Physical Chemistry Commons^™

Co2 Reduction Under Periodic Illumination Of Zns, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

The photoreduction of CO₂ to formate (HCOO^–) in sphalerite (ZnS) aqueous suspensions is systematically studied in the presence of Na₂S hole scavenger. A series of cut-on filters at λ_cut-on ≥ 280, 295, 305, 320, and 400 nm are used to measure the reaction rate of formate production. The dependence of the measured reaction rates on λ_cut-on indicates that a wavelength of λ = 345 nm is associated with the actual bandgap of the semiconductor nanocrystallites suspended in water. The results from apparent quantum yield measurements during periodic illumination experiments suggest that (1) valence-band …

Electrically Controlled Formation And Release Of Admicelles For Solid Phase Extraction, Sukyeon Lee

Masters Theses & Specialist Projects

Solid phase extraction is one of the most widely used methods to concentrate diluted compounds in a solution. Substances can be extracted into admicelles and hemimicelles, which are surface adsorbed micelles and surfactant monolayers, respectively. Investigations of the electrical control of surfactants on surfaces for the purpose of analyte preconcentration prior to chromatographic analysis are presented. The surfactant layer serves as the “stationary phase” in a solid phase extraction sorbent scenario. Analytes are adsorbed on this layer, and then released from the solid phase via surfactant removal. The attachment and removal of the surfactant are controlled by means of an …

The Analysis Of The Decomposition Of Hydrogen Peroxide Using A Schiff Base Copper Complex By Cyclic Voltammetry, Gavin James Rustin Mr.

Undergraduate Honors Theses

Copper(II) complexes of Schiff bases can be used in the catalysis of hydrogen peroxide to create water and oxygen. The mechanism and the kinetics of this disproportionation reaction by a dimeric copper(II) complex [CuSALAD]₂ are studied in this experiment, where SALAD refers to a Schiff Base ligand formed from salicyaldehyde and 1S,2S-D(+)-1-phenyl-2-amino-1,3-propanediol. By using cyclic voltammetry, the oxidation-reduction processes of a reaction may be monitored. The [CuSALAD]­₂ is initially reacted with a base such as imidazole to form the catalytic species, and the ratio of the copper(II) complex to the imidazole was found to be 1:4, consistent with …

Using A Spreadsheet To Solve The SchröDinger Equations For The Energies Of The Ground Electronic State And The Two Lowest Excited States Of H2, Yingbin Ge, Robert C. Rittenhouse, Jacob C. Buchanan, Benjamin Livingston

All Faculty Scholarship for the College of the Sciences

We have designed an exercise suitable for a lab or project in an undergraduate physical chemistry course that creates a Microsoft Excel spreadsheet to calculate the energy of the S₀ ground electronic state and the S₁ and T₁ excited states of H₂. The spreadsheet calculations circumvent the construction and diagonalization of the Fock matrix and thus can be accomplished by any undergraduate chemistry student with basic calculus skills. The wave functions of the S₀, S₁, and T₁ states of H₂ are constructed from the symmetry-adapted bonding and antibonding molecular …

Understanding The Influence Of Interfacial Chemistry In Core, Core/Shell And Core/Shell/Shell Quantum Dots On Their Fluorescence Properties, Omondi Bernard Omogo

Graduate Theses and Dissertations

Colloidal semiconductor nanocrystals (quantum dots) have received a great deal of attention due to their superior size tunable properties and promising applications in many areas. Some of the most practical areas of their applications include light emitting diodes (LED), photovoltaic and biological studies. Synthetic methods of these crystals is becoming more established with new strategies being reported every now and then. However, quantitative studies connecting the processes at the interface, namely core-ligand, core-shell and shell-shells, to the overall quantum dots fluorescence properties are not well understood. Specifically for cores, relating surface-atoms interactions, solvents, ligands nature, density and functional groups on …

Selection Of The Process Parameters For The Mass Plating Of Discrete Electronic Components, Ann Hopper

