Yuan, Wenxiang = CCTO陶瓷材料的制备和性质研究 / 苑文香. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 63-67). / Text in English; abstracts in English and Chinese. / Yuan, Wenxiang = CCTO tao ci cai liao de zhi bei he xing zhi yan jiu / Yuan Wenxiang. / Acknowledgement --- p.ii / Abstract --- p.iii / Contents --- p.v / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Background --- p.1 / Chapter 1.2 --- Structure --- p.1 / Chapter 1.3 --- Models --- p.3 / Chapter 1.3.1 --- Parallel RC --- p.3 / Chapter 1.3.2 --- Two parallel RCs in series --- p.5 / Chapter 1.4 --- Motivation --- p.7 / Chapter 1.5 --- Our work --- p.7 / Chapter Chapter 2 --- Experiment --- p.8 / Chapter 2.1 --- Sources and substrate --- p.8 / Chapter 2.2 --- Preparation of the CCTO samples --- p.8 / Chapter Chapter 3 --- Experimental equipment --- p.13 / Chapter 3.1 --- Furnace --- p.13 / Chapter 3.2 --- X-ray diffraction (XRD) --- p.13 / Chapter 3.3 --- Scanning electron microscopy (SEM) --- p.16 / Chapter 3.4 --- Impedance analyzers --- p.17 / Chapter Chapter 4 --- Selections of the experimental conditions --- p.18 / Chapter 4.1 --- Selection of calcining-process conditions --- p.18 / Chapter 4.1.1 --- Experimental results --- p.18 / Chapter 4.1.2 --- Comparison with the results of other research groups --- p.21 / Chapter 4.2 --- Selection of sintering-process conditions --- p.22 / Chapter 4.2.1 --- CuO volatilization --- p.22 / Chapter 4.2.2 --- CCTO decomposition --- p.24 / Chapter 4.3 --- Optimizing of the Cu/Ca ratio --- p.29 / Chapter Chapter 5 --- Results and discussion --- p.31 / Chapter 5.1 --- Properties of CCTO ceramics sintered at different temperatures for 10 h --- p.32 / Chapter 5.2 --- Properties of CCTO ceramics sintered for different durations at 1000°C --- p.43 / Chapter 5.3 --- Properties of CC3+ΧTO ceramics --- p.52 / Chapter 5.4 --- Discussion --- p.58 / Chapter Chapter 6 --- Conclusions --- p.61 / References --- p.63

Amostras de titânia foram sintetizadas por seis rotas diferentes: quatro pelo método sol-gel, utilizando condições e precursores distintos, por combustão de solução líquida e pelo método Pechini. Após tratamento térmico que variou de 100°C a 900°C, as amostras foram analisadas por difratometria de raios X, termogravimetria e pelo método BET de obtenção de áreas superficiais específicas. As amostras obtidas por sol-gel utilizando como precursores o isopropóxido de titânio (Pro) e o n-butóxido de titânio (But) geraram materiais de elevada área superficial, com alta fração molar de anatase e sem resíduos a 500°C. As amostras obtidas por sol-gel com excesso de íon peptizante (Nan) possuiam também altas áreas superficiais, além de estabilizarem a fase anatase a até 500°C, com resquícios de bruquita. As amostras obtidas por sol-gel utilizando um surfactante não iônico (Sur) demonstraram as maiores áreas superficiais, os menores tamanhos de cristais e estabilidade de anatase pura a 500°C. Esses materiais têm, pois, potencial para aplicação em fotocatálise, em células solares sensibilizadas por corantes e em células a combustível, entre outras. Os métodos da combustão (Com) e de Pechini (Pec) geraram produtos de baixa área superficial e com baixa ou com nenhuma fração de anatase. Porém, são métodos simples e eficientes de obtenção de titânia para aplicações que não necessitem da anatase como fase única. / Titania samples were prepared by six different routes, four of them by the sol-gel method using different precursors and reaction conditions, a solution combustion route and a Pechini method route. After thermal treatment ranging from 100 C to 900 C, the resulting materials were analyzed by X-ray diffraction, thermogravimetric analysis and surface area determination (BET method). The materials obtained by the sol-gel method using titanium isopropoxide (Pro) and titanium n-butoxide (But) as precursors yielded ceramics with high surface area, a high anatase molar fraction, without residues when heated at 500 C. Samples obtained by the sol-gel route using excess peptization agent (Nan) also showed high surface areas and yielded anatase with traces of brookite which was stable up to 500 C. Samples obtained using the sol-gel route with non-ionic surfactant (Sur) exhibit the highest surface area, smallest crystallite sizes and stable anatase with traces of brookite up to 500 C. These materials have, therefore, potential application in the areas of photocatalysis, dye- sensitized solar cells and fuel cells, among others. The combustion (Com) and Pechini (Pec) methods yielded materials with low surface area, with little or no presence of anatase. They are, however, simple and efficient methods for obtaining pure titania when the pure form of anatase is not a necessity.

