Wastewater Electrolysis Cell for Environmental Pollutants Degradation and Molecular Hydrogen Generation

This study proposes a wastewater electrolysis cell (WEC) for on-site treatment of human waste coupled with decentralized molecular H₂ production. The core of the WEC includes mixed metal oxides anodes functionalized with bismuth doped TiO₂ (BiO_x/TiO₂). The BiO_x/TiO₂ anode shows reliable electro-catalytic activity to oxidize Cl- to reactive chlorine species (RCS), which degrades environmental pollutants including chemical oxygen demand (COD), protein, NH4⁺, urea, and total coliforms. The WEC experiments for treatment of various kinds of synthetic and real wastewater demonstrate sufficient water quality of effluent for reuse for toilet flushing and environmental purposes. Cathodic reduction of water and proton on stainless steel cathodes produced molecular H2 with moderate levels of current and energy efficiency. This thesis presents a comprehensive environmental analysis together with kinetic models to provide an in-depth understanding of reaction pathways mediated by the RCS and the effects of key operating parameters. The latter part of this thesis is dedicated to bilayer hetero-junction anodes which show enhanced generation efficiency of RCS and long-term stability.

Chapter 2 describes the reaction pathway and kinetics of urea degradation mediated by electrochemically generated RCS. The urea oxidation involves chloramines and chlorinated urea as reaction intermediates, for which the mass/charge balance analysis reveals that N₂ and CO₂ are the primary products. Chapter 3 investigates direct-current and photovoltaic powered WEC for domestic wastewater treatment, while Chapter 4 demonstrates the feasibility of the WEC to treat model septic tank effluents. The results in Chapter 2 and 3 corroborate the active roles of chlorine radicals (Cl•/Cl₂^-•) based on iR-compensated anodic potential (thermodynamic basis) and enhanced pseudo-first-order rate constants (kinetic basis). The effects of operating parameters (anodic potential and [Cl^-] in Chapter 3; influent dilution and anaerobic pretreatment in Chapter 4) on the rate and current/energy efficiency of pollutants degradation and H₂ production are thoroughly discussed based on robust kinetic models. Chapter 5 reports the generation of RCS on Ir_0.7Ta_0.3O_y/Bi_xTi_1-xO_z hetero-junction anodes with enhanced rate, current efficiency, and long-term stability compared to the Ir_0.7Ta_0.3O_y anode. The effects of surficial Bi concentration are interrogated, focusing on relative distributions between surface-bound hydroxyl radical and higher oxide.

Trimethylsilyl anions: stereospecific deoxygenation of epoxides and trimethylsilyldehalogenation of aryl halides

I. Trimethylsilylpotassium reacts with epoxides to give olefins with inversion of stereochemistry. The reaction appears to proceed via the potassium β-silyl alkoxide (2) formed from the S_N2 attack of the silyl anion on the epoxide. Subsequent stereospecific synelimination of 2 affords the olefin of inverted stereo-chemistry. The reaction is convenient and preparatively useful.

The byproduct of the reaction, potassium trimethylsilanolate (17), effectively cleaves hexamethyldisilane to yield trimethylsilylpotassium. Since the latter reagent is generated and reacted in situ with epoxides, the overall reaction can be carried out with less than one equivalent of potassium methoxide.

II. The reaction of aryl halides with trimethylsilyl anions in HMPT provides good yields of aryltrimethylsilanes, useful synthetic intermediates. The choice of metal cation is unimportant. Chlorides and bromides give high yields of silylated products, while iodides give lower yields, with correspondingly increased amounts of reduced products. Arylammonium and arylphosphonium salts also undergo the reaction.

We have permissive evidence for the reaction proceeding via both aryl radical and aryl anion intermediates.

III. Trimethylsilyl and trimethylstannyl methoxycarbene complexes of chromium and tungsten have been prepared. One of these, (CO)_5WC(OMe)SnMe_3, reacts with norbornene at 80° to afford a new olefin polymer. Efforts to effect the alpha-elimination of the nonmetallic carbene ligands have not yet been successful. Reactions of these carbene complexes with acetone have been investigated.