Articles

The miniaturisation of electronic components coupled with requirements for high temperature lead free soldering has forced the improvement of the termination finish of surface mount components to meet the critical demands of the electronic industry. In the present work the processing parameters necessary to plate miniature multilayer varistors (MLV’s) have been explored. The tooling selected was a “Rotary flow-thru’ plater” which achieved high volume plating with

Investigation Of Energy Alignment Models At Polymer Interfaces, Wenfeng Wang

USF Tampa Graduate Theses and Dissertations

The presented study investigated the Induced Density of Interface States (IDIS) model at different polymer interfaces by using photoemission spectroscopy in combination with electrospray deposition.

In recent years, organic electronics have attracted considerable attention due to their advantages of low-cost and easy-fabrication. The performance of such devices crucially depends on the energy barrier that controls the interface charge transfer. A significant effort has been made to explore the mechanisms that determine the direction and magnitude of charge transfer barriers in these devices. As a result of this effort, the IDIS model was developed to predict the energy alignment at metal/organic …

Preparation And Electrochemical Performances Of Cofe2O4/Gns Nanocomposites As Anode Material For Lithium Ion Battery, Mo-Chao Cai, Sen-Rong Cai, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

The CoFe₂O₄/GNS was synthesized by a simple one-pot solvothermal method. The results obtained by X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that the CoFe₂O₄ particles with sizes of 15 nm dispersed on the surface of graphene uniformly. Electrochemical tests indicated that the CoFe₂O₄/GNS nanocomposite exhibited excellent cyclic stability with almost 95.8% capacity retention after 100 cycles at the current density of 500 mA·g^-1 and delivered a high reversible capacity of 482 mAh·g^-1 at the current density of 2 A·g^-1.

Effect Of Temperature On The Self-Humidifying Open-Cathode Proton Exchange Membrane Fuel Cell, Si-Chen Zhao, Ben Wang, Qiu-Hong Jia, Ming Han, Yu-Hong Xie

Journal of Electrochemistry

Based on the experiments about the output characteristics of a home-made temperature-controlled PEMFC system with atmospheric pressure and no external humidifying condition in different loading voltages and operating temperatures, the optimum operating temperature at different loading voltages can be obtained by tracking the output characteristics of PEMFC operating over a range of temperatures. By analyzing the fitted data the kinetic parameters are evaluated and the effect of different operating temperatures on the PEMFC performance is discussed from a view of electrode kinetics.

Electrochemical Deposition Of Gasb Thin Films For Phase Change Memory In Aqueous Solutions, Yu-Lin Xiong, Yuan-Chun Pan, Bai-Sheng Sa, Jian Zhou, Zhi-Mei Sun

Journal of Electrochemistry

The synthesis of GaSb thin films has been successfully performed by a method involving one-step potentiostatic electrodeposition and thermal annealing. The effect of ethylene glycol as a solvent in aqueous electrolyte solution on the crystallinity and morphology of the prepared thin films was discussed. The electrodeposition mechanisms of GaSb were studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to analyze structure, morphology and composition of the thin films. The results show that SbO⁺ is first reduced to Sb, and Ga³⁺ is deposited via the induced co-deposition mechanism. The …

Implementation And Application Of The Mmff94 Force Field, Hongbo Zhu

Department of Chemistry: Dissertations, Theses, and Student Research

MMFF94 is implemented for molecular mechanics calculation in the quantum chemistry polarizable force field program (QuanPol). As a general force field for organic molecules, the availability of MMFF94 expends the capability of the QuanPol program. The MMFF94 force field atom type determination and parameter matching methods are established and corresponding program routines are written in the FORTRAN language. In this implementation, the MMFF94 atom types can be determined automatically from the connectivity of the input atoms with no or minimum information of formal charges. This implementation of MMFF94 is validated using the 761 standard tests, thus is a complete implementation. …