Titanium Dioxide is a naturally occurring oxide of titanium. It has a wide range of uses in commercial products for providing whiteness and opacity. It has photocatalytic properties and can also be used to produce electricity in its nanoparticles form. This research is focused on investigating the effect of titanium dioxide nanoparticles in analysis of compounds using luminescence-based techniques. Quenching, which is one of the basic problems of fluorescent measurements, was studied in the presence of molecular oxygen and methyl iodide. The rutile phase of titanium dioxide nanoparticles was synthesized by the acid hydrolysis of titanium isobutoxide at low temperatures with nitric acid. The crystalline powder was dissolved at different concentrations and used to monitor the fluorescence intensities of carbazole, pyrene, and fluoranthene in the presence of methyl iodide and oxygen. Quenching by molecular oxygen was studied by comparing the fluorescence intensities of compounds with and without degassing the solutions. Titanium Dioxide was found to exhibit interesting effects on the fluorescent intensities of these compounds in the presence of quenchers.

This dissertation presents a method for enhancement of the efficiency and scalability of photocatalytic water purification systems, along with an experimental validation of the concept. A 3-dimensional photocatalyst structure, made from a TiO2-SiO2 composite, has been designed and fabricated for use in a custom designed LED-source illumination chamber of rotational symmetry that corresponds with the symmetry of the photocatalyst material. The design of the photocatalyst material has two defining characteristics: geometrical form and material composition. The design of the material was developed through the creation of a theoretical model for consideration of the system's photonic efficiency. Fabrication of the material was accomplished using a Ti alkoxide solution to coat a novel 3D support structure. The coatings were then heat treated to form a semiconducting thin-film. The resulting films were evaluated by SEM, TEM, UV-vis spectroscopy and Raman spectroscopy. The surface of the material was then modified by implantation of TiO2 and SiO2 nanoparticles in order to increase catalytic surface area and improve the photoactivity of the material, resulting in increased degradation performance by more than 500%. Finally, the efficiency of the photocatalytic reactor was considered with respect to energy usage as defined by the Electrical Energy per Order (EEO) characterization model. The effects of catalyst surface modification and UV-illumination intensity on the EEO value were measured and analyzed. The result of the modifications was an 81.9% reduction in energy usage. The lowest EEO achieved was 54 kWh per cubic meter of water for each order of magnitude reduction in pollutant concentration -- an improvement in EEO over previously reported thin-film based photoreactors.

