Part of the paramagnetic resonance spectrum observed has been interpreted on the assumption that Fe³⁺occupies eight equivalent Ti⁴⁺ sites in brookite, with four inequivalent orientations.. The spectra show an "intermediate" zero-field splitting at X-band and a "normal" zero field splitting at Q-band frequencies. The spin Hamiltonian parameters which fit the spectra are the following: g = 2.002 ± 0.005 . D = (1170 ± 30) x 10⁻⁴cm⁻¹ E = (330 ± 20) x 10⁻⁴cm⁻¹ [pa + (l/l2)qF]₀₁₀ = (13±10) x 10⁻⁴cm⁻¹ [pa + (l/l2)qF]₁₀₀ = (-13±15) x l0⁻⁴cm⁻¹ [pa + (l/l2)qF]₀₀₁ = (-66±4) x l0⁻⁴cm⁻¹ / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Paramagnetic resonances were observed in natural single crystals of anatase between 1 °K and 1230 °K and are interpreted as due to regular substitutional Fe(3+) (I) and to Fe (3+) combined with an oxygen vacancy at a nearest neighbour site (II) . The spin Hamiltonian parameter b(2)° of (I) decreases from +457 x 10(-4) cm(-1) at 1 °K almost linearly to -225 x 10(-4) cm(-1) at 1230 °K. This unusually strong temperature dependence of b(2)° and the observed temperature dependence of the orientation of the magnetic axes of spectrum (II) are both explained by assuming that the positions of the oxygen ions within the unit cell are temperature dependent. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

The exploration and application of nanomaterials have been attracting researchers’ attention in recent decades. Nanocatalysts, as one of the very important classes of nanomaterials, have been developed for several generations. Nanotechnology makes light be possibly utilized in catalysis rather than only heat and allows multifunctional parts to be assembled in one catalyst. The TiO2 (as the representative of hetero-photocatalyst) and iron-based magnetic catalysts (as multifunctional catalyst) will be discussed in detail in this thesis. The first chapter will introduce the background of catalysts and nanomaterials. TiO2, especially black TiO2, will be mainly discussed in the aspects of properties, synthesis, and applications. Another part of the chapter will talk about the separation-friendly catalyst – magnetic heterogenous catalysts’ synthesis and applications. Chapter 2 focuses on the synthetic route we used and the characterization of black TiO2 catalysts and magnetic catalysts. Both anatase and rutile black TiO2 catalysts were successfully prepared originally from Degussa P25 using the ethanol reduction method. The re-whitening treatment was also examined on both black TiO2 catalysts. All catalysts were characterized and compared by diffuse reflectance (DR), powder X-ray diffraction (XRD), and X-ray photoelectron spectroscope (XPS). Tauc plot results show that black TiO2 has smaller band gap than white TiO2. XPS revealed the existence of surface -OH species and Ti3+ in black TiO2. Furthermore, these two characterization techniques and XRD all proved that the blackening and re-whitening treatment does not change the crystalline phase of the catalysts, and the blackening treatment is reversible. For magnetic catalysts, we synthesized magnetic Fe2O3, Fe2O3@TiO2, copper/iron oxide magnetic TiO2, and black magnetic catalysts. Other than diffuse reflectance spectroscopy, Raman spectroscopy, scanning electron microscopy, and energy-dispersive X-ray elemental mapping analysis were used for determining the light-absorption properties, composition, and morphology of all synthesized magnetic catalysts. In addition, the magnetic separation was also achieved by simply applying an external magnetic field. Chapter 3 will discuss and compare the decarboxylation reaction activities of pristine, black, and re-whited TiO2 catalysts. The reactions were carried under the UV, blue, red, green, and white light irradiation. Unfortunately, the reaction was found only working under UV-light irradiation. The best solvent was dioxane which may be due to the proton affinity of the oxygen atom in dioxane molecule, which facilitates the deprotonation of the carboxylic acid. The optimal catalyst amount was found as 10 mg per 5 mL reaction mixture, and the kinetic study shows that the reaction is a pseudo-first order reaction. It is a pity that the performance of black TiO2 catalysts is worse than the pristine and re-whitened TiO2. Chapter 4 will talk about the sol-gel synthesized magnetic catalysts. These catalysts were used for aldehyde-alkyne-amine (A3) coupling reaction. The reaction was tested by light irradiating or traditional heating, but only heating can make the reaction proceed. Results also show that the coupling reaction requires copper to finish. The best solvent was found as toluene and the optimal reaction time is 6 hours at 120 ̊C. Sadly, the reactivity of copper/iron oxide magnetic TiO2 decreases a lot after three reaction cycles because of the copper leaching problem.

