Physical Chemistry Commons^™

Tetrabutylammonium Hexafluorophosphate As Flame Retardant Additive For Lithium Ion Batteries, Qing Zhao, Qian Zhang, Jing-Min Fan, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

Safety issues have been attracted more and more attentions due to the wide applications of lithium ion batteries. Introducing flame retardant additives are one of the effective strategies to improve the safety of lithium-ion batteries. In this paper, the tetrabutylammonium hexafluorophosphate (TBAPF₆) as a flame retardant additive was added to the electrolyte as a flame retardant additive to enhance the safety of lithium ion batteries. The self-extinguishing time (SET) and ionic conductivities of the electrolytes with different TBAPF₆ contents were investigated. It is found that TBAPF6 dramatically reduced the flammability of the electrolyte while slightly decreasing ionic …

Electrochemical Performance Of Sodium Difluoro(Oxalato)Borate As The Additive Of Non-Aqueous Electrolytes For Sodium-Ion Batteries, Ding Zhang, Qin Zhu, Ying Wang, Cheng-Long Zhao, Shi-Bin Liu, Shou-Dong Xu

Journal of Electrochemistry

Sodium ion battery has attracted worldwide and intensive attention recently, while the adoption of electrolyte additives has been considered as one effective strategy to promote the cell performance. Within this work sodium difluoro(oxalato)borate (NaDFOB) was prepared and adopted as an additive for the general non-aqueous electrolyte formula of 1 mol·L-1 NaClO4/EC/PC (Vol: Vol=1:1), and the effects of the additive concentration on ionic conductivity and oxidization decomposition voltage were investigated in detail. In addition, the cell performance evaluated by NaNi0.5Mn0.5O2 as the cathode was also studied. It reveals that the addition of NaDFOB into the NaClO4/EC/PC electrolyte resulted in the significantly …

Surface Chemical Properties Of Mo2C, W2C, Mo2N And W2N Probed With Co, Co2 And O2 Adsorption: A Dft Analysis, Jingyun Ye, Tianyu Zhang, Lingyun Xu, Shuxia Yin, Krishanthi Weerasinghe, Pamela Ubaldo, Ping He, Qingfeng Ge

Journal of Electrochemistry

Transition metal carbides and nitrides are attractive materials for electrodes in many electrochemical energy storage and conversion applications. In the present study, we use density functional theory slab calculations to characterize the surface chemical properties of molybdenum (Mo) and tungsten (W) carbides and nitrides, namely, Mo₂C, W₂C, Mo₂N and W2N with the adsorption of CO, CO₂ and O₂. These probing molecules provide measures of in both acidity/basicity and redox property of for the surfaces of these carbides and nitrides. Our results show that Lewis basic sites were responsible for CO_{2 …}

An Electrochemical Dissolution Study Of Ilmenite Fraction Of Beach Sand In Sulphuric Acid Solution, Rostom Ali M., K. Biswas R., Golam Zakaria Md.

Journal of Electrochemistry

Electrochemical techniques have been used to investigate the dissolution behaviors of ilmenite fraction of beach sand of Bangladesh in sulfuric acid solutions at various temperatures. It is seen from the cyclic voltammetric studies indicated that the dissolution of ilmenite is was very difficult without the addition of carbon powder in ilmenite. The effects of ilmenite-carbon ratio, acid concentration and temperature on cyclic voltammograms have been investigated to understand the dissolution process of ilmenite. The investigated results showed that the dissolution rate of ilmenite (FeTiO₃) is was slow at low applied reduction potentials and temperatures. However, the dissolution rate …

Preface For Special Issue On Theoretical And Computational Electrochemistry, Jun Cheng

Journal of Electrochemistry

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Electrostatic Interactions Of Water In External Electric Field: Molecular Dynamics Simulations, Qiang Zhu, Zigui Kan, Jing Ma

Journal of Electrochemistry

A series of molecular dynamics simulations with or without external electric field have been carried out for a bulk water with periodic boundary condition. The difference in radial distribution function of interatomic O…O distance is subtle, with and without external electric field, except for the orientation of dipole moments of water molecules. Without the applied external electric field, distribution of the orientation angle of dipole moments is rather broad. The induced local electric field is analyzed as a function of altitude in direction of electric field. The variation of the local induced electric field is increased as the increase of …

Thermo-Stability And Active Site Structure Of Fe/N/C Electrocatalyst For Oxygen Reduction Reaction, Chi Chen, Yu-Jiao Lai, Zhi-You Zhou, Xin-Sheng Zhang, Shi-Gang Sun