Preparation Of Pt/H-Tio2 Catalyst With Improved Catalytic Performance For Methanol Electrooxidation, Jin Han, Zhi-You Zhou, Qiang Wang, Miao-Qiang Lv, Chi Chen, Shi-Gang Sun

Journal of Electrochemistry

White TiO₂ nanorods were synthesized by hydrothermal method with TiCl₄ as a precursor. As-synthesized TiO₂ nanorods were further subjected to high-temperature (550 ^oC) heat treatment for 2 h under H₂ atmosphere to prepare gray black hydrogen-treated TiO₂ (H-TiO₂) nanorods with oxygen vacancies and Ti³⁺ interstitial atoms. The Pt nanoparticles of 1.9 nm were supported on these two types of TiO₂ nanorods to form Pt/TiO₂ and Pt/H-TiO₂ catalysts. XRD data indicates that the crystal structure of TiO₂ was still reserved as rutile after hydrogen treatment, but the surface …

An Equivalent Circuit Model For Redox Flow Battery Stack, Dong-Jiang You, Hua-Min Zhang

Journal of Electrochemistry

This paper introduces an equivalent circuit model for a redox flow battery stack. The model combines the electrochemical reaction of the battery cell and the shunt current of the battery stack. An all-vanadium redox flow battery stack of 1kW rated output power is tested through transient response and self-discharge experiments. All the parameters used for the modeling are obtained. Calculated shunt current and distribution of calculated battery voltage are shown in the results. It is concluded that the impedance of the battery stack can be obtained by the experimental results of the transient response and self-discharge measurements. The capacity lose …

In Situ Detection On Electrochemical Chloride Removal Of Reinforcement In Concrete By Combined Ph/Cl- Probes, Jing-Jing Wang, Shi-Gang Dong, Xiao-Juan Zhang, Hong-Wei Lv, Yun-Chang Wu, Rong-Gui Du, Chang-Jian Lin

Journal of Electrochemistry

In this work, the concrete samples polluted by chloride ion were electrochemically treated using galvanostatic technique, and the distributions of chloride ion concentration and pH value in the polluted concretes were in-situ monitored by embedding a combined pH/Cl^- probe during the electrochemical chloride removal. The corrosion behaviors of reinforcing steel in the concrete were simultaneously studied by using linear polarization and electrochemical impedance spectroscopy techniques (EIS). The micro environment of the concrete and corrosion rate of steel were explored during the electrochemical chloride removal. It was indicated that the Cl^- concentration in the concrete pore solution decreased with …

Effects Of Carbon Interlayer On Electrochemical Performance Of Lithium-Sulfur Cell, Jin-Peng Yu, Ming Zhang, Fei Ding, Zhi-Yuan Tang, Xing-Jiang Liu

Journal of Electrochemistry

Three kinds of conductive carbon films were prepared with Super-P (SP), KB and MWCNTs, and then the as-prepared carbon films were applied as an interlayer between a sulfur electrode and a separator for constructing a coin-type lithium-sulfur (Li-S) cell, respectively. The assessment results show that all the cells delivered the reversible capacities higher than 800 mAh·g^-1 after 40 cycles when the sulfur loading was up to 80% (by mass) in the sulfur electrode. Due to significant differences of physical properties among the carbon materials, the cell with a KB interlayer exhibited higher electrochemical polarization; the cycling performance of the …

Effect Of Al-Doping In Li-Rich Material Li1.2Mn0.543Co0.078Ni0.155Al0.030O2 For Lithium-Ion Batteries, Xiao-Xi Jin, Yi-Xiao Li, Yong Yang, Zhou-Cheng Wang

Journal of Electrochemistry

The Al-doped 0.5Li₂MnO₃·0.5Li(Mn_0.4Co_0.2Ni_0.4)O₂ compounds were successfully synthesized as cathode materials for lithium-ion batteries. The pristine and Al-doped materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and laser Raman spectroscopy. The results indicated that all the prepared materials were indexed as a hexagonal structure with R-3m space group, and Al element had been introduced into lattice. When cycled at 180 mA·g^-1 (1 C-rate), the capacity retention of 4% (by mole) Al-doped 0.5Li₂MnO₃·0.5Li(Mn_0.4Co_0.2Ni …

