Chemical and Electrochemical Behavior of Graphene-Covered Silicon Photoanodes

This dissertation describes efforts over the last five years to develop protective layers for semiconductor photoelectrodes based on monolayer or few-layer graphene sheets. Graphene is an attractive candidate for a protective layer because of its known chemical inertness, transparency, ease of deposition, and limited number of electronic states. Monolayer graphene was found to effectively inhibit loss of photocurrent over 1000 seconds at n-Si/aqueous electrolyte interfaces that exhibit total loss over photocurrent over 100 seconds. Further, the presence of graphene was found to effect only partial Fermi level pinning at the Si/graphene interface with respect to a range of nonaqueous electrolytes. Fluorination of graphene was found to extend the stability imparted on n-Si by the monolayer sheet in aqueous Fe(CN)₆^3-/4- electrolyte to over 100,000 seconds. It was demonstrated that the stability of the photocurrent of n-Si/fluorinated graphene/aqueous electrolyte interfaces relative to n-Si/aqueous electrolyte interfaces is likely attributable to the inhibition of oxidation of the silicon surface.

This dissertation also relates efforts to describe and define terminology relevant to the field of photoelectrochemistry and solar fuels production. Terminology describing varying interfaces employed in electrochemical solar fuels devices are defined, and the research challenges associated with each are discussed. Methods for determining the efficiency of varying photoelectrochemical and solar-fuel-producing cells from the current-voltage behavior of the individual components of such a device without requiring the device be constructed are described, and a range of commonly employed performance metrics are explored.

An annotated bibliography of aquatic sediment traps and trapping methods

This annotated bibliography is intended to give as reasonably complete a review of the existing literature as possible, and to offer some practical guidance in the selection and operation of sediment traps in future monitoring programmes.

Chemical and electrochemical investigations of cobalt cyanide and ruthenium ammine complexes

Part I.

The stoichiometry and kinetics of the reaction between Co(CN₅H^3- and HgX₂ (X = CN, OH) have been investigated. The products of the reaction are two new complexes, [(NC)₅Co-HgX]^3- and [(NC)₅Co-Hg-Co(CN)₅]^6-, whose spectra are reported. The kinetic measurements produced a value for the forward rate constant of the reaction Co(CN)₅H^3- + OH^- k₁/k_-1 Co(CN)₅^4- +H₂O, k1 = (9.7 ± 0.8) x 10^-2 M^-1 sec^-1 at 24°C, and an equilibrium constant for the reaction K = 10^-6 M^-1.

Part II.

Unusually large and sharp "adsorption waves" appear in cyclic voltammograms of Co(CN)₅^3- and several cobalt(III) pentacyano complexes at stationary mercury electrodes. The nature of the adsorbed species and the reasons for the absence of the adsorption waves in polarograms taken with a d.m.e. have been examined. The data are compatible with the adsorption, in all cases, of a coordinatively unsaturated cobalt(II) complex, Co(CN)₄^2-, by means of a cobalt-mercury bond. When the resulting adsorbed complex is reduced, a series of subsequent chemical and electrode reactions is initiated in which three faradays of charge are consumed for each mole of adsorbed complex. The adsorption of the anionic complex strongly retards the reduction of other negatively charged complexes.

Part III.

A number of formal redox potentials for Ru^III (NH₃)₅L + e = Ru^II (NH₃)₅L and Ru^III(NH₃)₄L₂ + e = Ru^II (NH₃)₄L₂ (where L is various ligands) has been measured by cyclic voltammetry, potentiometry, and polarography and are discussed in terms of the properties of the ligands, such as π-accepting capability. Reduction of coordinated pyrazine in the complexes, Ru(NH₃)₅ Pz²⁺, cis- and trans-Ru(NH₃)₄Pz₂²⁺, on a mercury electrode has been observed. The behavior of this reduction in various acidity of the solution as well as the reoxidation of the reduction products are discussed.