Geometrical effects on the resonance absorption of neutrons

An investigation was conducted to estimate the error when the flat-flux approximation is used to compute the resonance integral for a single absorber element embedded in a neutron source.

The investigation was initiated by assuming a parabolic flux distribution in computing the flux-averaged escape probability which occurs in the collision density equation. Furthermore, also assumed were both wide resonance and narrow resonance expressions for the resonance integral. The fact that this simple model demonstrated a decrease in the resonance integral motivated the more detailed investigation of the thesis.

An integral equation describing the collision density as a function of energy, position and angle is constructed and is subsequently specialized to the case of energy and spatial dependence. This equation is further simplified by expanding the spatial dependence in a series of Legendre polynomials (since a one-dimensional case is considered). In this form, the effects of slowing-down and flux depression may be accounted for to any degree of accuracy desired. The resulting integral equation for the energy dependence is thus solved numerically, considering the slowing down model and the infinite mass model as separate cases.

From the solution obtained by the above method, the error ascribable to the flat-flux approximation is obtained. In addition to this, the error introduced in the resonance integral in assuming no slowing down in the absorber is deduced. Results by Chernick for bismuth rods, and by Corngold for uranium slabs, are compared to the latter case, and these agree to within the approximations made.

Metallogenic Provinces of the Southwestern United States and Northern Mexico

Some of the metallogenic provinces of the southwestern United States and northern Mexico are defined by the geographic distribution of trace elements in the primary sulfide minerals chalcopyrite and sphalerite. The elements investigated include antimony, arsenic, bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, molybdenum, nickel, silver, tellurium, thallium, and tin. Of these elements, cobalt, gallium, germanium, indium, nickel, silver, and tin exhibit the best defined geographic distribution.

The data indicate that chalcopyrite is the preferred host for tin and perhaps molybdenum; sphalerite is the preferred host for cadmium, gallium, germanium, indium, and manganese; galena is the preferred host for antimony, bismuth, silver, tellurium, and thallium; and pyrite is the preferred host for cobalt, nickel, and perhaps arsenic. With respect to the two minerals chalcopyrite and sphalerite, antimony, arsenic, molybdenum, nickel, silver, and tin prefer chalcopyrite; and bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, and thallium prefer sphalerite. This distribution probably is the result of the interaction of several factors, among which are these: the various radii of the elements, the association due to chemical similarities of the major and trace elements, and the degree of ionic versus covalent and metallic character of the metal-sulfur bonds in chalcopyrite and sphalerite. The type of deposit, according to a temperature classification, appears to be of minor importance in determining the trace element content of chalcopyrite and sphalerite.

A preliminary investigation of large single crystals of sphalerite and chalcopyrite indicates that the distribution within a single crystal of some elements such as cadmium in sphalerite and indium and silver in chalcopyrite is relatively uniform, whereas the distribution of some other elements such as cobalt and manganese in sphalerite is somewhat less uniform and the distribution of tin in sphalerite is extremely erratic. The variations in trace element content probably are due largely to variations in the composition of the fluids during the growth of the crystals, but the erratic behavior of tin in sphalerite perhaps is related to the presence of numerous cavities and inclusions in the crystal studied.

Maps of the geographic distribution of trace elements in chalcopyrite and sphalerite exhibit three main belts of greater than average trace element content, which are called the Eastern, Central, and Western belts. These belts are consistent in trend and position with a beltlike distribution of copper, gold, lead, zinc, silver, and tungsten deposits and with most of the major tectonic features. However, there appear to be no definite time relationships, for as many as four metallogenic epochs, from Precambrian to late Tertiary, are represented by ore deposits within the Central belt.

The evidence suggests that the beltlike features have a deep seated origin, perhaps in the sub-crust or outer parts of the mantle, and that the deposits within each belt might be genetically related through a beltlike compositional heterogeneity in the source regions of the ores. Hence, the belts are regarded as metallogenic provinces.

