Chemistry Commons^™

Effects Of Oxygen Coverage And Hydrated Proton Model On The Dft Calculation Of Oxygen Reduction Pathways On The Pt(111) Surface, Li-Hui Ou, Sheng-Li Chen

Journal of Electrochemistry

DFT calculation is used to study various possible steps in the oxygen reduction reaction (ORR), including the adsorption and dissociation process of O₂ and the serial protonation process of dissociated products to form H₂O on the Pt(111) surface. By using slabs of different sizes, and different numbers of pre-adsorbed oxygen atoms, the coverage effects on the pathways are investigated. The calculated results using different hydrated proton models are also compared. It is shown that the initial step of the ORR is the formation of a protonated end-on chemisorbed state of OOH*, which can transform to an unprotonated …

Electrochemistry At Liquid/Liquid Interfaces And Its Recent Progresses, Jing Gu, Yong-Hui Qiao, Xin-Yu Zhu, Xiao-Hong Yin, Xin Zhang, Ye Chen, Zhi-Wei Zhu, Yuan-Hua Shao

Journal of Electrochemistry

Electrochemistry and electroanalytical chemistry at a liquid/liquid interface have attracted much attention in the past few decades since they have been closely related to many applications including exploration in mechanisms of extraction processes and chemical sensing, as well as investigations in phase transfer catalysis, drug release and mimicking the function of biological membranes. In this review, recent progresses in this field in the last decade, especially the investigations in microstructure of liquid/liquid interface, charge (ion and electron) transfer reactions and functionalization of liquid/liquid interfaces, are reviewed.

Synthesis, Characterization And Mechanistic Studies Of Biomolecules@Mesomofs, Yao Chen

USF Tampa Graduate Theses and Dissertations

Encapsulation of biomolecules is of great interest to research advances related to biology, physiology, immunology, and biochemistry, as well as industrial and biomedical applications such as drug delivery, biocatalysis, biofuel, food and cosmetics. Encapsulation provides functional characteristics that are not fulfilled by free biomolecules and stabilizes the fragile biomolecules. In terms of biocatalysis, solid support can often enhance the stability of enzymes, as well as facilitate separation and recovery for reuse while maintaining activity and selectivity. Various kinds of materials have been used for encapsulation of biomolecules, among which, porous materials are an important group. Metal-organic frameworks (MOFs) have attracted …

Metal Nanoparticles Immobilized On Basic Supports As Catalysts For Hydrogenation And Dehydrogenation Reactions Of Relevance To Cleaner Fossil Fuels And Alternative Sources Of Energy, Reena Rahi

Dissertations, Theses, and Capstone Projects

We developed a series of catalysts, composed of metal nanoparticles immobilized on basic supports for the hydrogenation of heteroaromatics of relevance to cleaner fossil fuels and biodiesel, and for the dehydrogenation of heteroaromatics of relevance to hydrogen storage in organic liquids. Our catalyst design involves nanostructured catalysts composed of metal particles immobilized on basic supports capable of ionic mechanism that may avoid catalyst poisoning and enhance catalytic activity.

We prepared a new catalyst composed of Pd nanoparticles immobilized on MgO by NaBH4 reduction of Na2PdCl4 in methanol in the presence of the support. TEM measurements revealed well-dispersed 1.7 nm Pd …

Reduction Of Ketoximes To Amines By Catalytic Transfer Hydrogenation Using Raney Nickel And 2-Propanol As Hydrogen Donor, Katherynne E. Taylor

Honors Theses

Ketoximes successfully underwent hydrogenolysis and hydrogenation under catalytic transfer conditions with Raney Nickel and 2-propanol as a hydrogen donor. Ketoximes were reduced to primary amines when 2% KOH was included in the reaction. In the absence of KOH N-isopropyl-secondary-amines were obtained in good yields.

Study Of The Structure-Property Relationships That Determine The Effects Of Latexes And Starch Containing Latex Emulsions On The Performance Of The Barrier Coatings (Sub-Coat) For Paper, Joanna Marie Monfils

Master's Theses

The history of carbonless paper dates back to the 1940s. Before this, a carbon copy sheet was needed between sheets of paper to be able to produce one or more copies simultaneously during writing. The pressure from a pen or typewriter would help deposit the ink of the carbon paper onto the blank sheet of paper under the original written sheet to create a “carbon copy.” This method did however, have its disadvantages. Not only did it produce a limited number of copies, but it was also a messy process. So came the creative process of using microencapsulated dyes to …

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 …

Homochiral Metal-Organic Materials: Design, Synthetic And Enantioseletive Separation, Shi-Yuan Zhang

USF Tampa Graduate Theses and Dissertations

Owing to the growing demand for enantiopurity in biological and chemical processes, tremendous efforts have been devoted to the synthesis of homochiral metal-organic materials (MOMs) because of their potential applications in chiral separation and asymmetric catalysis. In this dissertation, the synthetic strategies for homochiral MOMs are discussed keeping the focus on their applications. Two distinct approaches have been taken to synthesize chiral structures with different topologies and accessible cavities. The chiral MOMs have been utilized in enantioselective separation of racemates.