In this work, electrophotocatalytic disinfection on selected microorganisms was verified. The electrophotocatalytic system allows the application of electrical bias to the photoanode coated with a titanium dioxide layer. The disinfecting effect was observed on E.coli and C.glabrata in aqueous solution. The effect of radiation intensity on electrophotocatalysis and selected optimal conditions for further experiments was observed in the E. coli organism. Photocatalytic disinfection was carried out under suitable conditions on C.glabrata yeast and the effect of sodium sulfate electrolyte on electrophotocatalytic disinfection was observed in this case.

Titanium dioxide (TiO2) is an essential component in a white paint formulation due to its excellent light scattering ability. TiO2 also happens to make up most of the raw materials cost. Viable replacements to TiO2 do not currently exist in a feasible manner. Rising costs in the recent TiO2 supply shortage have forced coatings formulators to find a balance between cost and performance. One method includes partial substitution of TiO2 with cheaper material such as calcium carbonate (CaCO3), which serves to occupy volume. The purpose of this study was to compare the coating spread rate of paints with varying TiO2 and CaCO3 pigment volume concentration (PVC). Different sized CaCO3 particles were used in this study. A series of PVC ladder studies were performed at keeping CaCO3 PVC constant. Paints were formulated at the same volume solids to minimize variability. Weighed coating draw-downs were prepared to measure the contrast ratio. The coating spread rates were obtained with the DuPont Spread Rate program, which relies on Kubelka-Munk relationships, which takes into account the physical properties of the paint. These spread rate values were compared to one another across type and size to find common trends. Critical pigment volume concentration (CPVC) values were determined through regression of the spread rate values and compared to oil absorption tests. It was found that replacement of up to 20 PVC of TiO2 with CaCO3 could marginally increase the spread rate, thus increasing the efficiency of TiO2. The spread rate increased modestly as similarly sized extender particles were initially introduced, then dropped at higher extender levels. Data analysis revealed that CPVC was influenced based on the size and amount of the extender particle present, which can be used to predict resin demand of a paint system.