Electrochemical Behavior Of Ionic Liquid Confined Into Nanopores Of Silica Gel Matrix, Zuo-Peng Li, Ya-Qiong Wen, Mei-Xia Wu, Yong Guo

Journal of Electrochemistry

Imidazolium Ionic liquids (ILs) nano aggregates confined into nanopores of silica gel matrices (ILs-sg) modified electrodes were prepared by sol-gel process and characterized by cyclic voltammetry. Furthermore, the amounts of 15% ~ 28% ILs-sg and nano aggregates coated with ILs silica gel (ILs/sg) were prepared and their conductivities were evaluated by performing electrochemical AC impedance measurements from 20 ^oC to 80 ^oC. The abnormal results showed that, 1) comparing with the bulk IL, the confined IL had a positive shift effect of Fc/Fc+ redox potential; 2) when IL confined into a nanospace, the electrochemical stability became poor; 3) …

Electrodeposition Of Copper From A Choline Chloride Based Ionic Liquid, Rostom Ali M., Ziaur Rahman Md., Sankarsaha S.

Journal of Electrochemistry

The electrodeposition of copper from a solution containing copper chloride in either an ethylene glycol (EG)-choline chloride based or a urea-choline chloride based ionic liquid has been carried out onto a steel cathode by constant current and constant potential methods at room temperature. The influences of various experimental conditions on electrodeposition and the morphology of the deposited layers have been investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It is shown that very smooth, shiny and dense with good adherence and bright metallic coloured copper coatings can be obtained from both EG and urea based ionic liquids at …

Electrocatalytic Oxidation Of Glycerol At The Platinum Electrode Modified With An Nd-Fe-Moo42- Cyano-Bridged Mixed Coordination Polymer, Yong-Jun Ma, Yu-Xiu Tian, Jing Liu, Min Zhou, Jing Ding, Zhi-Mei Jin, Xiang-Mei Wang

Journal of Electrochemistry

A platinum electrode decorated with the ordered Nd-Fe-MoO₄^2- cyano-bridged mixed coordination polymer was successfully prepared by electrodeposition in virtue of the lyotropic liquid crystal soft template methods, and electrocatalytic oxidation behavior of glycerol was investigated on the chemically modified electrode by cyclic voltammetry. The influences of experimental factors such as the concentrations of H⁺ and SO₄^2- in electrolytes, glycerol concentration and scan rate on the electrocatalytic activity of glycerol at the modified electrode were also studied. It indicated that the proper amount of SO₄^2- in weakly acidic electrolyte could help to improve the …

Application Of Ionic Liquid Pp14Tfsi In Electrolyte Systems For Rechargeable Mg Batteries, Jin-Jie Zhu, Fei-Fei Wang, Yong-Sheng Guo, Jun Yang, Yan-Na Nuli, Jiu-Lin Wang

Journal of Electrochemistry

A phenolated-based Mg salt was prepared. The mixture of THF and N-methyl-N-butyl-piperidinium bis(trifluoromethanesulfonyl)imide (PP14TFSI) serves as the mixed solvent instead of pure THF for rechargeable Mg batteries systems. This new type of electrolyte system not only has optimal reversibility of Mg, but also owns a wide electrochemical window (2.7 V vs. Mg) and high ionic conductivity (7.77 mS·cm^-1). More importantly, the addition of Ionic Liquid suppresses the volatility of THF and improves the safety of rechargeable Mg batteries. The result shows that the mixture of THF and piperidyl-based Ionic Liquid could be regarded as a good solvent candidate …

Detection Of Glucosamine Hydrochloride By Ion Chromatography With Integrated Pulsed Amperometric Detector, Yan-Qun Fan, Qing-Yang Chen, Jin-Mei Xia, Jian-Zhong Xu, Xun Xu, Chen Xu

