Physical Chemistry Commons^™

Gas-Phase Ion/Ion Reactions Of Biomolecules: An Examination Of Carboxylate Reactivity And Arginine Based Non-Covalent Complexes, Nathan Zachary Barefoot

Open Access Theses

The advent of Electrospray Ionization with the ability to generate multiply charges ions has contributed significantly to the study of gas-phase ion/ion reactions. With the tools available in mass spectrometry it has been shown that these reactions are effective at transforming one type of gaseous ion into another through a series of reactions. This work examines some of these reactions and their application to field of proteomics specifically focusing on the amino acids of arginine and lysine. NHS reagents have been shown to react to both of these molecules with in the gas-phase under different conditions but have relies on …

Characterization Of Water-Solid Interactions In Crystalline Ingredients And Development Of Deliquescence Measurement Recommendations, Matthew C. Allan

Open Access Theses

There are five major mechanisms of water-solid interactions. The primary focus of this thesis was on two of these: deliquescence and hydrate formation. Many crystalline food ingredients are deliquescent compounds (e.g., NaCl, sucrose, and ascorbic acid) and some are both deliquescent and hydrate formers (e.g., glucose, thiamine HCl, citric acid). Deliquescence is the first order phase transformation of a crystalline solid to a solution above a critical relative humidity (RH) known as the deliquescence point (RH0). A crystalline hydrate is a pseudo-polymorph in which water is incorporated into the crystal structure, altering the molecular formula and the physical properties.^ To …

A New Silver Electrode Based On The Composite Silver Sulfide/Attapulgite As Ionophore, Wen-Zhuo Li, Ding-Jia Xu, Jun Wang, Jian-Long Wang

Journal of Electrochemistry

A novel silver ion selective electrode with its ionophore being a kind of organic/inorganic composite composed of silver sulfide and attapulgite has been prepared. Attapulgite is a type of natural inorganic polymer which has some properties similar to zeolite, such as a higher specific surface area and plenty of intercrystalline cavities. In this work, the silver ions were firstly adosrbed in the micropores of the attapulgite, then thioacetamidetiny was selected to mix with the prepared silver ions/ attapulgite composite. Owning to the existence of sulfur atoms in the structure of thioacetamide molecules, thioacetamide molecules can react with the silver ions/attapulgite …

Key Factors And Techno-Economic Analyses Of Manganese Electrolysis Process, Gui-Mei Han, Fu-Yuan Xu, Lin-Hua Jiang, Zhi-Gang Dan, Xiao-Juan Gao, Ning Duan

Journal of Electrochemistry

This paper first studied the key factors affecting the initial manganese electrolysis process, including concentration of Mn²⁺, electrolysis time, overpotential, and then optimized these processing parameters with the chronocoulometry method under a three-electrode system. The results showed that, during the initial manganese electrolysis process, hydrogen evolution occurred more significantly on the stainless steel surface. As electrolysis process continued, manganese covered the stainless steel surface gradually, and hydrogen evolution reaction restrained which all contributed to the higher current efficiency. Besides, the limiting current density appeared at high overpotential region, and the reaction was controlled by diffusion process. In 0.02 …

Surface Enhanced Raman Spectroscopic Studies Of Pyridine Adsorbed On Ti/Au@Sio2 Film Electrode, Min-Min Xu, Ke Liu, Qing-Hua Guo, Jian-Lin Yao

Journal of Electrochemistry

This study was performed based on shell-isolated nanoparticles-enhanced Raman spectroscopy (SHINERS) technology. The Au@SiO₂ nanoparticles were prepared and characterized by TEM and cyclic voltammetry. It was shown that the shell of SiO₂ was compact. The high quality signal measured by surface enhanced Raman spectroscopy (SERS) was obtained from the adsorbed pyridine on Ti/Au@SiO₂ electrode. The origin of the SERS signals was further confirmed by testing Pt and Ni electrodes. In addition, potential dependent adsorption behavior was investigated. It was found that pyridine was adsorbed parallel on the surface from -0.1 V to -0.6 V, and converted to …

Horseradish Peroxidase-Attapulgite Clay Nanocomposites: Fabrication And Application To Sensing The Extracellular H2O2 Released From Cells, Ping Wu, Chen-Xin Cai