Journal of Electrochemistry

The development of Fe/N/C electrocatalyst for oxygen reduction reaction (ORR) is vital for the large-scale applications of proton exchange membrane fuel cells. Understanding the active site structure will contribute to the rational design of highly active catalysts. In this study, the as-prepared Fe/N/C catalyst based on poly-m-phenylenediamine (PmPDA-FeN_x/C) catalyst with the high ORR activity was subjected to the high-temperature heat treatment again at 1000 ~1500 ^oC. The degradation of in the ORR activity of PmPDA-FeN_x/C by with various heat treatments was correlated to the change of elemental compositions, chemical states and textural properties. As the …

Electric Current Induced Flow And Electrocapillary Deformation Of Liquid Wood Alloy In Naoh Aqueous Solution, Guo-Di Zhang, Qiao-Li Lin, Jian-Hong Cheng, Rui Cao

Journal of Electrochemistry

The phenomena of the electric current induced flow and electrocapillary deformation for a liquid Wood alloy in a NaOH electrolyte were studied. Electrocapillary behaviors for the liquid Wood alloy in NaOH electrolytes by applying external low voltages were investigated. The electrode reaction (redox reaction) induced the formation or removing removal of an oxide film, and further caused the drop deformation by decreasing or increasing an interfacial tension. The same polar charge in the electric double layer would also decrease the interfacial tension. In order to maintain the stability of system, the contact area of the interface would be expanded, and …

An Investigation Of The Synergistic Effect Between (1,3-Dioxolan-2-Ylmethyl)Triphenylphosphonium Bromide And Iodide Ion For The Corrosion Inhibition Of Zinc In Citric Acid, Saadawy M.

Journal of Electrochemistry

The effect of (1,3-Dioxolan-2-ylmethyl)-triphenylphosphonium bromide (DTPB) on the zinc corrosion in 0.5 mol·L^-1 citric acid solution was investigated at 30 ^oC using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. An ecofriendly bath was used for acid cleaning of zinc, which has not been widely used in literatures. The results showed that DTPB could serve as an effective inhibitor for the zinc corrosion in a citric acid solution with the inhibition efficiency of 98.9% at the DTPB concentration of 3×10^-3 mol·L^-1. A synergistic effect between DTPB and potassium iodide (KI) enhanced the inhibition …

A New Type Carbon Composited Molybdenum Doped Vanadium Oxide Nanowires As A Cathode Material For Sodium Ion Batteries, Guang-Rui Zhang, Li-Qiang Hu, Bao-Zhu Zhang

Journal of Electrochemistry

In recent years, the development of lithium ion batteries (LIBs) has been limited due to the insufficient lithium resource and increasing cost. As a promising candidate, sodium ion batteries (SIBs) with the similar electrochemical mechanism and lower cost than LIBs are developing rapidly. However, as a result of the larger radius of Na⁺ compared with Li⁺, the crystalline structures of the most electrode materials are damaged severely during the intercalation of Na⁺, which limits the electrochemical properties of SIBs. Thus, developing new types of electrode materials for SIBs is particularly important. Among the cathode materials, …

Influence Of Typical Anions In Seawater Environments On Corrosion Behaviors Of 5083 Aluminum Alloy, Yang-Fan Tu, Li-Ming Feng, Zhi-Gang Fang, Hai-Tao Liu, Ming-Hua Jing, Yong Guan

Journal of Electrochemistry

The interaction effects of typical anions, namely, Cl^-, HCO₃^- and SO₄^2-, presented in seawater environments on corrosion resistance behaviors of AA5083 aluminum alloy have been studied. The corrosion resistances of the 5083 aluminum alloy in different simulated seawater environments were tested by factorial analysis method. The polarization curves, the corrosion potentials, corrosion current densities and the breakdown potentials were examined in different concentrations of Cl^-, HCO₃^- and SO₄^2-.The corrosion behavior was analyzed by electrochemical impedance spectroscopy (EIS). The results showed that both Cl^-,  and …

Effects Of Temperature On The Nucleation And Growth Mechanism Of Pbo2 Electrodeposition, Lei Wang, Juan-Qin Xue, Li-Hua Yu, Chang-Bin Tang, Qiang Bi

Journal of Electrochemistry

In order to investigate the effects of temperature on the nucleation and growth of lead dioxide (PbO₂), the in situ electrochemical depositions of PbO₂ were carried out on the glassy carbon electrode at different temperatures, namely, 25℃,35℃, 45℃, 55℃, and 65℃.The cyclic voltammetric curves, the time-current and the time-potential curves,SEM images and XRD patterns of the PbO₂ coatings deposited at different temperatures were obtained. The results showed that the PbO₂ underwent nucleation and grew at different temperatures. The 3D continuous nucleation mode of PbO₂ electrodeposition remained unchanged with the increase of temperature. However, the …