Radiosensitization is a novel targeted therapy strategy where chemical compounds are being explored to enhance the sensitivity of the tissue to the effects of ionizing radiation. Among the different radiosensitizers alternatives, nanomaterials have shown promising results by enhancing tumor injury through the production of free radicals and reactive oxygen species (ROS). In this work, Gold-supported titania (Au@TiO2) nanocomposites were synthesized through an innovative strategy using X-ray irradiation, and their potential as radiosensitizers was investigated. Radiosensitization of Au@TiO2 nanocomposites was assessed by monitoring the decomposition of Methylene Blue (MB) under X-ray irradiation in the presence of the nanomaterial. Radiosensitization of Au@TiO2 was thoroughly investigated as a function of parameters such as Au loading, TiO2 particle size, nanomaterial concentration, different irradiation voltages, and dose rates. Results showed that the presence of Au@TiO2 increases significantly the absorbed dose, thus enhancing MB decomposition. The mechanism behind Au@TiO2 radiosensitization relies on their interaction with X-rays. TiO2 produces reactive ROS whereas Au leads to the generation of photoelectrons and Auger electrons upon exposure to X-rays. These species lead to an enhanced degradation rate of the dye, a feature that could translate to cancerous cells damage with minimal side effects. The radiosensitization effect of Au@TiO2 nanocomposites was also tested in biological settings using Microcystis Aeruginosa cells. The results showed an increase in cell damage when irradiated in the presence of Au@TiO2 nanocomposites. Au@TiO2 nanocomposites were fabricated using X-ray radiolytic synthesis, a method that diverges from conventional fabrication processes and leads to negligible by-product formation, an important feature for medical and catalytic applications. In this work, Au nanoparticles are supported on TiO2 with a mean particle size of either 6.5 nm or 21.6 nm, using different ligands such as NaOH or urea, and under different absorbed doses to determine the effects of these parameters on the nanomaterials’ characteristics. Overall, Au@TiO2 synthesized by X-rays showed remarkable promise as radiosensitizers, a concept relevant to a number of medical, biological and environmental applications.

Small drinking water systems, often financially and resource-limited, face unprecedented challenges due to the current diversity and ubiquity of water pollutants. Well-characterized inorganic legacy pollutants, including arsenic, copper, hexavalent chromium, and lead, remain persistent in drinking water systems. In addition, emerging organic contaminants, like endocrine disrupting compounds and pharmaceuticals, are largely uncharacterized but prevalent in the environment and water supplies, calling into question what levels of these relatively new contaminants are truly safe in drinking water. Point-of-use (POU) and point-of-entry (POE) water treatment devices, installed at a specific tap or at the water entry point to a single facility, respectively, are necessary to ensure safe drinking water in contexts where centralized water treatment is not available or cannot adapt to meet new regulatory standards. While existing POU and POE technologies, including reverse osmosis and packed bed media filters, are effective for removing contaminants, installation costs, energy demands, and spatial footprints of these systems can inhibit their implementation. There is a need for new POU and POE technologies that remove a diversity of water contaminants while maintaining a small application footprint. Nanotechnology, referring to technology using material with at least one dimension or feature less than 100 nm in length, is ideal for meeting this need in drinking water treatment. With high surface area-to-volume ratios, nano-enabled treatment technologies exhibit enhanced reactivity with less material, keeping overall footprint relatively small. Specifically, electrospinning, a process in which a polymer precursor solution is electrified to produce a cohesive sheet of nanofibers, can be used to easily synthesize chemically active nanofiber filters for water treatment applications. In this study, we develop electrospun nanofiber filters that harness nano-scaled hematite (Fe2O3) for sorption of inorganic contaminants (e.g., As, Pb) and nano-scaled titanium dioxide (TiO2) for use with ultraviolet (UV) and visible light as an advanced oxidation process (AOP) for removal of emerging organic contaminants (e.g., benzotriazole, carbamazepine, DEET). Most importantly, we strive to optimize both reactivity and material strength to develop cohesive, durable filtration platforms that overcome barriers to use of nanomaterials in water treatment (e.g., concerns over leaching of nanoparticles deployed as suspensions). Herein, we first demonstrate reactivity optimization of pure (though brittle) TiO2 nanofiber photocatalysts by noble metal catalyst (Au) surface loading. Additionally, we optimize polymer-Fe2O3 composite nanofibers for reactivity while maintaining material flexibility by coating the doped polymer with additional Fe2O3 surfaces available for metal/metalloid uptake. Finally, we apply reactivity optimization and strategies to maintain material strength in the development of carbon/TiO2 nanofiber composites used for (photo)chemical filtration of water containing emerging organic contaminants. Ultimately, we find that nanofiber composites exhibit substantial reactivity and structural integrity in water treatment platforms. Outcomes of this work contribute to making nanomaterials, which have been studied for decades but have yet to be commercially employed for water treatment, practical for chemically active water filtration.