Journal of Electrochemistry

The nanostructured attapulgite clay was employed as a support matrix for immobilizing horseradish peroxidase (HRP). FTIR and electrochemical methods demonstrated that HRP had been effectively assembled on attapulgite surface with the formation of HRP-attapulgite nanocomposites. The HRP-attapulgite hybrid was deposited on the glassy carbon (GC) electrode forming the HRP-attapulgite/GC electrode. Cyclic voltammetric results showed a pair of well-defined redox peaks, which were ascribed to direct electron transfer (DET) of HRP, with the formal potential E₀′ = -335 mV (vs. SCE) in the phosphate buffer solution (PBS, pH 7.0). The dependence of E₀′ on solution pH indicated …

Novel Electrochemical Interfaces Based On Functional Nanomaterials And Their Related Applications, Cheng-Zhou Zhu, Lei Han, Shao-Jun Dong

Journal of Electrochemistry

Due to the unique optical, electronic, magnetic and catalytic properties, functional nanomaterials provide new opportunities for the rapid development in a variety of disciplines and show considerable promise in different fields. Specifically, constructions of the novel electrochemical interface using various nanomaterials and exploring their advanced electrochemical properties have received great attention to develop electrochemical devices with potential applications. In this account, we focus on our up-to-date progress in the construction of novel electrochemical interfaces based on nanomaterials, mainly highlighting our research advances on electrochemical sensors, fuel cells and fluorescence spectroelectrochemistry. These novel advanced nanomaterials endow them excellent performances and open …

Preparation And Photocatalytic Properties Of Zno Nanorod Arrays On Ti Substrates, Jia-Ming Yang, Ling-Jun Han, Li-Ping Zhong, Zhen-Hai Liang

Journal of Electrochemistry

In this paper, the uniform ZnO nanorod arrays were prepared by galvanostatic electrodeposition on Ti Substrates. The morphology and structure of samples were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effects of the concentration of Zn(NO₃)₂ and the deposition current on the morphology of the ZnO nanorod arrays were investigated. Photocatalytic properties of ZnO nanorod arrays were investigated by degradation of methyl orange (MO) under UV-light irradiation. The analysis revealed that the concentration of Zn(NO₃)₂ and the deposition current strongly influenced the morphology of the ZnO nanorod arrays. Compared with …

The Ionic Diffusion Model For The Solid Oxide Cathode And Its Verification By The Electrolysis Of Ta2O5 In Molten Cacl2, Hua-Lin Chen, Zhi-Yong Wang, Xian-Bo Jin, George Z. Chen

Journal of Electrochemistry

The deoxidation speed of a solid oxide cathode in molten CaCl₂ can be estimated by the PRS steady diffusion model of O^2-, which correlates the deoxidation speed with the precursor porosity, P, the metal-to-oxide molar volume ratio, R, and the cathode volume shrinkage S. The PRS model indicates that the porosity of the oxide cathode has important influence on the deoxidation speed, and provides a very simple equation for the prediction of the optimal cathode porosity. For the electrolysis of Ta₂O₅, the porosity of the cathode is better to be within 50%. …

Effects Of Conformational Transformations On Electronic Transport Properties Of Optical Molecular Switches: An Ab Initio Study, Yuan-Yuan He, Jian-Wei Zhao

Journal of Electrochemistry

A series of model molecules with 4 kinds of conformational transformations have been investigated as optical molecular switches by using density functional theory combined with nonequilibrium Green’s function method. The theoretical calculations show that molecules after conformational transformations have photoswitching characteristics. We find that the photochromic molecules with the same conformational transformation usually have a similar current on/off state when they are applied as photoshwitches. Among these transformations, the molecular switch with E(“trans”)/Z(“cis”)-isomerisation of the NN double bond has the highest current on-off ratio. The influences of the energy gap (HLG) between the highest occupied molecular orbital (HOMO) and the …

Microfabrication And Redox Properties Of The Single Microcrystal Of Na3Co(Cn)6/Nacl Solid Solution, Yi-Liang Zhu, De-Zhi Yang, Ya-Qiong Su, De-Yin Wu, Zhong-Qun Tian, Dong-Ping Zhan