Nanoparticle-Based Drug-Delivery Systems Studied By Second Harmonic Generation, Raju Ram Kumal

LSU Doctoral Dissertations

Second harmonic generation (SHG) is used to study different types of colloidal nanoparticle drug-delivery systems. The surface charge density, electrostatic surface potentials, and ion adsorptions of 50 nm colloidal gold nanoparticle samples coated with mercaptosuccinic acid are determined using SHG measurements under varying NaCl and MgCl₂ concentrations in water. Numerical solutions to the spherical Poisson-Boltzmann equation are fit to the SHG results to account for the nanoparticle surface curvature and ion adsorption to the Stern layer interface, showing excellent agreement with electrophoretic mobility measurements. In another study, nanoparticles of gold, silver and polystyrene are functionalized with microRNA using a …

Raman Spectroscopy Of Oxygen Evolution Catalysts And Psii Manganese Model Compounds, Sergei Shmakov, Daniel A. Hartzler, Alireza Karbakhsh Ravari, Yulia Pushkar

The Summer Undergraduate Research Fellowship (SURF) Symposium

Photosynthesis is the basis of life on earth, and oxygen evolution catalysts are key components of this complicated, yet not fully understood process. Photosystem II, a large membrane bound pigment-protein complex, is the key system that facilitates oxygenic photosynthesis via the oxygen evolving complex (a natural oxygen evolving catalyst). It is a key component in oxygen producing catalysts, which can be used in fields such as energy production and biomimetic catalysts. The oxygen evolution cycle, or Kok cycle going within it is still not studied completely. In this project, we were studying the vibrational (and structural) state of a Manganese …

Applying Machine Learning To Computational Chemistry: Can We Predict Molecular Properties Faster Without Compromising Accuracy?, Hanjing Xu, Pradeep Gurunathan, Lyudmila Slipchenko

The Summer Undergraduate Research Fellowship (SURF) Symposium

Non-covalent interactions are crucial in analyzing protein folding and structure, function of DNA and RNA, structures of molecular crystals and aggregates, and many other processes in the fields of biology and chemistry. However, it is time and resource consuming to calculate such interactions using quantum-mechanical formulations. Our group has proposed previously that the effective fragment potential (EFP) method could serve as an efficient alternative to solve this problem. However, one of the computational bottlenecks of the EFP method is obtaining parameters for each molecule/fragment in the system, before the actual EFP simulations can be carried out. Here we present a …

Temperature-Dependent Exciton Dynamics Of Superacid Treatment In Monolayers Of The Metal Dichalcogenide Mos2, Mingwei Zhou, Long Yuan, Jordan Snaider, Libai Huang

The Summer Undergraduate Research Fellowship (SURF) Symposium

To improve optoelectronic semiconductor materials, one of the most efficient research areas is the two-dimensional (2D) transition-metal dichalocogenides (TMDCs). It has been shown that organic nonoxidizing superacid bis(trifluoromethane)sulfonamide (TFSI) treatment of molybdenum disulfide (MoS₂) monolayer could uniformly enhance its photoluminescence by more than two orders of magnitude and also extend the lifetime of excitons. This could greatly improve the efficiency of the solar energy usage, but the mechanism behind it has not been fully understood. Extreme low temperatures (approximately 7K), which slow the surface exciton mobility, were applied to investigate the changes of treated MoS₂ monolayer surfaces. …

Transient Absorption Studies Of Cdse Nanocluster Passivated With Phenyldithiocarbamate Ligands., Yizhou Xie

Electronic Theses and Dissertations

Semiconductor nanocluster (SCNC) research is a rapidly growing field driven by the promising fact that properties of such materials can be tailored by modifying their size, shape, and structure. Combination of nanocluster and organic ligands provides even wider possibilities of design and development of effective and task-specific nanostructures. Understanding of and, eventually, control of energetics, interfacial interaction, and photoinduced processes in such highly heterogeneous structures is critical to invention of novel materials including those in photovoltaic devices. In the newly established Ultrafast Laser Facility (ULF), transient absorption pump-probe spectroscopy (TAPPS) has been employed to investigate the electron transfer (ET) and …

Controlled Electrochemical Synthesis Of Single One-Dimensional Metal Nanochains Across Microgap Electrodes., Amareshwari Konutham

