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/ line-height:115% / } @page Section1 {size:8.5in 11.0in / margin:1.0in 1.0in 1.0in 1.0in / mso-header-margin:.5in / mso-footer-margin:.5in / mso-paper-source:0 / } div.Section1 {page:Section1 / } --> </style><!--[if gte mso 10]> <style> /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal" / mso-tstyle-rowband-size:0 / mso-tstyle-colband-size:0 / mso-style-noshow:yes / mso-style-priority:99 / mso-style-qformat:yes / mso-style-parent:"" / mso-padding-alt:0in 5.4pt 0in 5.4pt / mso-para-margin-top:0in / mso-para-margin-right:0in / mso-para-margin-bottom:10.0pt / mso-para-margin-left:0in / line-height:115% / mso-pagination:widow-orphan / font-size:11.0pt / font-family:"Calibri","sans-serif" / mso-ascii-font-family:Calibri / mso-ascii-theme-font:minor-latin / mso-fareast-font-family:"Times New Roman" / mso-fareast-theme-font:minor-fareast / mso-hansi-font-family:Calibri / mso-hansi-theme-font:minor-latin / mso-bidi-font-family:"Times New Roman" / mso-bidi-theme-font:minor-bidi / } </style> <![endif]--> <p class="MsoNormal"><span style="font-size: 12pt / line-height: 115% / font-family: &quot / Times New Roman&quot / ,&quot / serif&quot / ">The heterogeneous photocatalytic oxidation of dinitrogen to nitrate, NO3 and/or nitrite, no2 using peroxy species of titanium (IV) in aqueous suspensions has been investigated. The photocatalysts used were titanium peroxide and Degussa p25 TiO2 pretreated with H2O2. These photocatalysts were investigated by SEM and FTIR spectroscopy. <span style="">&nbsp / </span><o:p></o:p></span></p> <span style="font-size: 12pt / font-family: &quot / Times New Roman&quot / ,&quot / serif&quot / "><o:p></o:p></span></p> </p>

We use different methods to deposit Ti thin film on the ITO glass substrate. Under the circumstances of using fixed concentration of electrolyte, changing anodic time, and applying voltage, we are able to use anodic method to make ordered nano TiO2 thin film,of which the smallest pore size is 18nm and the thickness is 4500

Photocatalytic oxidation is an alternative water treatment method under consideration for disinfecting water. Chlorine disinfection can form harmful byproducts, and some viruses (e.g. adenoviruses) are resistant to other alternative disinfection methods. Photocatalytic oxidation using nano-sized photocatalytic particles (e.g. TiO2, fullerene) holds promise; however, it is limited by its low efficiency and long required treatment times. This research focuses on improving virus inactivation by photocatalytic oxidation by modifying catalysts for improved activity, by analyzing virus inactivation kinetics, and by elucidating the inactivation mechanisms of adenovirus serotype 2 (AdV2) and bacteriophage MS2. Modifying TiO2 with silver (nAg/TiO2) or silica (SiO2-TiO2) improves the inactivation kinetics of bacteriophage MS2 by a factor of 3-10. nAg/ TiO2 increases hydroxyl radical (HO•) production while SiO2 increases the adsorption of MS2 to TiO2. These results suggest that modifying the photocatalyst surface to increase contaminant adsorption is an important improvement strategy along with increasing HO• production. The inactivation kinetics of AdV2 by P25 TiO2 is much slower than the MS2 inactivation kinetics and displays a strong shoulder, which is not present in the MS2 kinetics. nAg/TiO2 initially improves the inactivation rate of AdV2. SiO2-TiO2 reduces the AdV2 inactivation kinetics since adsorption is not significantly enhanced, as it is with MS2. Amino-C60 is highly effective for AdV2 inactivation under visible light irradiation, making it a good material for use in solar disinfection systems. The efficacy of amino-fullerene also demonstrates that singlet oxygen is effective for AdV2 inactivation. When exposed to irradiated TiO2, AdV2 hexon proteins are heavily damaged resulting in the release of DNA. DNA damage is also present but may occur after capsids break. With MS2, the host interaction protein is rapidly damaged, but not the coat protein. The kinetics of MS2 inactivation are rapid since it may quickly lose its ability to attach to host cells, while AdV2 kinetics are slower since the entire capsid must undergo heavy oxidation before inactivation occurs. Adenovirus inactivation likely occurs through breaching the capsid followed by radical attack of DNA and core proteins.