Titanium dioxide, TiO2, has potential applications as a photoelectrode for photoelectrochemical generation of hydrogen by splitting water using solar energy and as a photocatalyst for water purification. This study is part of the UNSW research program to process TiO2-based oxide semiconductors as high-performance photoelectrodes and photocatalysts. This study investigates the effect of defect disorder on semiconducting properties of polycrystalline TiO2. This study involved the processing of high-purity polycrystalline TiO2 and determination of its semiconducting properties through measurement of electrical conductivity and thermoelectric power at elevated temperatures (1073-1323K) in controlled oxygen activities [1x10-13 Pa < p(O2) < 75 kPa]. The study included two types of experiments: Determination of electrical properties under conditions of gas/solid equilibrium. The data obtained was used to derive defect disorder and related semiconducting properties Monitoring of electrical properties during equilibration. This data was used to determine the chemical diffusion coefficient. The data obtained under equilibrium conditions indicates that oxygen may be used as a dopant to impose controlled semiconducting properties. In reduced conditions TiO2 is an n-type semiconductor and under oxidizing conditions TiO2 is a p-type semiconductor. The n-type behaviour is associated with oxygen vacancies as the predominant defects and titanium interstitials as the minority defects. The p-type behaviour is closely related to titanium vacancies that are formed during prolonged oxidation. Charge transport at elevated temperature was shown to involve substantial contribution from ions. Analysis of electrical properties enabled determination of several defect-related quantities including the activation enthalpy for oxygen vacancy formation, and the activation energy of the electrical conductivity components related to electrons, holes and ions. The kinetic data obtained during gas/solid equilibration enabled determination of the chemical diffusion coefficient which exhibited a complex dependence on nonstoichiometry. In addition, prolonged oxidation showed that equilibration occurred in two kinetic regimes. One for highly mobile oxygen vacancies and titanium interstitials which quickly reached an ??operational equilibrium?? within hours and another slow kinetic regime for equilibration of titanium vacancies over many thousand hours. The determined chemical diffusion coefficient data may be used to select the processing conditions required to impose uniform concentration of defects within a TiO2.

Magnetic photocatalysts were synthesised by coating a magnetic core with a layer of photoactive titanium dioxide. This magnetic photocatalyst is for use in slurry-type reactors in which the catalyst can be easily recovered by the application of an external magnetic field. The first attempt at producing this magnetic photocatalyst involved the direct deposition of titanium dioxide onto the surface of magnetic iron oxide particles. The photoactivity of these Fe3O4/TiO2 was lower than that of single-phase TiO2 and was found to decrease with an increase in the heat treatment. These observations were explained in terms of an unfavourable heterojunction between the titanium dioxide and the iron oxide core. Fe ion diffusion from the iron oxide core into the titanium dioxide matrix upon heat treatment, leading to a highly doped TiO2 lattice, was also contributing to the observed low activities of these samples. These Fe3O4/TiO2 particles were found to be unstable, with photodissolution of the iron oxide phase being encountered. This photodissolution was dependent on the heat treatment applied, the greater the extent of the heat treatment, the lower the incidence of photodissolution. This was explained in terms of the stability of the iron oxide phases present, as well as the lower photoactivity of the titanium dioxide matrix. In fact, the observed photodissolution was found to be induced-photodissolution. That is, the photogenerated electrons in the titanium dioxide phase were being injected into the lower lying conduction band of the iron oxide core, leading to its reduction and then dissolution. Thus, the approach of directly depositing TiO2 onto the surface of a magnetic iron oxide core proved ineffective in producing a stable magnetic photocatalyst. The introduction of an intermediate passive SiO2 layer between the titanium dioxide phase and the iron oxide phase inhibited the direct electrical contact and hence prevented the photodissolution of the iron oxide phase. Improvements in the photoactivity were seen to be due to the inhibition of both the electronic and chemical interactions between the iron oxide and titanium dioxide phases. Preliminary optimisation experiments revealed that a thin SiO2 layer is sufficient for inhibiting the photodissolution. The thickness of the TiO2 coating was found not to have a significant effect on the photocatalytic performance of the coated particles. Finally, heat treating for 20 minutes at 450??C was sufficient for converting the titanium dioxide into a photoactive phase, longer heating times had no beneficial effect on the photoactivity.