Upconversion and fluorescence spectral studies of Er3+/Yb3+-codoped Bi(2)Q(3)-GeO2-Ga(2)Q(3)-Na2O glasses

The absorption spectra and upconversion fluorescence spectra of Er3+/-Yb3+-codoped natrium-gallium-germanium-bismuth glasses are measured and investigated. The intense green (533 and 549 nm) and red (672 nm) emission bands were simultaneously observed at room temperature. The quadratic dependence of the green and red emission on excitation power indicates that the two-photon absorption processes occur. The influence of Ga2C3 on upconversion intensity is investigated. The intensity of green emissions increases slowly with increasing Ga2O3 content, while the intensity of red emission increases significantly. The possible upconversion mechanisms for these glasses have also been discussed. The maximum phonon energy of the glasses determined based on the infrared (IR) spectral analysis is as low as 740 cm(-1). The studies indicate that Bi2O3-GeO2-Ga2O3-Na2O glasses may be potential materials for developing upconversion optical devices (c) 2006 Published by Elsevier B.V.

氧化铋薄膜用于蓝光可录存储的研究

利用直流磁控溅射法在不同氧氩分压比条件下制备了BiOx薄膜。通过对薄膜在蓝光作用前后的反射率对比度变化的研究发现，氧氩分压比为50％时制备的薄膜具有最佳的光学对比度。利用X射线衍射仪(XRD)、X光电子能谱(XPS)和光谱仪研究了薄膜热处理前后的结构和光谱性质的变化。研究结果表明薄膜光学性质变化主要由薄膜中氧化铋的相变引起。蓝光静态测试结果显示氧氩分压比为50％条件下制备的BiOx薄膜具有很好好的记录敏感度，在11mW的记录功率和800ns的记录脉宽条件下，得到了52％的反射率对比度。此外，BiOx薄膜表现出了非常好的读出稳定性。

Effects of melting temperature on the broadband infrared luminescence of bi-doped and Bi/Dy co-doped chalcohalide glasses

Bismuth (Bi)-doped and Bi/Dy co-doped chalcohalide glasses are investigated as promising materials for amplifiers in optical communication. The samples synthesized at lower melting temperatures (MTs) are characterized by more intensified infrared emissions. With respect to the redox process of a liquid mixture at different MTs, we attribute an emission at 1230 nm to low-valent Bi ions. The lower MT favors the formation of LVB ions, i.e. Bi+ or Bi2+, while the higher MT promotes the production of higher-valent Bi ions Bi3+. An enhanced broadband infrared luminescence with the full-width at half-maximum over 200 nm is achieved from the present Bi/Dy co-doped chalcohalide glasses.

Ultrabroad infrared luminescences from Bi-doped alkaline earth metal germanate glasses

We report on ultrabroad infrared (IR) luminescences covering the 1000-1700-nm wavelength region, from Bi-doped 75GeO(2) 20RO-5Al(2)O(3) 1B(2)O(3) (R = Sr, Ca, and Mg) glasses. The full width at half-maximum of the IR luminescences excited at 980 nm increases (315 -> 440 -> 510 nm) with the change of alkaline earth metal (Mg2+ -> Ca2+ -> Sr2+). The fluorescence lifetime of the glass samples is 1725, 157, and 264 mu s when R is Sr, Ca, and Mg, respectively. These materials may be promising candidates for broad-band fiber amplifiers and tunable laser resources.

Ultrabroad infrared luminescence from Bi-doped aluminogermanate glasses

We report ultrabroad infrared luminescence from Bi-doped aluminogermanate glasses. The infrared luminescence almost covers the whole low loss wavelength region (1200-1650 nm) of silica glass fiber when excited by a diode laser at 980 nm. The full width at half maximum (FWHM) of the luminescence is 510 nm. The luminescence peak can be divided into three Gaussian peaks, and the fluorescence lifetime of the three emissions are 297 mu s, 470 mu s and 1725 mu s, respectively. These fluorescence properties indicate that the glasses are promising material for broadband optical amplifiers. (C) 2007 Elsevier Ltd. All rights reserved.

