Physical Chemistry Commons^™

Van Der Waals Trilayers And Superlattices: Modification Of Electronic Structures Of Mos2 By Intercalation, Ning Lu, Hongyan Guo, Lu Wang, Xiaojun Wu, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We perform a comprehensive first-principles study of the electronic properties of van der Waals (vdW) trilayers via intercalating a twodimensional (2D) monolayer (ML = BN, MoSe₂, WS₂, orWSe₂) between a MoS₂ bilayer to form various MoS₂/ML/MoS₂ sandwich trilayers. We find that the BN monolayer is themost effective sheet to decouple the interlayer vdW coupling of the MoS₂ bilayer, and the resulting sandwich trilayer can recover the electronic structures of the MoS₂ monolayer, particularly the direct-gap character. Further study of the MoS₂/BN superlattices confirms the effectiveness of …

Unraveling Crystalline Structure Of High-Pressure Phase Of Silicon Carbonate, Rulong Zhou, Bingyan Qu, Jun Dai, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Although CO₂ and SiO₂ both belong to group-IV oxides, they exhibit remarkably different bonding characteristics and phase behavior at ambient conditions. At room temperature, CO₂ is a gas, whereas SiO₂ is a covalent solid with rich polymorphs. A recent successful synthesis of the silicon-carbonate solid from the reaction between CO₂ and SiO₂ under high pressure [M. Santoro et al., Proc. Natl. Acad. Sci. U.S.A. 108, 7689 (2011)] has resolved a long-standing puzzle regarding whether a Si_xC_1−xO₂ compound between CO₂ and SiO₂ exists in nature. Nevertheless, the detailed …

Visible Light Mediated Intermolecular [3 + 2] Annulation Of Cyclopropylanilines With Alkynes, Theresa H. Nguyen, Soumitra Maity, Nan Zheng

Chemistry & Biochemistry Faculty Publications and Presentations

Intermolecular [3 + 2] annulation of cyclopropylanilines with alkynes is realized using visible light photoredox catalysis, yielding a variety of cyclic allylic amines in fair to good yields. This method exhibits significant group tolerance particularly with heterocycles. It can also be used to prepare complex heterocycles such as fused indolines.

Computational And Experimental Studies Of Non-Covalent Interactions: Characterization Of Ch...Π Interactions And Structure Of 1,1-Difluoroethylene...Carbon Dioxide, Ashley M. Anderton

Masters Theses

Weakly bound CH/π interactions, due to the abundance of C-H bonds and π systems that exist in larger organic molecules, are an important driving force in the construction of biomacromolecules, supramolecular assemblies and crystal packing of organic compounds. To assist in the characterization of CH/π interactions, a density functional theory (DFT) study has been conducted to determine a quick and cheap method for accurate determination of the binding energy and rotational constants for CH/π interactions. Seven complexes were used in this study: five benzene-HY complexes (where Y= C≡CH, Cl, F, Br and C≡N) and two fluorobenzene-HY complexes (where Y= C≡CH …

Electron And Ion Spectroscopy Of Metal Hydrocarbon Complexes, Sudesh Kumari

Theses and Dissertations--Chemistry

Metal-hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE and MATI spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the spectroscopic measurements with quantum chemical calculations and spectral simulations.

In this dissertation, the metal complexes of mesitylene, aniline, cyclooctatetraene, benzene, ethene, and propene were studied. For each complex, different effects from metal coordination have been identified. Although metal-bis(mesitylene) sandwich complexes …

Structures And Electronic States Of Small Group 3 Metal Clusters, Lu Wu

Theses and Dissertations--Chemistry

Group 3 metal clusters are synthesized by laser vaporization in a pulsed cluster beam source and identified with laser ionization time-of-flight mass spectrometry. The adiabatic ionization energies and vibrational frequencies of these clusters are measured using mass-analyzed threshold ionization (MATI) spectroscopy. Their structures and electronic states are determined by combining the MATI spectra with quantum chemical calculations and spectral simulations. This dissertation focuses on the study of several small molecules, which include LaO₂, La₂, M₂O₂, M₃O₄, M₃C₂, and La₃C₂O, where …

Electrode And Electrolyte Additives For Lifetime Extension In Lithium-Ion Batteries, Kishore Anand Narayana

Theses and Dissertations--Chemistry

Lithium-ion batteries (LIBs) are the most commonly used type of rechargeable batteries with a global market estimated at $11 billion, which is predicted to grow to $60 billion by 2020. The global commercialization of Li-ion batteries is impeded by issues such as poor cycle life (5000 cycles achieved in some LIBs) in high energy and power density applications because of the rising internal resistance due to aging and safety concerns such as overcharge which ultimately leads to thermal runaway and explosions. A battery’s performance mainly depends on external factors such as electrode thickness and degree of compacting, and the type …

