D.Phil. (Chemistry) / Elimination of toxic organic compounds from wastewater is currently one of the most important subjects in water-pollution control. Among the many organic pollutants are dyes and emerging pollutants such as natural organic matter (NOM). Dyes such as Eosin Yellow (EY), an anionic xanthene fluorescent dye, can originate from many sources such as textile industrial processes, paper pulp industries and agricultural processes. Most dyes are problematic because they are resistant to conventional chemical or biological water-treatment methods and therefore persist in the environment. NOM consists of a highly variable mixture of products found in water and soils. NOM is formed as a result of the decomposition of plant and animal material and is a precursor to the formation of disinfection by-products (DBP) during water disinfection. These organic compounds cause undesirable colour, taste and odour in water. NOM affects the capacity of other treatment processes to effectively remove organic micro-pollutants or inorganic species that may be present in the water. Its removal also uses up chemicals and energy and so it is expensive to treat. Titanium dioxide (TiO2) has emerged as one of the most fascinating materials in the modern era due to its semiconducting and catalytic properties. TiO2 is a large band-gap semiconductor that exists mainly in the anatase (band gap 3.2 eV) and rutile (band gap 3.0 eV) phases. Its response to UV light has led to increased interest in its application in the photocatalysis research field. It has been investigated extensively for its super hydrophilicity and use in environmental remediation and solar fuel production. In spite of extensive efforts to apply TiO2 for environmental remediation, photocatalytic activity in the visible region has remained quite low hence the ultimate goal of this research was to fabricate highly photoactive catalysts composed of non-metal, platinum-group metal (PGM) co-doped TiO2 and carbon nanotubes (CNTs) and to apply them for water purification using solar radiation...

The use of nanomaterials (NMs) in orally ingestible products raises concerns about potential hazards. Titanium dioxide (TiO2) particles (of which some are incidentally produced at the nanoscale) are used in cosmetics, biological remediation (photo-catalysis), toothpastes, ingestible pharmaceuticals and food products. The increased surface area to mass ratio of nanoparticles (NPs) potentially makes them more biologically reactive than their coarser (bulk) material counterparts. There is limited data available on the uptake kinetics across the mammalian gastrointestinal tract, and the potential hazard posed to humans. In this study, the uptake and accumulation of TiO2 (nano and bulk) into and across the human intestinal cell line, the isolated perfused rat jejunum and the whole rat were evaluated. Caco-2 monolayers exhibited time-dependent, accumulation, uptake and transport of Ti/TiO2 from TiO2 exposures of 1 mg L-1 over 24 h, which was influenced by the crystal type, irrespective of cell maturity and growth substrate (Chapters 2-3). Electron micrographs of the Caco-2 monolayer showed the presence of particles inside the cells within vesicles and energy dispersive spectroscopy (EDS) confirmed the composition as TiO2. Addition of pharmacological inhibitors altered the Ti concentration in the cells suggesting diffusion is not the primary mechanism of uptake, rather, an active process is responsible (Chapter 2). Whole gut sacs exposures of 1 mg L-1 bulk or nano TiO2 demonstrated the primary regions of the gut associated with accumulation are the small and large intestine, with 70 % or more of the TiO2 accumulating in the mucosa rather than the underlying muscularis. Perfused intestines exposed to 1 mg L-1 bulk or nano TiO2 for 4 h showed a time-dependent accumulation of Ti in the serosal perfusate with the initial rates of Ti flux from the nano exposures being 5 fold higher than the bulk form. Addition of pharmacological inhibitors caused increases in tissue Ti concentration and significantly reduced Ti serosal flux rates for NP exposures. Overall, the data suggests an active absorption mechanism is responsible for Ti uptake from both bulk and nano TiO2 exposures across the perfused rat intestine that is drug sensitive (Chapter 4). In vivo work demonstrated feed status and rat age effected Ti tissue concentrations. Critically, Ti tissue concentrations reduced with increasing age and removal of Ti containing feed caused transient decreases in Ti tissue concentrations in 23 day old rats. Transient decreases in Ti tissue concentration following feed removal were not observed in older rats suggesting young rats may be more sensitive to the uptake hazards presented by titanium (Chapter 5). Overall, the findings presented in this thesis demonstrate Ti/TiO2 from both bulk and nano TiO2 exposures are accumulated and transported across intestinal epithelium and these processes are drug sensitive and affected by crystal structure and particle size. The results in this thesis have contributed to a better understanding of the uptake kinetics and sub-lethal hazards presented by bulk and nano forms of TiO2 exposed to intestinal epithelium which could be used to partially inform policy makers on human dietary risk assessments.