Journal of Electrochemistry

Factors (integral potential, concentration of NaOH and flow rate) affecting detection of Glucosamine hydrochloride by ion chromatography with integrated pulsed amperometric detector were studied. As the integral potential increased, the detection signal first increased and then decreased, while the detection background and noise increased directly. The suitable integral potential should be 0.1 V. With the concentration of NaOH increased, the retention time descended sharply, while the integral area increased quickly before they are coming back into balance. The number of theoretical plates increased firstly and then decreased. The optimum concentration of NaOH was 50 mmol·L^-1. As the flow …

Electro-Catalytic Oxidation Of Hydrogen Peroxide On Au/ L-Methionine /Gc Electrode, Jian-Feng Fan, Xue-Mei Luo, Jing Li, Lou-Zhen Fan

Journal of Electrochemistry

The modified electrodes have been fabricated by generation of Au nanoparticle chains, which was produced by reaction between HAuCl4 and sodium citrate without any additional capping agents or surfactants. The self-assembled Au nanoparticles were attached to the surface of glassy carbon electrode (GCE) layer by layer, using L-methionine (L-Met), thiourea (TU), allyl thiourea (ATU) and polyvinylpyrrolidone (PVP) as a crosslinking agent, respectively. The experimental results showed that the electrochemical performance of the different modified electrodes varied in [Fe(CN)₆]^3-/4- solution. The Au/L-Met/GCE exhibited an excellent electrochemical property, which is superior to other modified electrodes. In addition, the catalysis …

Fabrication And Electrochemical Properties Of Graphene-Zno Nanocomposite, Chuan-Ling Men, Wan Wang, Jun Cao

Journal of Electrochemistry

In this work, the graphene-ZnO nanocomposite was successfully synthesized through a one-step solvothermal approach, using ethylene glycol as the solvent and reducing agent. The ZnO particles could be attached to the surfaces and edges of graphene sheet. The electrochemical performance of the nanocomposite was investigated by performing cyclic voltammetry, A.C. impedance and chronopotentiometry tests in 6 mol·L^-1 KOH. The results showed that the graphene-ZnO nanocomposite exhibited a nice electrochemical specific capacitance of 115 F·g^-1 determined in cyclic voltammetry test, or 71 F·g^-1 evaluated in chronopotentiometry test and good reversible charge/discharge behavior.

Preparation Of A New Laccase Biosensor Based On Bimetallic Pt/Au Particles And Chitosan/Silica Sol-Gel Hybrid Films For Determination Of Catechol, Tong-Fang Lou, Jian-Ying Qu, Huan-Huan Xing, Xue-Ping Du, Ying Dong

Journal of Electrochemistry

A novel laccase (Lac) biosensor was fabricated successfully by means of entrapping Lac into bimetallic Pt/Au particles and chitosan/silica (CS-SiO₂) sol-gel hybrid films, and then applied to determine catechol (CC) concentration. The experiment results showed that the biosensor can electrocatalyze the reduction of CC, and the peak current increased linearly with the concentration of CC in the range of 8×10^-7 ~ 1×10^-4 mol·L^-1 (r = 0.9993) with a detection limit of 7.9×10^-8 mol·L^-1 by cyclic voltammetric response. The biosensor exhibited good sensitivity, stability and reproducibility, with a broad linear range for potential applications.