Laser Spectroscopy Of Radicals Containing Group Iiia And Va Elements, Robert A. Grimminger

Theses and Dissertations--Chemistry

Radicals are interesting to study because of importance in so many processes such as semiconductor growth or stellar evolution. Laser induced fluorescence (LIF) and wavelength resolved emission spectra of jet cooled HPS, HAsO, AsD₂, H₂PS, and F₂BO have been measured using the pulsed discharge jet technique.

Several bands in the à ¹A′′ − X̃ ¹A′ transition of HPS were observed and assigned with the help of ab initio calculations. The ab initio geometries showed that HPS does not follow Walsh’s predictions for the angle change upon electronic excitation; Walsh predicts an increase …

Surface Complexation Of Monosubstituted Organoarsenicals On Hematite: Atr-Ftir Investigations, Md Abdus Sabur

Theses and Dissertations (Comprehensive)

Little is known about the surface chemistry of organoarsenic compounds with iron-containing materials commonly found in geosorbents and arsenic removal technologies. In this thesis, these organoarsenicals include aliphatic and aromatic arsenicals that historically have been used as herbicides, pesticides and in the poultry feed industry, respectively. Attenuated total internal reflectance Fourier transform infrared spectroscopy has been used to study the surface interactions of organoarsenicals at the molecular level under various environmentally-relevant conditions. Kinetic and thermodynamic parameters extracted from these molecular level experiments provide trends that are not observed in any published bulk experiments. Apparent initial rates of adsorption and desorption …

A Computational Study Of Small Gold Clusters With H2s, Thiols, H2o, And Alcohols, Silvija C. Smith

Theses and Dissertations (Comprehensive)

Alkane thiols, RSH, are commonly used in aqueous solution to stabilize and prevent aggregation of gold clusters, Au_n. Initially a RSH-Au_n complex is formed and, subsequently, there is hydrogen atom transfer to form a RSAu_nH complex. We examine the rate of this reaction for small neutral gold clusters, with n=1-2 and short-chain thiols with R = H, CH₃, and CH₃CH₂, using transition state theory. The comparison of DFT (with the functionals, BP86 and M06-2X), and MP2 was performed. A pseudopotential was employed to account for the large relativisitic effects …

Localized Corrosion Behavior Of Sensitized 304 Stainless Steel By Scanning Reference Electrode Technique, Chen-Qing Ye, Rong-Gang Hu, Rui-Qing Hou, Xiao-Ping Wang, Rong-Gui Du, Chang-Jian Lin

Journal of Electrochemistry

Based on a home-built setup of scanning reference electrode technique, and combined with conventional electrochemical measurements, the localized corrosion behavior of sensitized 304 stainless steel (304ss) had been investigated in this work. The results showed that, the non-sensitized 304ss or 304ss sensitized at 550 oC was susceptible to pitting; while 304ss sensitized at 650 oC or 750 oC suffered severe intergranular corrosion in 10% FeCl3 solution.

Application Of Synchrotron Radiation Based Electrochemical In-Situ Techniques To Study Of Electrode Materials For Lithium-Ion Batteries, Zheng-Liang Gong, Wei Zhang, Dong-Ping Lv, Xiao-Gang Hao, Wen Wen, Zheng Jiang, Yong Yang

Journal of Electrochemistry

Due to its merits of high brightness and high intensity, high level of polarization and wide tunability in energy, etc., synchrotron radiation technique provides an unique platform for analysis of the relationship among composition–structure–performance of materials for lithium ion batteries, especially for in-situ, real time dynamic investigation of the electrochemical reaction mechanism, aging process and failure mechanism during charge-discharge cycling. In this paper, we review the latest developments in application of synchrotron based electrochemical in-situ experimental methods to studies of lithium ion batteries. The paper mainly focuses on the application of electrochemical in-siu XRD and XAFS techniques to the investigations …

Controllable Synthesis Of Dispersed Spherical Fe3O4 Nanoparticles As Lithium-Inserted Materials, Hong-Li Zou, Wei-Shan Li

Journal of Electrochemistry

Dispersed spherical Fe₃O₄ nanoparticles were synthesized by a hydrothermal method. The influences of odecyl trimethyl ammonium bromide (DTAB) concentration on the morphology and particle size of the as-prepared Fe₃O₄ were studied. Electrochemical performance of the as-prepared sample as anode materials of lithium ion battery was investigated. It is found that the as-prepared sample exhibits superior rate performance and cycle performance. The nano-sized materials provide structural stability and favor the transfer of lithium ions.