Photocatalytic oxidation is an alternative water treatment method under consideration for disinfecting water. Chlorine disinfection can form harmful byproducts, and some viruses (e.g. adenoviruses) are resistant to other alternative disinfection methods. Photocatalytic oxidation using nano-sized photocatalytic particles (e.g. TiO2, fullerene) holds promise; however, it is limited by its low efficiency and long required treatment times. This research focuses on improving virus inactivation by photocatalytic oxidation by modifying catalysts for improved activity, by analyzing virus inactivation kinetics, and by elucidating the inactivation mechanisms of adenovirus serotype 2 (AdV2) and bacteriophage MS2. Modifying TiO2 with silver (nAg/TiO2) or silica (SiO2-TiO2) improves the inactivation kinetics of bacteriophage MS2 by a factor of 3-10. nAg/ TiO2 increases hydroxyl radical (HO•) production while SiO2 increases the adsorption of MS2 to TiO2. These results suggest that modifying the photocatalyst surface to increase contaminant adsorption is an important improvement strategy along with increasing HO• production. The inactivation kinetics of AdV2 by P25 TiO2 is much slower than the MS2 inactivation kinetics and displays a strong shoulder, which is not present in the MS2 kinetics. nAg/TiO2 initially improves the inactivation rate of AdV2. SiO2-TiO2 reduces the AdV2 inactivation kinetics since adsorption is not significantly enhanced, as it is with MS2. Amino-C60 is highly effective for AdV2 inactivation under visible light irradiation, making it a good material for use in solar disinfection systems. The efficacy of amino-fullerene also demonstrates that singlet oxygen is effective for AdV2 inactivation. When exposed to irradiated TiO2, AdV2 hexon proteins are heavily damaged resulting in the release of DNA. DNA damage is also present but may occur after capsids break. With MS2, the host interaction protein is rapidly damaged, but not the coat protein. The kinetics of MS2 inactivation are rapid since it may quickly lose its ability to attach to host cells, while AdV2 kinetics are slower since the entire capsid must undergo heavy oxidation before inactivation occurs. Adenovirus inactivation likely occurs through breaching the capsid followed by radical attack of DNA and core proteins.

Pulsed laser ablation ¡]PLA¡^in single shot on polycrystalline Ti thin foil ca. 20

In this research, hills-like hierarchical structured TiO2 photoanodes for dye-sensitized solar cells (DSSCs) have been prepared. We expected these appropriately aggregated TiO2 clusters in photoanode layer could cause stronger light scattering and higher dye loading that increased efficiency of photovoltaics. For detailed light-harvesting study, different molecular weight of polyvinyl alcohol (PVA) polymers were used as binders for TiO2 nanoparticles (P-25 Degussa) aggregation. After preparing a series of TiO2 films with dissimilar morphology, the reflection of TiO2 films, absorbance of attached dye, amount of dye loading, and performance of fabricated DSSC devices were measured and investigated. An optimized device had higher dye loading and well light harvesting at the same time that induced a 23% increase of short-circuit current Jsc in DSSCs. Moreover, we found that electrolyte could penetrate or diffuse easily in this higher porous structure. We fabricated dye-sensitized solar cells with MPN-based liquid electrolyte and gel polymer electrolyte. From this structure, the short-circuit current Jsc was increased around 16% and 19% respectively compared to conventional layers with liquid electrolyte and gel polymer electrolyte devices. The increase in highly viscous system of gel polymer electrolyte is due to easier penetration by such hills-like hierarchical structure.

