Chemistry Commons^™

Effect Of Peg-Coating On Properties Of Lithium-Sulfur Battery Cathode Material Containing Carbon Fiber Conductive Agent, Jie-Cheng Tan, Yan-Hong Tian, Xue-Jun Zhang, Kai-Le Fan

Journal of Electrochemistry

The composite materials contained high modulus carbon fiber (HMCF) were successfully prepared by employing a ball-milling process based on the coating treatment of polyethylene glycol (PEG), and their structures and morphologies were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) techniques．The influences of PEG content on sulfur cathode capacity, cycle stability and rate performance were systematically studied. It was found that by the pre-coating of PEG, the cathode exhibited the high initial discharge specific capacity of 1312.5 mAh•g^-1 at a current rate of 0.2C, and the reversible discharge capacity of 650 mAh•g …

Effect Of Fe2+/Fe3+Interconvertion On Reduction Behavior Of Fe3+ In Acidic Electrolytes, Jian-Xin Qin, Feng Lin, Wen-Ping Liu, Chao Chen, Meng-De Ren

Journal of Electrochemistry

The influences of ferrous/ferric (Fe²⁺/Fe³⁺) interconvertion on electrochemical reduction and electrode reaction of Fe³⁺ were investigated by using linear sweep voltammetry, potentiostatic method and cyclic voltammetry (CV) in acidic electrolytes containing chloride ion (Cl^- ) and sulfate ion (SO₄^2-). It was shown that the reduction process of Fe³⁺/Fe²⁺ would take place in two independent stages: (1) the reduction of Fe³⁺ to Fe²⁺ at E=0.35V and (2) the co-precipitation of Fe²⁺ by forming Fe(OH)₂ (E≤-0.3 V) instead of Fe. The major effect of Fe^{2+ …}

Electroactivities Of Pd/Fe3O4-C Catalysts For Electro-Oxidation Of Methanol, Ethanol And Propanol, Tao Zou, Qing-Feng Yi, Yuan-Yuan Zhang, Xiao-Ping Liu, Guo-Rong Xu, Hui-Dong Nie, Xiu-Lin Zhou

Journal of Electrochemistry

Development of palladium (Pd) catalysts with high electroactivity for alcohol oxidation is significant for alcohol fuel cells. In this work, Pd nanoparticles were formed by sodium borohydride (NaBH₄) reduction method and subsequently deposited on the surface of carbon supported ferriferrous oxide (Fe₃O₄/C) composites to obtain the Pd/Fe₃O₄-C catalysts with different Fe₃O₄ loadings. Their transmission electron microscopic (TEM) images show that the Pd nanoparticles were uniformly dispersed on the Fe₃O₄/C. Electroactivities of the prepared Pd/Fe₃O₄-C catalysts toward oxidations of C1-C3 …

Electrochemical Behaviors Of Ce3+/Ce4+ Couple In A Mixed-Acid Medium Of Ch3So3H And H2So4, Zhao-Hua Li, Jiao-Long Xu, Ting Wu

Journal of Electrochemistry

In order to determine the optimum molar ratio between methanesulfonic acid (MSA) and sulfuric acid, linear sweep voltammetry (LSV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical behaviors of cerium (III)/cerium (IV) (Ce³⁺/Ce⁴⁺couple on a Pt electrode in a mixed acid solution. Various concentrations of sulfuric acid were considered in the experiments, while the concentration of MSA was fixed at 1.0 mol·L^-1. It was found that the optimum concentration of sulfuric acid was 0.8 mol·L^-1 since the current response was the highest in the control groups and …

Effect Of Calcium On Atmospheric Corrosion Resistance Of Bridge Steel, Dong-Liang Li, Gui-Qin Fu, Miao-Yong Zhu

Journal of Electrochemistry

The corrosion behavior of bridge steel in simulated hot and humid industrial-marine atmosphere was investigated by mass loss analysis, XRD, SEM, electrochemical methods and a wet/dry alternate immersion corrosion test using 0.1 mol•L^-1 NaCl+0.01 mol•L^-1 NaHSO₃ solutions. The corrosion depth (W) of experimental steels before and after calcium treatment versus time (t) curves showed a good agreement with the power function of W=Atⁿ. The corrosion products were mainly composed of amorphous phase and a small amount of crystals including α-FeOOH, β-FeOOH, γ-FeOOH and Fe₃O₄. Trace calcium could promote the formation of …

Effects Of Jet Milling And Classifying Process On The Performance Of Lifepo4/C In Full Batteries, Xing-Liang Liu, Mao-Ping Yang, Wei-Wei Wang, Yong Cao

Journal of Electrochemistry

The carbon coated lithium iron phosphate (LiFePO₄/C) composite cathode material was prepared by using iron phosphate process. The effects of jet milling and classifying process on the electrochemical performance of LiFePO₄/C cathode material in full batteries were investigted. Scanning electron microscopic analyses suggested that the globose secondary particles were crustily crushed during the jet milling and classifying process, which would further result in lower tap density and carbon content. The LiFeP₄/C composite cathode materials with different physical characteristics were further tested in full batteries to evaluate the electrochemical properties. The results showed no obvious …