Study On Hydrogen Bubble Template Fabrication Of Porous Biomaterials Coatings By Electrochemically Induced Deposition, Hui Wang, Chang-Jian Lin, Ren Hu, Ke-Qin Zhang, Hong-Ping Duan, Xiang Dong

Journal of Electrochemistry

So far, the pore architecture in biomaterials plays a critical role on the cell response and integration between the biomaterials and implanted environment. In this study, porous calcium phosphate (CaP) coatings and CaP/protein composite coatings have been successfully constructed on titanium substrate by using an electrochemically induced deposition technique. The shape, size and pliability of CaP crystals are controlled by electrolyte concentration, temperature, current density, time and protein additive in preparing process. In addition, the formation mechanism of the porous structure is discussed based on the “hydrogen bubble template” model. It demonstrates that the growth velocity of CaP crystals should …

An Investigation On The Solid Electrolyte Interphase Of Silicon Anode For Li-Ion Batteries Through Force Curve Method, Jie-Yun Zheng, Hao Zheng, Rui Wang, Hong Li, Li-Quan Chen

Journal of Electrochemistry

Non-aqueous electrolyte has been widely used in commercial Li-ion batteries. Optimized choices are proceeding among the various types of salts and solvents in an effort to achieve higher performance of electrolyte. However, the electrolyte will be reduced in low potential and the reductive product will be deposited on the surface of anode to form a passivating layer, solid electrolyte interphase (SEI). Herein an atomic force microscopy (AFM) based method was introduced to study the structure and mechanical property of SEI on silicon thin film anode during the first cycle. Silicon has been known as the most potential candidate anode for …

Preparation And Electrochemical Properties Of Flake-Like Liv3O8 By Soft Template Assisted Sol-Gel Method As Anode Material For Aqueous Li-Ion Battery, Shuai Tan, Dan Sun, Hai-Yan Wang, Tian-Li Hou, Zhong-Xing Xiao, You-Gen Tang

Journal of Electrochemistry

Composite electrode of CuF₂/MoO₃/C was fabricated through high energy mechanical milling. The properties of CuF₂/MoO₃/C were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), galvanostatic charge-discharge measurements, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the grain sizes of CuF₂ and MoO₃ after milling were 200 ~ 300 nm, and the initial discharge capacity of CuF₂/MoO₃/C was 647 mAh·g^-1 at room temperature and at a current density of 10 mAh·g^-1. However, the …

Synthesis And Electrochemical Performance Of Nano Licopo4 By Polyol Method, Fei Wang, Yang Jun

Journal of Electrochemistry

High potential LiCoPO₄ cathode material was synthesized by polyol method. Carbon layer of ca. 3 nm thick was coated on the LiCoPO₄ surfaces by chemical vapor deposition from methylbenzene. Crystalline structure, morphology and electrochemical performance of the sample were studied by XRD, SEM, TEM, CV and galvanostatic charge/discharge curve. The synthesized material via polyol method showed a pure phase of LiCoPO₄. The LiCoPO₄/C electrode delivered a high discharge capacity of 132 mAh·g^-1 and maintained 78% of the initial capacity after 50 cycles at 0.1C rate. The two-step extraction/insertion behavior of Li⁺ in …

Aqueous Solution-Evaporation Route Synthesis And Phase Structural Research Of The Li-Rich Cathode Li1.23Ni0.09Co0.12Mn0.56O2 By In-Situ Xrd, Chong-Heng Shen, Shou-Yu Shen, Zhou Lin, Xiao-Mei Zheng, Hang Su, Ling Huang, Jun-Tao Li, Shi-Gang Sun

Journal of Electrochemistry

The Li-rich Li_1.23Ni_0.09Co_0.12Mn_0.56O₂ material was synthesized via aqueous solution-evaporation route. The structure and morphology of the material were characterized by means of XRD and SEM. The results indicated that the single particle of the product was polygonal with the size of 330 nm and the structure was layered solid solution with a certain amount of Li₂MnO₃. Electrochemical tests showed that the first discharge capacity of the Li-rich layered material was 250.8 mAh·g^-1 at 0.1C, the capacity retention was 86.5% after 40 cycles. Through in-situ XRD study …