Journal of Electrochemistry

Although the molecular structures are similar to each other, the redox property of Co(CN)₆^3- at solid/liquid interface is not so good as Fe(CN)₆^3-. In this paper, scanning electrochemical microscopy (SECM) was adopted to construct an electrochemical microsystem with a volume of fL~pL, in which a micropipette with micrometer-sized orifice was employed as the scanning tip. Due to the evaporation of water, the NaCl electrolyte is concentrated to form a microcrystal. During the crystallization, the redox species Co(CN)₆^3- replaced the sites of NaCl₆^5- unit due to their matching lattice parameters, i.e., the …

23Na Mas Nmr Spectroscopic Study Of Na2Mnpo4F As Cathode Material For Sodium-Ion Battery, Xu Hou, Gui-Ming Zhong, Xiao-Chen Lin, Zi-Geng Liu, Xiao-Biao Wu, Yong Yang

Journal of Electrochemistry

The Na₂MnPO₄F is one of the promising cathode materials for the sodium ion batteries. In the paper, we employed the ex situ X-ray diffraction and solid state NMR techniques to study the charge and discharge processes of this material, including the crystal structure and sodium sites changes. The ex situ x-ray diffraction patterns showed that two new diffraction peaks could be observed at 31^o and 36^o indicating an intermediate phase formed with the extraction of Na⁺. From the ²³Na MAS NMR spectrum of the material, three peaks were seen at -209 …

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.

Nitroxide Radicals For Low Frequency Electron Paramagnetic Resonance Imaging (Epri), Joshua R. Biller

Electronic Theses and Dissertations

Optimization of nitroxides as probes for EPR imaging requires detailed understanding of spectral properties such as spin lattice relaxation times, spin packet linewidths, and nuclear hyperfine splitting. Initial measurements of relaxation times for six low molecular weight nitroxides at X-band stimulated further measurement at frequencies between 250 MHz and 34 GHz. The impact of tumbling was studied with perdeuterated 2,2,6,6-tetramethyl-4-piperidinyl-1-oxyl (PDT) in five solvents with viscosities resulting in tumbling correlation times, τ_R, between 4 and 50 ps. A set of three ¹⁴N/¹⁵N pairs of nitroxides in water was selected such that τ_R varied between …

Ab-Initio Study Of H2 Adsorption Upon The 001, 110, And 100 Surface Of Magnesium, Thomas F. Armstrong

Theses and Dissertations

Until recently, the only pathway for H2 adsorption onto conventional magnesium thin films was the [001] surface. With the discovery of Mg nanoblade/nanotree fabrication, there are now multiple surfaces for adsorption. A keen understanding of each surface's hydrogen adsorption kinetics is a key part of deciding if these surfaces present a more attractive hydrogen storage material than conventional thin films. This study focused on the use of ab-initio methods to compare the adsorption of H2 molecules onto the [001], [100], and [110] surfaces as well as an analysis of hybrid functionals and their advantages over traditional functionals for minimum energy …

Organic-Inorganic Hybrid Nanostructures For Solar Cell Applications, Samir Mahdi Abdulalmohsin

Theses and Dissertations

The enticing electro-optical properties of nanostructured materials such as carbon nanotubes, graphene, CdS nanocrystals and ZnO nanowrie bring new vigor into the innovation of photovoltaics. The main purpose of this dissertation is to develop novel nano-structured materials for low cost solar cell applications. Fabrication, characterization, and solar cell application of organic-inorganic hybrid structures are the main focus of this research. Polyaniline (PANI)/multi-walled carbon nanotube (MWNT) composite films were synthesized by an electrochemical polymerization of aniline with airbrushed MWNTs on ITO substrates. It was found that the incorporation of MWNTs in PANI effectively increase the film conductivity with a percolation threshold …

X-Ray Structure Analysis And Topological Charge Density Studies Of Gossypol Derivatives, Carlos Zelaya

LSU New Orleans Theses and Dissertations

Gossypol and gossypol derivatives are natural byproducts of a variety of cotton plant species that poses interesting chemical, biological, and medicinal properties that are currently heavily researched. Supporting evidence suggest that gossypol and gossypol derivatives act on the Bcl-2 proteins that have been linked to certain cancers. Gossypol amine derivatives, specifically, are actively researched and a variety of amine derivatives have already been synthesized. However, gossypol and its derivatives are challenging compounds to work with because many of its derivatives tend to exist in various tautomeric forms. When analyzing gossypol and its derivatives it is the complex electron configuration that …

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 …