Philosophiae Doctor - PhD / The aim of this study was to design and build an electrohydraulic discharge reactor in such a way that the synthetic immobilized TiO2 nanophotocatalytic components could be integrated, for the production of active species such as OH radicals, ozone and hydrogen peroxide, as a cocktail to clean drinking water without the addition of chemicals. The research objectives include: • To design and construct the different AOP prototypes based on various electrode configurations and compare their operation. • To optimize the discharge parameters and conditions of the best AOP system. • To determine the effectiveness of the best prototype for the degradation of methylene blue as model pollutant. • To compare the designed AOP system with the Sodis method for the disinfection of contaminated river water. • To prepare supported TiO2 nanoparticles via electro spinning, followed by combustion and study the effect on the morphology of TiO2 nanoparticles. • To determine the stability and robustness of composite nano-crystalline TiO2 photocatalysts by sonication • To determine the enhanced effect of combining the composite TiO2 in the AOP system on degradation of methylene blue under the same conditions. • To detect the active species promoting disinfection.

There is a range of feed materials available for the production of Ti02 pigment. These range from natural materials like ilmenite and rutile to synthetic materials like synthetic rutile. There is a large increase in the price of titaniferous feed materials as the Ti02content of the material increases. To take advantage of the difference in price between chloride grade slag and natural rutile a process was developed to increase the Ti02 content of chloride grade slag from ~85% to more than 95%. This beneficiated titania slag product (BTS) should be ideal as feed material to the chloride pigment process. Initially several processes were evaluated. Particular emphasis was placed on the slag pre-treatment procedure. This was necessary as impurities could only be leached with difficulty from as-cast slag. A suitable pre-treatment procedure would render the impurities easily leachable, while the titanium is retained in an insoluble form. The results indicated that a process consisting of oxidation and reduction roasting would satisfy these requirements. Detailed process development was then undertaken on this process. The first phase of the process development was conducted in a coal fired fluid bed roaster. This allowed a set of semi optimised process parameters to be established, but the highest Ti02 content that could be achieved was 94%. A second stage of process development was under taken under more controlled conditions, using a small fluid bed reactor connected to a gas mixing system. Based on the results in this phase of the process development a new set of optimum process parameters was established. They are oxidation at 850°C for 1.5 h in an atmosphere containing 8% O2; reduction at 850°C for 10 min in a 100% CO atmosphere and leaching in boiling 20% hydrochloric acid for 12 h. Under these conditions it was possible to produce BTS containing > 97% Ti02. During oxidation of titania slag several important morphological changes occur. These are the conversion of the original M305 phase in the slag to a mixture of rutile/anatase, hematite and ferric M305. In the process the iron in the slag migrates to the outside surfaces of the slag particles where it is easily accessible during leaching. The iron containing phases are converted to ilmenite during reduction and during leaching the ilmenite is removed. This yields the BTS product. As the oxidation roast appeared to be a very important of the BTS process it was decided to investigate the mechanism of titania slag oxidation. A mechanism based on the nucleation energy that is required to form the relevant phases during oxidation was proposed. This mechanism was tentatively confirmed through selected experiments. / Thesis (PhD)--University of Pretoria, 2009. / Materials Science and Metallurgical Engineering / unrestricted

Three studies were performed to obtain fundamental mechanistic information on the TiO2 catalyzed photooxidations of organic substrates irradiated at 350 nm in dilute aqueous solutions under oxygenated conditions: (a) The photodecomposition of three haloethers, 2-chloroethyl ether, 4-chlorophenyl phenyl ether, and 4-bromophenyl phenyl ether, was investigated in an aqueous media at pH 7.0. (b) A comparative study of structure-reactivity was conducted on para-substituted phenols whose substituents range from electron-withdrawing to electron-donating in an aqueous media at pH 3.0. (c) The initial rates of the TiO2 catalyzed photodegratation of phenol were studied in an aqueous media at pH 1.0, 3.0, 5.0, 7.0, 9.0, 11.0, and 13.7 and a pH effect profile was obtained and compared to the removal efficiency after four hours of irradiation. Controls were carried out throughout the three studies in the absence of light and under anoxic conditions, as well as without the semiconductor to evaluate the role of photolysis. The Langmuir-Hinshelwood model was employed in an attempt to characterize and evaluate differences in reactivity.

