Thesis (doctoral)--University of Tartu, 2006. / This dissertation is based on 6 papers. Includes bibliographical references.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

In this study, the properties of nickel and antimony doped tin oxide (NATO) electrode materials were investigated in relation to the electrochemical generation of ozone. The performance of NATO materials was correlated to ·OH radical generation and oxygen adsorption properties. Long-time ozone generation results suggested that surface property changes, including surface morphology, chemical composition and electro-catalyst thickness, could lead to ozone production rate decreased from 137 to 0 mg·h-1 and the current efficiency declined from 18% to 0. The loss of Ni in the electrode was suggested for the decrease in ozone generation. Moreover, material characterization results indicated the presence of NiOOH and multiple oxidation states of Sb (+3 and +5), which were proposed as the critical sites for the electrochemical generation of ozone. In addition, NATO nanocrystals of 3.5 ~ 7.5 nm in size prepared by the hydrothermal method were used as an alternative route to fabricate electrodes. The highest current efficiency of 41% was achieved on NATO material of 6% Sb in the precursor, which led to the lowest resistivity of 2.38 ± 0.03 Ω·cm in the product NATO material. This further demonstrated the applicability of NATO materials used as electro-catalysts for the electrochemical generation of ozone. Hydroxyl free radicals (·OH) can be regarded as one of the most important intermediates for ozone generation. The presence of ·OH radicals was quantified by fluorescence spectroscopy with terephthalic acid as probes. Quantitative analysis results showed that Ni dopant could significantly enhance ·OH generation, while over-doping of Sb and Ni can decrease the generation of ·OH radicals. An oxygen chemisorption study on NATO materials showed that more active sites available for oxygen chemisorption lead to higher catalytic activity for ozone generation. The highest oxygen chemisorption capacity of 49.76 μmol·g-1 was achieved on NATO-5 (Sn:Sb:Ni=1000:16:2), which showed the highest current efficiency of 43%. In addition, temperature programmed oxygen adsorption and desorption showed different patterns on different NATO materials. This suggested that oxygen adsorption on NATO materials has a correlation to the electrochemical generation of ozone. In addition, oxygen adsorption was further investigated with near ambient oxygen adsorption. Oxygen adsorption isotherm results indicated that both physisorption and chemisorption can occur on the surface of SnO2 based material (NATO-5) with or without hydrogen pretreatment. When NATO-5 was treated with hydrogen, adsorption was mainly in the form of chemisorption. However, it was mainly in the form of physisorption without hydrogen pretreatment. By comparing NATO-6 (Sn:Sb:Ni=1000:16:0) with NATO-7 (Sn:Sb:Ni=1000:0:2), it was found that Sb was more important in the oxygen adsorption ability of NATO materials compared to Ni doping. Based on the findings in this study, two active sites (Sb and Ni sites) were proposed for ·OH generation and oxygen adsorption in order to explain the mechanism of ozone generation on NATO materials. Also, electrochemical generation of ozone was correlated with oxygen adsorption and ·OH generation. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Thesis (M. Sc.)--University of Canterbury, 2009. / Typescript (photocopy). Includes bibliographical references (p. 51-55). Also available via the World Wide Web.

Thesis (M.S.)--Oregon State University, 2008. / Printout. Includes bibliographical references (leaves 52-56). Also available on the World Wide Web.

The adsorption of a number of Brønsted acids of differing strengths has been studied on stoichiometric and defective Sn0₂ (110) surfaces. The extent of dissociation of these acids depends on the surface composition and the strength of the acid. Two crystallographically inequivalent types of oxygen vacancies can be introduced onto SnO0₂ (110) surfaces, and the kinetics of the reactions of Brønsted acids is influenced by the number and type of oxygen vacancies present on each surface. The site requirement for dissociation of Brønsted acids has been described as a coordinatively unsaturated cation and an available anion. On the Sn00₂ ( 110) surfaces studied, this site requirement was seen to be a necessary but not sufficient condition for dissociation. In contradiction to the generally accepted idea that the presence of defects increases reactivity, the most defective SnO₂ (110) surface considered showed the lowest activity for dissociation for all adsorbates studied. / Ph. D.

Thesis (M.Sc. (Physics)) -- University of Limpopo, 2015 / Nanocrystalline materials of defect free anatase and rutile SnO2 together with Ti and Y in anatase SnO2 have been modelled successfully using classical molecular dynamics simulations together with Buckingham potential. The structural properties of these SnO2 phases were analysed using radial distribution functions (RDFs). The effect of increasing temperature in pure SnO2 and doped SnO2 were studied. In both pure and doped materials, RDFs suggest phase transition at higher temperature, where anatase SnO2 transforms to rutile SnO2. Rutile SnO2 was found to be more stable than anatase SnO2. The results showed that the dopants have different effects on the SnO2 material. Ti defect is found to lower the transformation temperature of anatase to rutile SnO2. Y defect is found not to have any effect on the anatase to rutile SnO2 transformation. Thermodynamic properties such as volume thermal expansion coefficient and specific heat capacity were also calculated from above Debye temperature. Volume thermal expansion coefficient was obtained from volume versus temperature curves. Volume thermal expansion coefficient for rutile and Ti-anatase SnO2 were found to be not of the same order with the calculated results. Specific heat capacity calculated from energy versus temperature curves was found to be in agreement with the Dulong and Petit law of solids. Nanocrystalline Al/Y co-doped SnO2 powders were successfully synthesized using the sol-gel method. The samples were subjected to different temperatures 100 (as prepared) 200, 400, 600, 800 and 1000 oC. The effects of co-doping and temperature on the structural and optical properties of Al/Y co-doped SnO2 nanoparticles as well as morphology were investigated. The characterization techniques used were X-ray powder diffraction (XRD), Raman spectroscopy, Scanning electron microscopy (SEM) and UV-visible spectroscopy (UV-vis). The average particle sizes were found to be in the range between 2.5–8 nm and the strains were calculated to be 2.76–0.53 with increasing temperature for as prepared and the sample sintered at different tempe-ratures. The Raman bands were found to correspond with the literature. At a higher temperature of about 800 oC the materials were found to contain the second phase which is yttrium stannate. However no information about aluminium was found. The optical band gap were found to be between 3.3–3.99 eV in the temperature range 200–1000 oC.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 189-197).

Thesis (M.S.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.