Ti thin films were deposited by a radio frequency ion-beam sputtering system. Deposition resulted from sputtering a Ti target (99.995%) with an Ar ion beam. Epitaxial TiO thin films with different orientations, which came from oxidizing Ti thin films, were prepared on single-crystal NaCl substrate. The formation of epitaxial TiO2 thin films (anatase or rutile phase) by oxidation of epitaxial TiO thin films was investigated. The composition, microstructure, and orientation relationships between interfaces were analyzed by TEM and Fourier transformation in the present report. Epitaxial TiO thin films with different orientations were prepared on single-crystal NaCl substrate in the present study. The formation of epitaxial TiO2 thin films (anatase or rutile) by oxidation of epitaxial TiO thin films, which were first grown on different NaCl surfaces, was investigated. The composition, microstructure, and orientation relationships between interfaces were analyzed by TEM and Fourier transformation in this report. The TiO to anatase phase transformation has been studied by transmission electron microscopy in this Article. It is shown that prior formation of TiO from Ti film can induce the formation of anatase by thermal oxidation in air, otherwise only rutile is formed. Ti film deposited on the NaCl (001) surface is induced to form epitaxial TiO film by thermal oxidation in air. Further thermal oxidation in air partially transformed TiO into anatase (A) with a parallel orientation relationship of {200}A // {200}TiO. Detailed analysis of the lattice fringes image of the specimen reveals the presence of very high density of misfit dislocations. The TiO to anatase transformation is reversible as further annealing in a vacuum can turn the anatase back into TiO and eliminates the misfit dislocations. The transformation is analyzed in terms of the crystal structure, orientation relationship, and the dislocation distribution, which show that the TiO to anatase transformation is due to the close similarity between their structures. (Chapter 1) The anatase TiO2 (001) surface was shown to have superior photoreactivity. Epitaxial anatase (001) films used to be grown on single-crystal SrTiO3 and LaAlO3 substrates. It is shown in this report that these films can be grown also on the NaCl substrate, which is much cheaper and easily prepared. Epitaxial TiO (001) films were first grown on the NaCl (001) substrate. By testing the TiO-to-anatase transformation over temperature and time ranges, an epitaxial anatase (001) film was prepared by simple thermal oxidation in air. The formation of a single-variant anatase (001) film instead of a multiple-variant film is discussed in this report. (Chapter 2) An epitaxial rutile (100) thin film has been grown on NaCl substrate instead of other more expensive substrates. An epitaxial TiO (111) thin film with minor Ti phase was first deposited on the NaCl (111) surface by thermal evaporation. It was then transformed into the epitaxial rutile (100) thin film by subsequent thermal oxidation in air. TEM was used to analyze the phases and the orientation relationship. Our previous result showed that an epitaxial anatase (001) film was formed on the NaCl (001) surface in a similar process. The substrate-dependent formation of different TiO2 phase is also discussed in terms of the mismatch of the interfaces. (Chapter 3)

Nitrogen-doped TiO2 nanotubes with enhanced visible light photocatalytic activity have been synthesized using commercial titania P25 as raw material by a facile P25/urea co-hydrothermal method. Morphological and microstructual characteristics were conducted by transmission electron microscopy, powder X-ray diffraction, and nitrogen adsorption/desorption isotherms; chemical identifications were performed using X-ray photoelectron spectroscopy, and the interstitial nitrogen linkage to the TiO2 nanotubes is identified. The photocatalytic activity of all nitrogen-doped TiO2 nanotubes synthesized by different urea content, evaluated by the decomposition of rhodamine B dye solution under visible light using UV¡VVis absorption spectroscopy, is found to exhibit higher degradation rate than that of P25. Factors affecting the photocatalytic activity of RB were analyzed and a possible mechanism of photodegradation was also proposed. The high photocatalytic activity was attributed to the process of two different mechanisms, one was the direct degradation of the chromophoric system and the other was successive deethylation of the four ethyl groups.