Electronic Theses and Dissertations

This study mainly focuses on the fabrication of single one dimensional (1D) NP chains across the 5-micron gap of Au two electrode devices (TED). This has been achieved by electrochemical deposition of Ag onto the two electrodes, soaking the TED in 0.1 M Cetyltrimethyl ammonium bromide for 2-3 hours, and then close monitoring of the current as a function of time while a voltage across the two Ag coated Au electrodes in air. One dimensional Ag nanoparticle chain formation occurred by oxidation of Ag to Ag⁺ at the positive electrode followed by movement of Ag⁺ ions to the …

Synthesis And Catalytic Evaluation Of Novel C-Alpha-Methyl-Beta-Proline Analogues, And Concise Synthetic Approach To Nh-Fmoc-S-Trityl-C-Alpha-Methyl Cysteine, Hari Kiran Kotapati

Dissertations

In the field of chemistry there is a growing demand for small molecule organocatalysts such as amino acids, more specifically proline and its analogues, which could catalyze various key chemical reactions in the synthesis of several biologically important molecules. Even though natural proline is reported to catalyze various chemical reactions, its use as organocatalyst is limited mainly due to the solubility issues in the reaction media and high catalyst loadings, which is not very ideal for bulk scale manufacturing. To address these limitations we planned to develop unnatural analogues of proline that could catalyze the reactions with lower catalyst loadings …

Property Morphology Correlations Of Organic Semiconductor Nanowires, Frederick Marshall Mcfarland

Dissertations

Chemically doped and non-doped P3HT nanoaggregates are studied to establish a comprehensive understanding of the interplay between their morphology and various optoelectronic properties. One-dimensional nanoaggregates of P3HT are chosen as the model systems here due to their high surface/volume ratio and suitability for microscopic investigations.

Atomic force microscopy (AFM) and kelvin probe force microscopy (KPFM) are used to correlate property/morphology characteristics of non-doped P3HT nanowhiskers. Topographical measurements indicate that individually folded P3HT motifs stack via interfacial interactions to form nanowhiskers in solution. Further aging leads to multi-layered nanowhiskers with greater stability and less instances of π-π sliding of interfacial edge-on …

Ab Initio Methyl Linoleate Bond Dissociation Energies: First Principles Fishing For Wise Crack Products, Zachary Ryan Wilson

Graduate Theses/Dissertations

With the prices of petroleum reflecting demand for this finite resource, attention has been turned to alternative sources of energy. Biodiesel, defined as fatty acid methyl esters (FAMEs), exhibits many of the same properties as conventional diesel but is derived from biological sources. FAMEs are subsequently thermally cracked to form more light-weight petrochemical products. I aim to further understand the thermal cracking procedure, at an atomic-level, in hopes that this may aid in future engineering of viable fuels. I studied the effective computational modeling of bond disassociations in the FAME methyl linoleate. Bond dissociation in a 44-reaction database with known …

Electronic Structure Evaluation Of Competing Pathways In The Gold(Iii)-Catalyzed Ohloff-Rautenstrauch Cyclosimerization Converting Propargylic Acetates To Carene-Like Natural Products, Jeremy M. Hines

Graduate Theses/Dissertations

Propargylic acetates can lead to complex transformations upon exposure to a gold catalyst. Gold catalyzed transformations also allow for simple synthesis of a number of natural products. Gold (III)-cycloisomerization of a 5-acetoxy-1,6-enyne is reported to proceed through two pathways that differ in the order of major events: cyclization followed by ester migration (“cyclization first”) or the reverse (“migration first”). Both pathways could theoretically proceed in either order. This rearrangement is called the Ohloff-Rautenstrauch rearrangement and has high regio- and stereocontrol affording a bicylo[4.1.0]heptane carbon substructure. This rearrangement allows for the synthesis of the carene class of natural products. Computational modeling …

Novel Design Strategies For Platinum-Containing Conjugated Polymers And Small Molecules For Organic Solar Cells, Wenhan He

Chemistry and Chemical Biology ETDs

Current state-of-the-art organic solar cells (OSCs) adopt the strategy of using conjugated polymers or small molecules as donors and fullerene derivatives as acceptors in their active layers. Regarding to the donors of interest, the conjugated polymers and small molecules coupled with heavy metals have been less explored compared to their counterparts. Among various transition metal complexes applied, Pt(II) complexes are unique because of their intrinsic square planar geometries and ability to serve as building blocks for conjugated systems. Furthermore, the heavy metal Pt facilitates the formation of triplet excitons with longer life times through spin-orbital coupling which are of benefit …