In the present research, a novel method, namely sol-gel/laser-induced technique (SGLIT), has been developed to generate nano-structured TiO2-based films. The TiO2 films based on unloaded (pure) TiO2, Ce-TiO2, W-TiO2 and Ag-TiO2, have been investigated in attempt to stabilise the formation of anatase and consequently of enhancing photo-catalytic and anti-bacterial activities. The TiO2 precursor loaded with Ce2+, W6+ and Ag2+ ions (Ce-TiO2, W-TiO2 and Ag-TiO2) were separately prepared by sol-gel method and spin-coated on microscopic glass slides. A pulsed KrF excimer laser with a wavelength of 248 nm and pulse width of 13-20 ns was employed to irradiate on the sol-gel prepared films at various operating parameters, in terms of laser fluence, number of laser pulses and repetition rate. The work has been focussed on microstructural characterisation of various films prepared by both SGLIT and furnace, in the consideration of crystallographic structure, phase transformation, crystallite sizes, surface morphology, film thickness and optical properties, by means of Raman spectroscopy, XRD, FEG-SEM/EDX, TEM/HR-TEM/EDX, AFM and UV-Vis spectroscopy etc. The results showed that nano-crystallisation of the films after laser irradiation has been achieved, with controllable amount of anatase formation. These coatings presented a unique feature of surface morphology with meso-porosity and much enlarged surface areas, compared with the films prepared by furnace sintering technique. The addition of Ce and Ag, stabilized the anatase structure during the laser irradiations, whereas the addition of W destabilized the anatase structure. The Ce-TiO2 films prepared by SGLIT exhibited anatase structure which was stable up to 500 laser pulses at 35 mJ cm-2 fluence. The anatase was formed after 10 laser pulses only at 65-75 mJ cm-2 fluence in the W-TiO2 films. When a higher number of laser pulses, fluence or higher W6+ loading were chosen, rutile structure started to form. On the other hand, the Ag-TiO2 nano-composite films prepared by SGLIT presented the anatase up to 200 laser pulses at 85 mJ cm-2 fluence. On average, anatase crystallite size of about 38 nm was achieved from both the W-TiO2 and Ag-TiO2 films prepared by SGLIT. In contrast, the furnace-sintered W-TiO2 and Ag-TiO2 films produced anatase crystallite size of 49.4 nm and 29.8 nm respectively. Another achievement of the present research is the development of a single-step laser irradiation technique to generate an Ag-TiO2 nano-composite film on the glass substrate. A pulsed laser beam produced hexagonal Ag nanoparticles along with the crystallization of anatase-based nano-structured TiO2 film which was accomplished in 1 µs only. The films prepared by SGLIT displayed a higher photo-absorption compared to their furnace-sintered counterparts due to the unique surface features with a higher surface roughness. Overall, an enhanced bactericidal activity against E. coli cells was demonstrated under UV light by each of the W-TiO2 films compared to furnace-sintered films except the 1W-TiO2. The E. coli cells did not survive on the W-TiO2 films prepared by SGLIT, after 80 minutes under UV (365 nm) light. In contrast, E. coli cells still survived on the surface of furnace-sintered W-TiO2 films under the same conditions. Ag-TiO2 nano-composite films prepared by SGLIT, demonstrated an enhanced anti-bacterial activity against E. coli compared to the conventionally- made Ag-TiO2 films. No bacteria survived on the Ag-TiO2 films prepared by 50 laser pulses at 85 mJ cm-2 fluence, whereas E. coli colonies always survived on the furnace-sintered Ag-TiO2 films under the UV, natural light and the dark room conditions.

Biomimicry means literally ‘imitation of life’ and is providing sustainable solutions for challenges that are occurring in the human lives. To date, the biomimic research reports that wettability in nature, e.g. self-cleaning effect on a lotus leaf and a striking water strider’s leg, is related to the cooperation between the chemical composition and the topography of the surface. Moreover, this study is developing a textile substrate that goes one step further than biomimic, called ‘Biomimicking beyond nature’. The focus of this study is establishing a 100% polyamide-66 textile substrate that is switchable and reversible between hydrophobic and hydrophilic states under stimulation of UV. In this study the behaviour of a polyamide-66 textile substrate, coated with three individual photoresponsive materials (azobenzene, titanium dioxide and zinc oxide), was investigated, under stimulation of 24 hours UV and one-week of storage period in dark conditions. Silicone was added to enhance the hydrophobicity of a titanium dioxide coated substrate. A switchability effect was detected, but no reversibility effect could be observed. The only organic photoresponsive material, azobenzene, obtained no significant results to conclude that an alternation between hydrophobic and hydrophilic was even present after 24 hours of UV radiation. However, azobenzene obtained more promising results on a 100% polyester textile substrate. Even though, the H0 cannot be rejected for all three individual photoresponsive materials, the zinc oxide coated polyamide-66 substrate, did exhibit the strongest results in switchability and reversibility. Based on the characterization measurements, a switchability effect from a hydrophobic surface (ca. 120°) to a hydrophilic surface (0°) can be observed after 24 hours of UV radiation. Moreover, a reversibility effect was only reported on a zinc oxide coated polyamide-66 substrate. The substrate partially reversed back to its original state with ca. 50%. Fabricating intelligent substrates could enhance many challenges confiscating today’s life. For instance, the development of smarts membranes or microfluidic switches, that alternate their wettability upon light radiation, could improve the exhausting manual labour in watering the harvest good in the agricultural industry. Therefore, it is of great importance that further research will be conducted upon the photoresponsive material, zinc oxide, in order to achieve more stable results. This study can be added to the relatively small area of knowledge around switchability phenomenon on textile substrates and can even been reported as one of the first attempts on developing a textile substrate with switchable and reversible characteristics, by use of a facile and possibly industrialized method.