The present project has made a comprehensive assessment of the effect of Nb doping on various charge-transfer related properties of TiO2. Of particular focus, the electrical properties of Nb-doped TiO2 (0.65 at %) have been investigated using the simultaneous measurement of electrical conductivity and thermoelectric power. This investigation was undertaken at elevated temperatures (1073 K -- 1298 K) in equilibrium with a gas phase of controlled oxygen activity (10-10 Pa < p(O2) < 75 kPa). In addition, the effect of segregation on the surface versus bulk composition of Nb-doped TiO2 was also investigated at a function of temperature and oxygen activity. Specifically, the following determinations were undertaken: The effect of oxygen activity, p(O2) and temperature on both electrical conductivity and thermoelectric power The effect of Nb on the defect disorder and related electrical properties of TiO2 The determination of equilibration kinetics and the associated chemical diffusion data for Nb-doped TiO2 The determination of Nb bulk diffusion in TiO2 The effect of p(O2), temperature and dopant content on Nb segregation and the related surface composition of Nb-doped TiO2 The obtained electrical properties enable the determination of a defect disorder model for Nb-doped TiO2, which may be considered within the following p(O2) regimes: Strongly Reduced Regime. In this regime, the predominant ionic defect was anticipated to be oxygen vacancies compensated electronically by electrons. While the transition to this regime (from higher p(O2)) was clearly observed, the predominant defect disorder existing beyond this transition was not confirmed due to an inability to obtain sufficiently low oxygen activity. Metallic-type conductivity behaviour was observed within this transition region. Reduced Regime I. In this regime, the predominate defect disorder defined by the electronic compensation of incorporated Nb ions by electrons was clearly observed. Reduced Regime II. In this regime, the predominate defect disorder defined by the ionic compensation of incorporated Nb ions by quadruply-charged titanium vacancies, was clearly observed. The present project included the determination of diffusion data which included: Temperature dependence of 93Nb tracer diffusion in single crystal TiO2 over the temperature range 1073 K -- 1573 K Chemical diffusion coefficient over the temperature range 1073 K -- 1298 K and oxygen activity range, 10-10 Pa < p(O2) < 75 kPa These pioneering studies are significant as they enable the prediction of the processing conditions required to reliably 1) incorporate Nb into the TiO2 lattice, and 2) achieve equilibrium with the gas phase. Finally, the present project included investigations on the effect of Nb segregation on the surface composition of Nb-doped TiO2, with the following outcomes: Due to segregation, the surface can be significantly enriched in Nb compared to the bulk The extent of enrichment increases as the bulk Nb content or the oxygen activity is decreased Following enrichment, the surface Nb concentration could be sufficiently high to assume a unique surface phase The outcomes of the present project are significant as they can enable the processing of TiO2 with enhanced charge transport and controlled surface properties.

<p>In today’s society there is an increasing need for energy, an increase which for the most part is supplied by the use of fossil fuels. Fossil fuel resources are limited and their use has harmful effects on the environment, therefore the development of technologies that produce clean energy sources is very appealing. Natural photosynthesis is capable of converting solar energy into chemical energy through a series of efficient energy and electron transfer reactions with water as the only electron source. Thus, constructing an artificial system that uses the same principles to convert sunlight into electricity or storable fuels like hydrogen is one of the major forces driving artificial photosynthesis research.</p><p>This thesis describes supramolecular complexes with the intention of mimicking the electron transfer reactions of the donor side in Photosystem II, where a manganese cluster together with a tyrosine catalyses the oxidation of water. All complexes are based on Ru(II)-trisbipyridine as a photosensitizer that is covalently linked to electron donors like tyrosine or manganese. Photochemical reactions are studied with time-resolved transient absorption and emission measurements. Electrochemical techniques are used to study the electrochemical behavior, and different photoelectrochemical techniques are used to investigate the complexes adsorbed onto titanium dioxide surfaces. In all complexes, intramolecular electron transfer occurs from the linked donor to photo-oxidized Ru(III). It is also observed that coordinated Mn(II) quenches the excited state of Ru(II), a reaction that is found to be distance dependent. However, by modifying one of the complexes, its excited state properties can be tuned in a way that decreases the quenching and keeps the electron transfer properties. The obtained results are of significance for the development of multinuclear Ru-Mn complexes that are capable of multi-electron transfer.</p>