Access to clean water is essential for human health and dignity. The increasingly rapid population growth, combined with the emergence of resistant chemical compounds and more concentrated toxic residues in the effluent streams of treatment plants, point towards a decline in freshwater resources resulting in a global water crisis in the next decades. Current wastewater treatment plants rely on Advanced Oxidation Processes (AOPs) for the tertiary (or advanced) step of the treatment. Photocatalysis is one of such processes, by which semiconductors are exposed to radiation of specific wavelengths (traditionally UV) to generate Reactive Oxygen Species (ROS) that can degrade organic molecules through a chain of radical oxidation reactions. Anatase titania (TiO2) has been used for many decades as a photocatalyst. Its electronic band structure has a band gap of 3.2 eV, requiring radiation in the UV range to trigger its photocatalytic properties. One way to reduce the band gap energy and shift the absorption peak wavelength to the visible part of the spectrum (thus reducing operation costs) is by doping the photocatalyst particles with transition metal atoms. Iron (III) is a great candidate due to the placement of its conduction/valence bands within titania’s band gap, its atomic radius similar to titanium (IV) and its variety of oxidation states. However, iron-doped anatase titania synthesized by ordinary sol-gel methods shows a photodegradation efficiency that is much lower than undoped anatase. Previous studies have shown that this is caused by an inconspicuous iron oxide layer on the surface of the catalyst particle, forming a physical barrier to the mobility of charge carriers that trigger the formation of ROS radicals. Small changes to the synthesis protocol, namely slowing down the hydrolysis of the Ti precursor by lowering the solution’s pH and acid-washing the final product, have been shown to result in particles that are photoactive under visible radiation and boast an unobstructed reactive surface. In this work, the novel Fe-TiO2 photocatalyst is studied and characterized in terms of its particle size distribution, inner structure and composition using electron microscopy techniques. It is important to know the particle size profile arising from this novel synthetic method, as the presence of nanoparticles could pose a health risk whereas an abundance of oversized particles is undesirable from the perspective of chemical reaction engineering (low surface-to-volume ratio). Inner structure/composition analyses could reveal whether the iron content inside the photocatalyst segregates into iron oxides, which would hinder reaction rates by behaving as a recombination center for charge carriers. As well, gathering more information about the inner structure of the catalyst (such as degree of crystallinity) is desirable as that could help fine-tune the synthesis protocol in order to obtain optimal photocatalytic activity. The particle size distribution studies using scanning electron microscopy revealed that the catalyst samples contain a significant fraction of nanoparticles (31.55% smaller than 100 nm), even though those particles represent a very small fraction of total sample volume (0.00015%) and reactive area (0.03%). Moreover, oversized particles (bigger than 5 m) account for the biggest fraction of sample volume and reactive surface. It was suggested that the size distribution of the catalyst be shifted to intermediate particle sizes by introducing additional grinding and separation steps into the synthesis protocol. The inner structure studies were carried using a combination of scanning, transmission and scanning-transmission electron microscopy, as well as spectroscopy methods such as EDX and EELS to map composition. It was found that the original anatase lattice structure remained unchanged in terms of interplanar spacings and crystallographic orientations, indicating that the addition of iron impurities at the small concentrations used here (0.5at%) did not result in discernible changes to the lattice. The monocrystalline units of Fe-TiO2 (termed crystallites) often appear to be bound together by amorphous material. No segregation of Fe was observed inside the particles at this concentration, as shown by the apparent homogenous composition of the catalyst across crystalline and amorphous regions. The external iron oxide contamination layer observed in previous studies was theorized to form during the later steps of the sol-gel process due to the precipitation of the iron content in solution that failed to be incorporated into the TiO2 gel network. More in-depth studies must be carried to assess whether preferential segregation of iron within the catalyst could occur at higher dopant concentrations. / Graduate

Titanium dioxide (TiO2) is an established photocatalyst utilized for the photo-oxidation of organics in wastewater. Aqueous suspensions of TiO2 require separation and re-suspension steps to be used on an industrial scale. A method of immobilizing TiO2 within the mesoporous structure of silica has been developed at the University of Alabama. The objective of this thesis was to design and evaluate a bench-scale, continuous, photocatalytic reactor utilizing these films. This was accomplished in two phases of work: (1) batch reactions and (2) continuous reactions. The batch reactor was a one-liter standard photochemical reactor from Ace Glass. The continuous photocatalytic reactor designed for this study consisted of nine 12-inch long, 6-mm ID quartz tubes aligned around the medium-pressure, ultra-violet lamp (UV) used in the batch reactor. The tubes were coated on the inside with a thin film of mesoporous silica impregnated with TiO2 and connected in series with 6-inch pieces of Masterflex tubing. Experimental conditions were as follows: 190 ppm solutions of 2,4-dichlorophenol (2,4-DCP), UV lamp, TiO2 in either 0.05 wt% suspensions (slurry) or thin films of mesoporous silica (film); and/or 750 ppm hydrogen peroxide (H2O2). In batch and continuous experiments the UV/H2O2 and the UV/TiO2 (slurry)/H2O2 systems were the most successful with respect to the oxidation of 2,4 ? DCP. The loss of 2,4 ? DCP in continuous UV/TiO2 (film) systems was not significantly different from continuous UV only systems. However, the continuous UV/TiO2 (film)/H2O2 system degraded more 2,4 ? DCP than the systems utilizing UV light alone. The continuous reactor developed in this study showed enhanced by-product degradation using UV/TiO2 (film)/H2O2 over the UV/H2O2 system.

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