>Magister Scientiae - MSc / The aim of this study was to enrich electrospun fibres with the active mineral phase TiO2 nanoparticles and then to evaluate how well the composite fibres performed in the photocatalytic degradation of methylene blue (MB). Electrospun hydrophobic PAN polymer fibres were used as support structures for the TiO2 nanoparticles. The photocatalytic activity of the TiO2 enriched fibres for dye degradation was evaluated and the effect of external stressors on the fibres was assessed. A comparison was also made to determine whether the TiO2 - photocatalyst catalyst should be coated on top of, or loaded inside the electrospun PAN fibres

Orientador: Luiz Fernando Zagonel / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-28T03:52:44Z (GMT). No. of bitstreams: 1 Ramos_Raul_M.pdf: 5673835 bytes, checksum: 005e134cbd8cbb241cbdf367a75f35a3 (MD5) Previous issue date: 2015 / Resumo: Eletrodos condutores transparentes (TCE) possuem grande importância para tecnologias de informação e geração de energia. O TCE mais eficiente na atualidade é o ITO (In2O3 dopado com Sn), que pode alcançar resistividades em torno de 2.10-4 ?cm e uma transmitância ótica de 80% a 90% na região do visível. Entretanto, a escassez dos recursos naturais de Índio e sua grande demanda sugerem a necessidade de materiais alternativos. O presente estudo tem por objetivo investigar as propriedades óticas, eletrônicas e estruturais de filmes finos de TiO2 (fase anatase) dopados com Nitrogênio. A deposição dos filmes foi feita por Deposição por Feixe de Íons (IBD) por bombardeamento de um alvo de titânio puro com íons de Ar+ em atmosfera de O2. Os filmes, com uma espessura de ?90 nm, foram depositados em substrato de quartzo amorfo (Herasil-1) a temperaturas de 400 ou 500°C. Depois, os filmes são dopados com implantação iônica, variando o tempo de 10 a 60 minutos, com feixe de íons misto a baixa energia de N2+ e H2+ com 150 eV e sob a mesma temperatura de crescimento. Após a implantação, medidas Hall indicam que a densidade de portadores majoritários nos filmes de anatase dopados com nitrogênio chegam até ?1019 cm?3 (enquanto filmes não dopados tem densidade de cargas de ?1012 cm?3). A resistividade dos filmes dopados chegam até 10?1 ?cm enquanto mantem boa transmissão ótica (>80%). De fato, dependendo do tempo de dopagem e da temperatura do substrato durante o processo, a transmissão de até 85% podem ser obtida em 550 nm com tal resistividade (?10?1 ?cm). Espectroscopia de fotoelétrons emitidos por raio-x (XPS) realizadas in situ mostram que a composição na superfície é compatível com TiO2?xNx com concentração de nitrogênio de até ? 20%. Difração de raio-x com ângulo de incidência rasante (GIXRD) confirmaram a estrutura cristalina anatase dos filmes antes e após a implantação iônica à baixa energia (150 eV). Este estudo indica que é possível dopar a amostra anatase com nitrogênio através do uso de um feixe de íons de baixa energia. Tal abordagem é interessante por permitir um controle da concentração de dopantes (Nitrogênio através de um precursor gasoso) de forma mais controlada do que usualmente obtido por sputtering reativo / Abstract: Transparent conductive electrodes (TCE) have great importance for information and energy technologies. The most efficient TCE is currently the ITO (Sn-doped In2O3), which may have a resistivity lower than 2·10?4 ?cm and an optical transmittance of 80% to 90% in the visible region. However, the scarcity of natural resources of Indium and its great demand suggests the need of alternative materials. The present study aims to investigate the optical, electronic and structural properties of thin films of TiO2 (anatase phase) doped with nitrogen. The films deposition is made by Ion Beam Deposition (IBD) by bombarding a pure titanium target with Ar+ ions in O2 atmosphere to a thickness of about 90 nm. The films are deposited on an amorphous quartz substrate (Herasil-1) at 400 or 500 °C. Afterwards, the films are doped by ion implantation with low-energy ion beam mixed of N2+ and H2+ at 150 eV and under the same temperature of the growth for times ranging from 10 to 60 minutes. After implantation, Hall measurements indicated that the majority carrier density in the nitrogen doped anatase films reaches up to ? 1019 cm?3 (while the undoped films have a carrier density of ? 1012 cm?3). The resistivity of the doped films is as low as 10?1 ? cm while maintaining good optical transmission. Indeed, depending on the doping time and substrate temperature, transmission of up to 90% could be obtained at 550 nm with this resistivity. X-ray photoelectron spectroscopy (XPS) performed in situ shows that the surface composition is compatible with N:TiO2?x with nitrogen concentrations of up to ? 20%. Small angle x-ray diffraction measurements (SAXRD) confirmed the anatase crystal structure of the films before and after the low energy ion implantation. This study indicates that it is indeed possible to dope anatase thin films with nitrogen by low energy ion beam. This approach is interesting for allowing a greater control of doping concentration with respect to what is usually obtained by reactive sputtering / Mestrado / Física / Mestre em Física / 2013/118682-8 / CAPES