Cmk-3/Sulfur Composite (CXSY) And Room-Temperature Na/S Battery, Qing Zhao, Yu-Xiang Hu, Kai Zhang, Li-Jiang Wang, Zhan-Liang Tao, Jun Chen

Journal of Electrochemistry

A series of ordered mesoporous carbon (CMK-3)/sulfur composite (C_xS_y) with different sulfur contents were synthesized via a melt-diffusion method. XRD, Raman, BET, SEM, and TEM techniques were used to characterize the structure and morphology of the as-prepared composite. The electrochemical performance of CMK-3/sulfur composite as the electrode of Na/S battery was tested at room temperature. Cyclic voltammograms show that one obvious reduction peak was located at about 1.61V, which is corresponding to the formation of Na₂S_x (x=2~5), while two oxidation peaks were displayed at about 1.82V and 1.95V, which are belonging to the …

Preparation Of The Particle Size Controllable Lifepo4/C And Its Electrochemical Profile Characterization, Ming-E Wang, Jing-Yuan Liu, Meng-Yan Hou, Yong-Yao Xia

Journal of Electrochemistry

We adopted an effective route to prepare the particle size controllable core-shell structure carbon-coated LiFePO₄ from different sized FePO₄ precursors, varying from 80 nm, 200 nm and 1 μm by an in situ polymerization method integrated with a surface modification technology. The discharge capacities of the three sized LiFePO₄/C are, respectively, 162 mAh·g^-1, 142 mAh·g^-1 and 92 mAh·g^-1 at 0.1C rate. The nano-sized LiFePO₄-a/C (80 nm) delivers a discharge capacity as large as 100 mAh·g^-1 even at 30C, while the macroscopic LiFePO₄-c/C (1 μm) exhibits a much …

Surface Composition Structure And Electrochemical Performance Of Aluminum Doped Lifepo4, Huai-Fang Shang, Wei-Feng Huang, Wang-Sheng Hu, Ding-Guo Xia, Zi-Yu Wu

Journal of Electrochemistry

Despite there are many successful reports about the preparation of electrode materials with surface coating for lithium ion batteries, the study in surface self-coating of cathode materials using segregation of doping elements and their electrochemical properties is still very rare. The LiFePO₄ particles with rich-Al on the surface were synthesized by one step solvothermal route. TEM results demonstrated that the surface of the obtained LiFePO₄ particles was well-covered by the amorphous coating. The soft X-ray absorption spectroscopy (XAS) and Auger electron spectroscopy (AES) component analyses revealed that the amorphous coating was composed of LiFe_1-xAl_xPO …

Effect Of Vanadium Substitution On Structure Of Li2Fesio4/C Composites, Yang Hong, Zhang Ying, Cheng Xuan

Journal of Electrochemistry

The carbon coated lithium iron silicate (Li₂FeSiO₄/C) composites were prepared using less expansive iron starting material of soluble ferric nitrate through sol-gel process and solid state reaction. The theoretically calculated amounts of 5, 10, 15, 20, 25, 30, and 50% of vanadium (V) were introduced using NH₄VO₃ to obtain V-substituted Li₂FeSiO₄/C composites. It was found that the pure Li₂FeSiO₄/C composite exhibited a good crystallinity with P2₁/n and nearly no impurities being detected, while the V-substituted Li₂FeSiO₄/C composites showed major …

Preparation And Electrochemical Properties Of Amorphous Znsno3/C By Hydrothermally Carbonization Method, Guo-Qing Fang, Rui-Xue Zhang, Wei-Wei Liu, Bing-Bo Xia, Hong-Dan Sun, Hai-Bo Wang, Jing-Jing Wu, Shinko Kaneko, De-Cheng Li

Journal of Electrochemistry

The amorphous ZnSnO₃@C composite was synthesized via a simple glucose hydrothermal and subsequent carbonization approach. The structure, morphology and electrochemical property of the composite were characterized by XRD, TEM and electrochemical measurements. Compared to bare ZnSnO₃, the ZnSnO₃/C composite exhibited markedly enhanced lithium storage property and cycle performance, delivering a reversible capacity of 659 mAh·g^-1 after 100 cycles at a current density of 100 mA·g^-1.

Synthesis And Electrochemical Property Of Li2Fesio4/C Cathode Material By Solid State Method, Jiao-Li Sun, Zhi-Jiao Chen, Yi-Xiao Li, Hu Cheng

Journal of Electrochemistry

Li₂FeSiO₄/C cathode material was synthesized using Li₂SiO₃ and FeC₂O₄ as raw materials by solid state method. The structure and morphology of the material were characterized by XRD and SEM. The electrochemical properties of the material were studied by constant-current cyclic testing. The results show that Li₂FeSiO₄/C has a good electrochemical performance. The first discharge capacity of Li₂FeSiO₄/C cathode material at 30oC reached 167 mAh∙g^-1 when cycled at 10 mA∙g^-1 between 1.5 and 4.8 V.