Chiral variants of the prototypal metal-organic framework MOF-5, δ-CMOF-5 and [lambda]-CMOF-5, have been synthesized by preparing MOF-5 in the presence …

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.

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 …

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 …

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 …

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 …

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 …

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) …

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 …

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 …

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.

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.

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 …

Effect Of Multivalent Ions On The Swelling And Mechanical Behavior Of Superabsorbent Polymers (Saps) For Mitigation Of Mortar Autogenous Shrinkage, Qian Zhu

Open Access Theses

The chemical and physical structure-property relationships of model superabsorbent polymer (SAP) hydrogels were characterized with respect to swelling behavior and mechanical properties in different ionic solutions (Na+ , Ca2+ , and Al3+ ). The model hydrogels were composed of poly(sodium acrylate-acrylamide) (PANa-PAM) copolymer with varying concentrations of PANa (0, 17, 33, 67, and 83 wt.%) and covalent crosslinking densities of 1, 1.5, and 2 wt.%. By synthesizing the hydrogels in-house, systems with independently tunable amounts of covalent crosslinking and anionic functional groups were created, allowing for the relative effects of covalent and ionic crosslinking on the properties of the hydrogels …

The Development Of 6.7% Efficient Copper Zinc Indium Selenide Devices From Copper Zinc Indium Sulfide Nanocrystal Inks, Brian Kemp Graeser

Open Access Theses

As solar cell absorber materials, alloys of CuIn(S,Se)2 and Zn(S,Se) provide an opportunity to reduce the usage of indium along with the ability to tune the band gap. Here we report successful synthesis of alloyed (CuInS2 )0.5(ZnS)0.5 nanocrystals by a method that solely uses oleylamine as the liquid medium for synthesis. The reactive sintering of a thin film of these nanocrystals via selenization at 500 °C results in a uniform composition alloy (CuIn(S,Se)2 )0.5 (Zn(S,Se)) 0.5 layer with micron size grains. Due to the large amount of zinc in the film, the sintered grains exhibit the zinc blende structure instead …

Size-Dependent Interactions Of Metal Nanoparticles With Fluorophores And Semiconductors, Liyana A. Wajira Ariyadasa

Dissertations

In recent years, nanoscale metallic particles have gained considerable interest due to their potential applications in advanced technology. Despite such interest, synthetic procedures that produce gram-scale, well-defined metallic nanoparticles with controlled size and shape, especially with diameters less than 5 nm remains a challenge. Our work has focused on developing synthetic procedures that produce well-defined platinum and palladium metal nanoparticles in the 1-5 nm size range. Thioether ligands were used as stabilizers and resulted in metal nanoparticles with controlled size. The nanoparticles were characterized using transmission electron microscopy (TEM), x-ray diffraction (XRD), selected area electron diffraction (SAED), x-ray photoelectron spectroscopy …

Ultraviolet Light Emitting Diode Use In Advanced Oxidation Processes, Kelsey L. Duckworth

Theses and Dissertations

Cleanup from a hazardous chemical release can result in large volumes of water containing hazardous materials, such as organophosphates. Unfortunately, this water cannot be treated in a municipal wastewater treatment plant without adversely affecting the performance of the plant. A known method for pretreating this water to prepare it for processing in a traditional treatment plant includes the addition of hydrogen peroxide, followed by ultraviolet (UV) light exposure to form reactive hydroxyl radicals which oxidize the chemical. Light emitting diodes (LEDs) are explored as a UV source as they are durable; compact; can be powered by low voltage, direct current …

[M3(Μ3-O)(O2cr)6] And Related Trigonal Prisms: Versatile Molecular Building Blocks For 2-Step Crystal Engineering Of Functional Metal-Organic Materials, Alexander Schoedel

USF Tampa Graduate Theses and Dissertations

Metal-organic materials (MOMs) assembled from metal-based building blocks and organic linkers have attracted much interest due to their large pore dimensions and their enormous structural diversity. In comparison to their inorganic counterparts (zeolites), these crystalline materials can be easily modified to tailor pore dimensions and functionality for specifically targeted properties.

The work presented herein encompasses the development of a synthetic 2-step process for the construction of novel families of MOMs or 'platforms' and allow us exquisite design and control over the resulting network topologies. Examples of cationic mesoporous structures were initially exploited, containing carboxylate based centers connected by metal-pyridine bonds. …

Electrochemical Performance Of Si-C Composites Prepared By Discharge-Plasma Assisted Milling, Yu-Long Chen, Ren-Zong Hu, Hui Liu, Wei Sun, Min Zhu

Journal of Electrochemistry

Silicon-carbon (Si-C) composites, with microstructure of multi-scaled Si particles being homogenously dispersed in micro-sized carbon matrix, had been prepared by dielectric barrier discharge plasma assisted two-step milling for the first time. The Si-C composite anode had a discharge capacity of 1259 mAh·g^-1 at the first cycle, while the capacity retained 474 and 396 mAh·g^-1 after 20 and 100 cycles, respectively. Charge-discharge curves and AC impedance response indicated that both silicon and carbon phases in the composite anode were involved during the lithiation/delithiation reactions and the electron transport resistance in the Si-C composite anode was much lower than that …