稀土离子掺杂的多组分玻璃光纤

abstract {Rare earth ions doped multi-component glass fibers have important application in broad band fiber amplifier and up-conversion fiber lasers. In this paper, the mechanism and the progress of study on rare earth ions doped multi-component glass fibers in broad band fiber amplifier and up-conversion fiber lasers are introduced and reviewed. The questions and the applications of rare earth ions doped multi-component glass fibers in the future are also prospected. Based on the present research progress, it is suggested to further study the tellurite and bismuth glasses, which are used as fiber materials in broad band fiber amplifier. To up-conversion fiber laser, it is still need to further investigate novel glasses, which has low phonon energy and good physical and chemical properties.}

SiO2 对Bi2O3-B2O3 玻璃体系光学、热学及结构的 影响

Glasses with compositions 50Bi2O3-xB2O3- (50-x)SiO2(x=0, 10, 20, 30, 40, 50) in mol% have been prepared by using a normal melt-quench technique. The effect of SiO2 addition on thermal stability, optical properties and structural characteristic on Bi2O3-B2O3 glass were systematically investigated by using XRD, DTA, ultraviolet-visible transmittance spectra, midinfrared transmittance spectra and Raman spectra. The experimental results demonstrate that, with the addition of SiO2, thermal stability of glass samples has been obviously improved. Once the amount of SiO2 is too much, the glass samples tend to be phase seperation which results in the decrease of thermal stability. With increasing SiO2 content, the UV cutoff edge firstly shifts to short-wave band and then shifts to long-wave band, and the transmittance of mid-infrared has been greatly improved. With substitution of SiO2 for B2O3, the [BO3] triangles and [BO4] tetrahedral groups are gradually replaced by [SiO4]. [BiO6] octahedral and [SiO4] tetrahedral units are connected forming a vibrational mode of Bi-O-Si. The physical chemistry and optical performance of Bi2O3-B2O3 glass were greatly improved by addition of SiO2.

Intense frequency upconversion luminescence in Yb3+/Tm3+-codoped oxychloride germanate glasses

Yb3+/Tm3+-codoped oxychloride germanate glasses for developing potential upconversion lasers have been fabricated and characterized. Structural properties were obtained based on the Raman spectra analysis, indicating that PbCl2 plays an important role in the formation of glass network and has an important influence on the maximum phonon energies of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4), respectively, were observed at room temperature. With increasing PbCl2 content, the intensity of blue (477 nm) emission increases significantly, while the red (650 nm) emission increases slowly. The results indicate that PbCl2 has more influence on the blue emissions than the red emission in oxychloride germanate glasses. The possible upconversion mechanisms are discussed and estimated. Intense blue upconversion luminescence indicates that these oxychloride germanate glasses can be used as potential host material for upconversion lasers. C (c) 2005 Springer Science + Business Media, Inc.

Frequency upconversion fluorescence emission of Er3+-doped oxychloride germanate glass

Frequency upconversion fluorescence property of Er3+-doped oxychloride germanate glass is investigated. Intense green and red emissions centred at 525, 546, and 657nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> 4I(15/2), and F-4(9/2) -> I-4(15/2), respectively, were simultaneously observed at room temperature. The quadratic dependence of the 525, 546, and 657nm emissions on excitation power indicates that a two-photon absorption process occurs under 975nm laser diode (LD) excitation. The Raman spectrum investigation indicates that oxychloride germanate glass has the maximum phonon energy at similar to 805 cm(-1). The thermal stability of this oxychloride germanate glass is evaluated by differential scanning calorimetry, and thermal stability factor Delta T (Delta T = T-x-T-g) is 187 degrees C. Intense upconversion luminescence and good thermal stability indicate that Er3+-doped oxychloride germanate glass is a promising upconversion laser material.

Upconversion emission in Er3+ doped novel bismuthate glass

Novel Er3+-doped bismuth lead strontiam glass was fabricated and characterized, and the absorption spectrum and upconversion spectrum of the glass were studied. The Judd-Ofelt intensity parameters Omega(t)(t = 2, 4, 6) were found to be Omega(2) = 3.27 x 10(-20) cm(2), Omega(4) = 1.15 x 10(-20) cm(2), and Omega(6) = 0.38 x 10(-20) cm(2). The oscillator strength, the spontaneous transition probabilities, the fluorescence branching ratios, and excited state lifetimes were also measured and calculated. The upconversion emission intensity varies with the power of infrared excitation intensity. A plot of log I-up vs log I-IR yields a straight line with slope 1.86, 1.88 and 1.85, corresponding to 525, 546, and 657 nm emission bands, respectively, which indicates that a two-photon process for the red and green emission.