In This study a thin film of nanometric TiO2 was sol-gel prepared and used for heterogeneous photocatalytic reaction to treat chlorobenzene in testing solution and to evaluate its removal efficiency. Conventionally, the material of photocatalyst was mainly fabricated in form of powder used in the suspension system. Although TiO2 powder has a high specific surface area for heterogeneous photocatalysis, it still leaves a great number of suspended solids in solution awaiting proper handling after the treatment is completed. Also, such suspended solids would pose ¡§shielding¡¨ effect from UV light, and thus affected the efficiency of photocatalytic degradation. To overcome this drawback, a proper mesh size of stainless steel webnet was first selected as a treatment substrate and TiO2 dip-coated, followed by calcination at 500¢J. The end product was used as the TiO2 photocatalytic film for this study. The film of TiO2, verified as anatase type of crystal lattice by XRD and SEM, contained particle sizes ranging from 10 to 20 nm. A solution containing chlorobenzene was used in the study to assess the extent of photocatalytic degradation by UV/TiO2 film. The test was to evaluate the effects of the number of dip-coating and calcining (thickness), initial pH, UV light intensity (@365 nm), and applied electric voltage on photocatalytic removal of chlorobenzene in the solution. The test results indicated that TiO2 film was capable of degrading chlorobenzene; however, enhancement of the degradation efficiency was found to be needed. It was also found that the degradation rate of chlorobezene increased with an increasing thickness of the film and UV light intensity. The pH of test solution was found to be insensitive to degradation of chlorobenzene, probably due to its non-dissociation nature. It was found that electric voltage exerted was unable to prevent electrons and holes from re-combining, and a negative effect of external voltage was even observed. Therefore, it was believed that voltage exertion was not beneficial to phtocatalysis in this study. Kinetics of the tests in this study assumed a pseudo-first-order reaction, which resulted in a rate constant k' = 1.3¡Ñ10-5¡]min-1¡^. The reaction rate was found to be proportional to the 0.7507 order of UV light intensity.

This thesis is about the phase transformation, shape, size distribution and coalescence of TiO2 (part I) and ZrO2 (part II) nanopartilces produced by Nd-YAG laser ablation on metal targets under oxygen background gas, and characterized by analytical electron microscopy. The optimum laser ablation condition that satisfactory and routinely yield high-pressure phases of TiO2 (i.e. £\-PbO2-type and fluorite-related structures) and ZrO2 with high residual stress were reported. Part I-1 focuses on physical coagulation, by Van der Waals force, of the TiO2 condensates at temperatures up to about 1000 K as a result of post-condensation radiant heating. In part I-2, imperfect oriented attachment of nanoparticles over specific surfaces is rationalized to cause accretion and defects for the rutile condensates. Brownian motion may proceed above a critical temperature for anchorage release at the interface of imperfect attached nanoparticles until an epitaxial relationship is reached. Part I-3 deals with further the Brownian-type rotation of the imperfectly impinged £\-PbO2-type TiO2 and rutile nanocondensates until interfacial-energy cusp was reached. In part I-4 laser ablation condensation synthesis of dense TiO2 polymorphs and their phase transformations were documented. Part II-1 is about dense tetragonal (t)-ZrO2 and cubic (c-) nanocondensates which were synthesized under very rapid heating and cooling by pulsed Nd-YAG laser ablation with oxygen background gas. The t-ZrO2 nanoparticles were found to form deformation twins/faults and followed unique transformation path upon local electron dosage. Electron diffraction indicated that the dense c- and t- phase with specific size and residual stress were allowed to relax and/or kinetically phase change into lower-energy state as constrained by the intersections of the internal energy vs. cell volume plots calculated for the two polymorphs (Part II-2).