Nesse estudo procurou-se avaliar o impacto do aditivo dióxido de titânio, mistura anatase-rutila, no comportamento fotocrômico de nanocompósitos baseados em materiais híbridos do tipo silicatos orgânicos (Ormosis) contendo ácido fosfotúngstico, \'H IND.3\'PW IND.12\'O IND.40\'. O material híbrido foi obtido via processo sol-gel tendo sido caracterizado quanto à sua morfologia por Microscopia óptica e Microscopia Eletrônica de Varredura (MEV), que mostrou que os filmes em geral são pouco rugosos e homogêneos. Estudos de Espectroscopia Vibracional (Espectroscopia de Absorção na Região do Infravermelho e Raman) confirmaram a integridade do heteropoliânion fosfotungstato e a formação de uma rede tridimensional de silicatos, assim como, permitiram identificar a abertura do anel oxirano para formar um poli(óxido de etileno) ramificado, caracterizando a formação de um material híbrido classe II. A Espectroscopia de absorção na região do Ultra-violeta visível (UV-vis) ou espectroscopia eletrônica, além de confirmar a integridade química da espécie fosfotungstato, permitiu acompanhar a formação de heteropoliazuis mono- e duplamente reduzidos de maneira quantitativa. A cristalinidade dos materiais foi avaliada por Difração de raios-x (DRX) e mostrando que o sólido resultante é amorfo. Os estudos espectroscópicos permitiram inferir que a interação entre os polioxometalatos e as nanopartículas de \'TI\'O IND.2\' deve ser fraca, entretanto, estudos posteriores são necessários para confirmar isto. A adição de nanopartículas leva a um material mais sensível à radiação UV, entretanto, não há uma correlação linear entre massa de nanopartículas adicionada e variação de absorbância devido à irradiação. / In this study we evaluated the impact of the additive titanium dioxide, anatase-rutile mixture, Photochromic behavior of nanocomposite materials based on hybrid organic-type silicates (Ormosia) containing phosphotungstic acid, \'H IND.3\'PW IND.12\'O IND.40\'. The hybrid material was obtained via sol-gel process has been characterized for their morphology by optical microscopy and scanning electron microscopy (SEM), which showed that the films are often little rough and smooth. Studies of Vibrational Spectroscopy (Absorption Spectroscopy in the infrared and Raman) confirmed the integrity of phosphotungstic acid and the formation of a three-dimensional network of silicates, as well as the opening of the oxirane ring to form a poly (ethylene oxide) branched characterizing the formation of a hybrid class II material. The absorption spectroscopy in the region of Ultra-violet visible (UV-vis) to confirm the chemical integrity of phosphotungstate species, allowed us to track the formation of mono-and doubly heteropolyblues reduced quantitatively. The crystallinity of the materials was evaluated by x-ray diffraction (XRD) and showed us that the resulting solid is amorphous. The spectroscopic studies allowed us to infer that the interaction between polyoxometalates and \'TI\'O IND.2\' nanoparticles should be weak, however, further studies are needed to confirm this. The addition of nanoparticles leads to a material more sensitive to UV radiation, however, there is not a linear correlation between mass of nanoparticles added and absorbance variation due to irradiation.