Synthesis Of Platinum Nanocrystallites And Possible Electrocatalytic Properties For Methanol, Lei-Lei Lu, Bao-Zhong Du, Sha Sun, Jin-Fen Niu, Jie Zhao

Journal of Electrochemistry

Platinum nanocrystallites were synthesized by the colloidal method using oxamide as the stabilizer. The morphologies and electrocatalytic performances for methanol of platinum nanocrystallites prepared at different pH values and with different reactant ratios of precursor and stabilizer were investigated. It was found that the platinum nanocrystallites synthesized at pH=5 and with the reactant ratio of 1:20 showed the best electrocatalytic activity for methanol. The peak current density reached up to 1709 μA·cm^-2. Furthermore, the electrocatalytic activity of platinum nanocrystallites for methanol reduced significantly although the cyclic voltammograms in the blank solution were not obviously changed after exposing in …

Combustion Products Of Ethyl Tert-Butyl Ether Using Synchrotron Photoionization, Rong Yao, Martin Ng, David Osborn, Craig Taatjes, Giovanni Meloni

Creative Activity and Research Day - CARD

The photolytically Cl initiated oxidation reaction of ETBE was investigated at the Advanced Light Source located in the Lawrence Berkeley National Laboratory. Using the multiplex photoionization mass spectrometer data were collected at the low pressure (4-8 Torr) and temperature (298 – 700 K) regimes. Data analysis was performed via characterization of the reaction species photoionization spectra and kinetic traces. A reaction schematic including branching fractions determination is presented and discussed.

Investigation Of Oxidation Reaction Products Of 2-Phenylethanol Using Synchrotron Photoionization, Magaly Wooten, Anthony Medrano, David Osborn, Craig Taatjes, Giovanni J. Meloni

Creative Activity and Research Day - CARD

Photolytically Cl-initiated oxidation reaction of 2-phenylethanol (2-PE) was carried out at the Advanced Light Source (ALS) in the Lawrence Berkeley National Laboratory. Using the multiplex photoionization mass spectrometer, coupled with the tunable vacuum ultraviolet radiation of the ALS, data were collected at low pressure (4 – 6 Torr) and temperature (298 – 550 K) regimes. Data analysis was performed via characterization of the reaction species photoionization spectra and kinetic traces.

A Small Molecule That Binds And Inhibits The Etv1 Transcription Factor Oncoprotein, Marius C. Pop, Nicolas Stransky, Colin W. Garvie, Jean-Philippe Theurillat, Emily C. Hartman, Timothy A. Lewis, Cheng Zhong, Elizabeth K. Culyba, Fallon Lin, Douglas S. Daniels, Raymond Pagliarini, Lucienne Ronco, Angela N. Koehler, Levi A. Garraway

Chemistry Faculty Publications

Members of the ETS transcription factor family have been implicated in several cancers, where they are often dysregulated by genomic derangement. ETS variant 1 (ETV1) is an ETS factor gene that undergoes chromosomal translocation in prostate cancers and Ewing's sarcomas, amplification in melanomas, and lineage dysregulation in gastrointestinal stromal tumors. Pharmacologic perturbation of ETV1 would be appealing in these cancers; however, oncogenic transcription factors are often deemed “undruggable” by conventional methods. Here, we used small-molecule microarray (SMM) screens to identify and characterize drug-like compounds that modulate the biological function of ETV1. We identified the 1,3,5-triazine small molecule BRD32048 as a …

Hydration Of The Sulfuric Acid−Methylamine Complex And Implications For Aerosol Formation, Danielle J. Bustos, Berhane Temelso, George C. Shields

Faculty Journal Articles

The binary H₂SO₄−H₂O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H₂SO₄), methylamine (NH₂CH₃), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H₂SO₄(NH₂CH₃)(H …

Dipole Bound Excited States Of Polycyclic Aromatic Hydrocarbons Containing Nitrogen And Their Relation To The Interstellar Medium, Mallory L. Theis

Honors College Theses

Polycyclic aromatic hydrocarbons (PAHs) are the most abundant type of molecule present in the interstellar medium (ISM). It has been hypothesized that nitrogen replacement within a ring is likely for PAHs present in the ISM. Additionally, electrons, protons, and hydrogen atoms are readily added to or removed from PAHs creating a truly diverse set of chemistries in various interstellar regions. The presence of a nitrogen within a PAH (called a PANH herein) that is additionally dehydrogenated leads to a neutral radical with a large dipole moment. It has recently been shown through the use of high-level quantum chemical computations for …