Electrochemical Na-Storage Materials And Their Applications For Na-Ion Batteries, Jiang-Feng Qian, Xue-Ping Gao, Han-Xi Yang

Journal of Electrochemistry

Oncoming large scale electric energy storage (EES) requires battery systems not only to have sufficient storage capacity but also to be cost-effective and environmentally friendly. Li-ion batteries for widespread EES applications may be limited due to the constraint of global lithium resource. From the considerations of available resources and environmental impact, Na-ion batteries have potential advantages as next generation secondary batteries and an alternative to Li-ion batteries. However, in the present state of the art, the Na-storage cathodes reported so far are still deficient both in energy density and power capability, while the carbon and alloy anodes for Na-ion batteries …

High Resolution X-Ray Diffraction Analysis Of Cb1 Receptor Antagonists As A Means To Explore Binding Affinity, Steven P. Fournet

LSU New Orleans Theses and Dissertations

Abstract

Charge density studies have been conducted on ten CB₁ cannabinoid receptor antagonists via high resolution x-ray crystallography. Bond critical point values and various other properties derived from these studies including the electrostatic potential were analyzed in correlation to the affinity of each compound with the CB₁ receptor. Correlation/anti-correlation was found between several properties and K_i. The data was also interpreted by principal component analysis with three principal components accounting for 85% of the data variation. Data mining was limit due to the low sample count and the requirements set for the inclusion of correlated/anti-correlated variables …

Solar Energy Conversion And Control Using Organic Photovoltaic Cells, Kurt Wade Woods

Masters Theses & Specialist Projects

Organic photovoltaic (OPV) cells are advanced, newly emerging technologies that are lightweight, mechanically flexible devices with highthroughput processes from low cost material in a variety of colors. Rathnayake et al. of Western Kentucky University have developed a nanostructure-based OPV cell. Presented in this thesis is a model and simulation of a generalized PV powered system that can predict the performance of solar arrays in various environmental conditions. The simulation has been carried out in Matlab/Simulink, and upon entering the cell’s parameters, it provides key electrical characteristics such as the cell’s I-V curve and efficiency information. The total system that is …

Phosphate Esters, Thiophosphate Esters And Metal Thiophosphates As Lubricant Additives, David W. Johnson, John E. Hils

Chemistry Faculty Publications

Phosphate esters, thiophosphate esters and metal thiophosphates have been used as lubricant additives for over 50 years. While their use has been extensive, a detailed knowledge of how they work has been a much more recent development. In this paper, the use of phosphate esters and thiophosphate esters as anti-wear or extreme pressure additives is reviewed with an emphasis on their mechanism of action. The review includes the use of alkyl phosphates, triaryl phosphates and metal containing thiophosphate esters. The mechanisms of these materials interacting with a range of iron and steel based bearing material are examined.

Morphology And Conformation Of Polythiophene Derivatives In Anisotropic Core-Shell Nanocomposites And Solution, Neil Redeker

Master's Theses

Conjugated semiconducting polymers have garnered substantial interest in recent years due to the potential for use in various applications, particularly in the field of electronic devices such as photovoltaic cells and light emitting diodes. Conjugated polymers offer numerous advantages in these applications, including low cost and high flexibility, but electronic devices based on these materials are currently limited by poor performance. Because of these limitations, increased focus has been placed on improving conjugated polymers for use in commercially viable products. Here, a novel core shell hybrid nanocomposite based on anisotropic zinc oxide nanowires and a side-chain functionalized polythiophene is reported. …

Monodentate, Bidentate And Photocrosslinkable Thiol Ligands For Improving Aqueous Biocompatible Quantum Dots, Hiroko Takeuchi

Graduate Theses and Dissertations

Water-soluble Quantum Dots (QDs) are highly sensitive fluorescent probes that are often used to study biological species. One of the most common ways to render QDs water-soluble for such applications is to apply hydrophilic thiolated ligands to the QD surface. However, these ligands are labile and can be easily exchanged on the QD surface, which can severely limit their application. As one way to overcome this limitation while maintaining a small colloidal size of QDs, we developed a method to stabilize hydrophilic thiolated ligands on the surface of QDs through the formation of a crosslinked shell using a photocrosslinking approach. …