Exploring Two Approximate Coupling Models In Exciton Transport, James Irish-Ryan

DePaul Discoveries

Point dipole and line dipole coupling approximations are two methods for approximating the transition dipole coupling between two conjugated organic molecules. Transition dipole couplings are an important factor in determining energy transfer between two non-covalently-bonded molecules. Transition dipole couplings were mathematically calculated by two methods, applying the point dipole and line dipole approximations. The calculations were implemented using Octave, an open source computer programming language. Using this tool, software was created to efficiently analyze the differences between transition dipoles calculated using the two methods, for a variety of relative orientations of two model conjugated organic molecules. Custom-built software was created …

High Resolution Spectra Of Carbon Monoxide, Propane And Ammonia For Atmospheric Remote Sensing, Christopher Andrew Beale

OES Theses and Dissertations

Spectroscopy is a critical tool for analyzing atmospheric data. Identification of atmospheric parameters such as temperature, pressure and the existence and concentrations of constituent gases via remote sensing techniques are only possible with spectroscopic data. These form the basis of model atmospheres which may be compared to observations to determine such parameters. To this end, this dissertation explores the spectroscopy of three molecules: ammonia, propane and carbon monoxide.

Infrared spectra have been recorded for ammonia in the region 2400-9000 cm^-1. These spectra were recorded at elevated temperatures (from 293-973 K) using a Fourier Transform Spectrometer (FTS). Comparison between …

Mixed Quantum/Classical Theory (Mqct) For Rotationally And Vibrationally Inelastic Scattering And Its Application To The Molecules Of Astrochemical Importance, Alexander Semenov

Dissertations (1934 -)

This thesis presents developments and applications of the mixed quantum/classical theory (MQCT) for inelastic scattering. In this approach, translational motion of collision partners is treated classically, while the internal degrees of freedom – rotational and/or vibrational motion – are treated quantum mechanically. Within this framework calculations of rotationally inelastic cross sections are carried out in a broad range of collision energies and results are compared against the exact full quantum data for several real systems. For CO +He, N2 + Na and H2 + He the agreement is excellent through six orders of magnitude range of cross sections values and …

Functional And Structural Studies Of Cytochromes P450 By Resonance Raman Spectroscopy, Yilin Liu

Dissertations (1934 -)

Cytochrome P450 is a broad class of heme monooxygenase enzymes which catalyze various oxidative transformations. There are two main kinds of mammalian P450s: steroidogenic and drug metabolizing P450s. The first project involves a steroidogenic P450, CYP17A1, occupying a central role in the biosynthesis of steroid hormones. It catalyzes hydroxylation reaction on pregnenolone and progesterone, generating 17OH-pregnenolone and 17OH-progesterone, presumably utilizing a “Compound I” species. However, these hydroxylated products can be further processed in a second oxidative cycle to cleave the C17–C20 bond to form dehydroepiandrosterone or androstenedione, respectively, a crucial step in androgen production. Interestingly, it is well known that …

Electrocarboxylation: An Effective Process For Fixation Of Co2 Into Organic Carboxylic Acids, Huan Wang, Jia-Xing Lu

Journal of Electrochemistry

Conversion and utilization of greenhouse gas carbon dioxide (CO₂) have become more and more significant to the sustainable development of the global economy. Among them, electrocarboxylation of organic substrates is an effective process. Under mild conditions such as ambient temperature and pressure, carbocations generated by electroreduction of organic substrates can react with CO₂ into corresponding carboxylic acids. This paper introduces the recent progress of our group in electrochemical carboxylation, including electrocarboxylation of varies active organic substrates and asymmetric electrocarboxylation.

Research Progresses Of Α-C-H Bond Functionalizations Under Electrochemical Conditions, Peng Qian, Mei-Xiang Bi, Yu-Kang Wang, Zheng-Gen Zha, Zhi-Yong Wang

Journal of Electrochemistry

Recently, organic electrochemical synthesis has emerged as the most important and attractive method to construct carbon-carbon bond and carbon-heteroatom bonds in organic synthetic chemistry. This review mainly summarizes the electrochemical syntheses at present, especially focused on the recent progresses in our research group using an iodine radical as a mediator to promote α-C?H bond functionalization. The organic electrosynthesis provides an alternative approach and a new research direction in the development of green organic synthesis.

Electrochemical Synthesis Of Homoallylic Alcohols And Homoallylic Amines, Wei-Qiang Zhong, Xiang-Hui Liang, Jing-Mei Huang

Journal of Electrochemistry

Electrochemical technique has been widely applied in the organic synthesis. This review focuses on the electrochemical synthesis of homoallylic alcohols and homoallylic amines from the allylation of carbonyl compounds and imines. This method has been developed impressively, especially in the field of electrochemical allylation in a green solvent of aqueous media. Improvement of the efficiency of the electricity, regio-selectivity and chiral synthesis are expected.