Trapping success and population analysis of Siren lacertina and Amphiuma means

Siren and Amphiuma are two poorly known genera of aquatic salamanders that occur in the Southeastern United States. A primarily bottom-dwelling existence makes these salamanders difficult to detect with conventional sampling methodologies. Therefore, the current status of their populations is unknown. I compared the capture success of modified crayfish traps and plastic minnow traps in capturing these salamanders. In addition, a mark-recapture study of S. lacertina (Greater siren) and A. means (Two-toed amphiuma) was conducted at Okefenokee National Wildlife Refuge (southern Georgia) and at Katharine Ordway Preserve (north-central Florida) from August 2001 until September 2002. Crayfish traps were much more successful than minnow traps in catching siren and amphiuma. Crayfish traps yielded 270 captures for an overall capture success of 16%, whereas minnow traps yielded only 13 captures for an overall success rate of 0.05%. In addition, several marking techniques were evaluated, and of these, only passive integrated transponder (PIT) tags were retained for the duration of the study. Therefore, I recommend this marking technique for long-term monitoring of S. lacertina and A. means. Several variables were found to have significant effects on capture rates of salamanders. A. means were most often captured in summer and the number of captures was positively correlated with water temperature, water level, and rainfall. S. lacertina were most often captured during winter and spring. Number of captures was negatively correlated with water temperature, while no relationship was found with water level or rainfall. Trap day and baiting had no significant effect on number of A. means or S. lacertina captured. Recapture probabilities of both species were low, 0.025-0.03 for S. lacertina and 0.08-0.11 for A. means. Monthly survival rates were high, 0.77-0.97 for A. means and 0.88-1.00 for S. lacertina. Density estimates of 1.3 salamanders/m2 (S. lacertina) and 0.28 salamanders/m2 (A. means) were obtained for Lake Suggs using Jolly-Seber models. Siren and amphiuma make up a substantial part of wetland biomass and can impact many other wetland species. Thus, more attention must be focused on evaluating and monitoring their populations.

Comment on: Computation of the optical trapping force using an FDTD based technique

In this comment, problems associated with an oversimplified FDTD based model used for trapping force calculation in recent papers "Computation of the optical trapping force using an FDTD based technique" [Opt. Express 13, 3707 (2005)], and "Rigorous time domain simulation of momentum transfer between light and microscopic particles in optical trapping" [Opt. Express 12, 2220 (2004)] are discussed. A more rigorous model using in Poynting vector is also presented.

Influences of radiation trapping on spectroscopic properties of Er3+-doped fluorophosphate glasses

Fluorophosphate glasses with different contents of ErF3 were prepared. Due to the radiation trapping of Er, concentration dependence of the fluorescence lifetime is subject to distortion, and the stimulated-emission cross section calculated by the Fuchtbauer-Ladenburg equation is underestimated. The influence of radiation trapping on the measured fluorescence lifetime and width are investigated quantitatively. By comparing the intensity ratio of the 1556-1532 nm peak in the fluorescence spectrum with that in the stimulated-emission cross-section spectrum obtained according to the McCumber theory, the distortion ratio of fluorescence spectrum due to radiation trapping is obtained. An empirical way to quantitatively evaluate the influences of radiation trapping on fluorescence lifetime and width is proposed. (c) 2007 Optical Society of America.

Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels.

Effects of chloride substitution on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses

Effect of the substitutions of chloride for fluoride on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses has been investigated. The characteristic temperature of the glass does not changed obviously when the fluoride was taken place by chloride. Compared with samples of being free of ErF3, the doping samples are more inclined to be surface crystallization. Optical basicity in the glass system increases with increasing the negative charge provided by the chloride atoms and the absorption peak red shifted is observed in absorption spectra. XRD measurements show that not a single crystalline phase appears in the heated glass samples, which indicate the substitutions of chloride for fluoride with a variety of crystalline precipitation trends. (c) 2007 Elsevier B.V All rights reserved.

Effect of Al(PO3)(3) content on physical, chemical and optical properties of fluorophosphate glasses for 2 mu m application

The effect of Al(PO3)(3) content on physical, chemical and optical properties of fluorophosphate glasses for 2 mu m application, such as thermal stability, chemical durability, surface hardness, absorption spectra and emission spectra, is investigated. With the increment of Al(PO3)(3) content, the thermal stability characterized by the gap of T-g and T,, increases first and then decreases, and reaches the maximum level containing 5 mol% Al(PO3)(3) content. The density and chemical durability decrease monotonously with the introduction of Al(PO3)(3) content increasing, while the refractive index and surface hardness increase. Above properties of fluorophosphate glasses are also compared with fluoride glasses and phosphate glasses. The Judd-Ofelt parameters, absorption and emission cross sections are discussed based on the absorption spectra of Tm-doped glasses. The emission spectra are also measured and the 1.8 mu m fluorescence of the sample is obvious indicating that it is suitable to 2 mu m application. (c) 2008 Elsevier B.V. All rights reserved.

Blue-yellow ZnO homostructural light-emitting diode realized by metalorganic chemical vapor deposition technique

We report on the realization of ZnO homojunction light-emitting diodes (LEDs) fabricated by metalorganic chemical vapor deposition on (0001) ZnO bulk substrate. The p-type ZnO epilayer was formed by nitrogen incorporation using N2O gas as oxidizing and doping sources. Distinct electroluminescence (EL) emissions in the blue and yellow regions were observed at room temperature by the naked eye under forward bias. The EL peak energy coincided with the photoluminescence peak energy of the ZnO epilayer, suggesting that the EL emissions emerge from the ZnO epilayer. In addition, the current-voltage and light output-voltage characteristics of ZnO homojunction LEDs have also been studied. (c) 2006 American Institute of Physics.