Engineering The Electrochemical Capacitive Properties Of Activated Carbon By Correct Selection Of Ionic-Liquid Electrolytes, Qiu-Hong Zhang, Bao-Shou Shen, Song-Lin Zuo, Xin-Yu Wei

Journal of Electrochemistry

In order to improve the electrochemical capacitive properties and to apply coconut shell activated carbon (AC) serving as electrode materials in ionic liquid (IL)-based supercapacitor (SC), the coconut shell AC material was re-activated using a steam as an activating agent in this work, forming a secondary AC (W-AC). The results showed that the specific capacitance of the W-AC electrode was much larger than that of the raw activated carbon electrode (R-AC) in 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF₄). The electrochemical techniques including cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) measurement, and electrochemical impedance spectroscopy (EIS) were used to systematically study the capacitive …

Kinetics And Mechanism Toward Electrochemical Reductions Of Sodium Bromide And Methanol Over Iron Electrodes, Qun Liao, Shu-Feng Zhang, Wen-Hua Leng

Journal of Electrochemistry

It is of technological value and scientific interest to the electro-synthesis of ferrocene, conversion of carbon dioxide (CO₂) and organic electro-synthesis in non-aqueous solutions by investigating the kinetics and mechanism toward electrochemical reductions of sodium bromide (NaBr) and methanol over iron electrodes. However, few reports in the related researches are available. In this article, the kinetics and mechanism toward electrochemical reductions of NaBr and methanol over iron electrodes were examined in detail by carrying out the polarization curve and electrochemical impedance spectroscopic measurements. The results showed that methanol was the reactant, while Na⁺ ions were functioned only …

Capacity Fading Analyses Of Lini 0.5Co 0.2Mn 0.3O2And Lini 0.5Co 0.2Mn 0.3O2/Lifepo4 Cathode Materials For Lithium-Ion Battery, Yi Hu, Xiang-Zhu He, Zhong-De Deng, Ling-Yong Kong, Wei-Li Shang

Journal of Electrochemistry

The LiNi _0.5Co _0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP) composite cathode material for lithium-ion battery was prepared by wet ball-milling. The capacity fading behaviors of LiNi _0.5Co _0.2Mn _0.3O₂ (NMC532) and LiNi _0.5Co _0.2Mn _0.3O₂/LiFePO₄ (NMC532/LFP) were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), charge/discharge and electrochemical impedance spectroscopy (EIS) tests. The results indicated that the capacity retention values of NMC532/LFP were 97.80% and 86.48%, respectively, after 50 cycles and 60℃ high temperature storage. The NMC532/LFP exhibited better cycle performance and high temperature storage performance. …

Core-Shell Pd@Pt Ultrathin Nanowires As Durable Oxygen Reduction Electrocatalysts, Xin Wang, Yun-Jie Xiong, Liang-Liang Zou, Qing-Hong Huang, Zhi-Qing Zou, Hui Yang

Journal of Electrochemistry

This paper describes a simple CO-assisted reduction approach for the controllable synthesis of ultrathin Pd nanowires along the one-dimensional (1D) direction. Ultrathin Pt films from one to several atomic layers were successfully decorated onto ultrathin Pd nanowires by utilizing Cu UPD deposition, and followed by in-situ redox replacement reaction of UPD Cu by Pt. The core–shell structure and composition of the Pd@Pt ultrathin nanowires have been verified using transmission electron microscopy and energy dispersive X-ray spectrometry. The core–shell Pd@Pt ultrathin nanowires exhibited comparative electrocatalytic activity and improved durability for the oxygen reduction reaction in comparison with commercial Pt black. The …

Cobalt-Based Nitrogen-Doped Carbon Non-Noble Metal Catalysts For Oxygen Reduction Reaction, Meng-Xiu Jiang, Jing Zhang, Yue-Hua Li, Rong Zhang

Journal of Electrochemistry

Transition metal-nitrogen co-doped carbon catalysts have attracted significant attention because of their reasonable activity and remarkable selectivity toward oxygen reduction reaction (ORR) as cathodic reaction in fuel cells. However, the role of transition metal in the active sites of the catalysts still is uncertain. In this work, the Co_x-N_y/C-T catalysts were prepared with BP2000 as a carbon source, urea (Ur) as a nitrogen source and Co(OAc)₂•4H₂O as a metal precursor by a simple chemical method. Meanwhile, in order to optimize the ORR activity, the catalysts were synthesized with different amounts of Co …

Effect Of Allyl Thiourea On Nickel Electrodeposition From Solution Containing Ammonia And Chloride, Ya-Ning He, Liang Yuan, Zhi-Ying Ding, Shi-Jun Liu

Journal of Electrochemistry

The effects of allylthiourea (ATU) concentration on the cathodic polarization behaviour, nucleation and surface morphology of nickel electrodeposited on the glassy carbon electrode from ammonia-ammonium chloride-water (NH₃-NH₄Cl-H₂O) solutions were investigated by cyclic voltammogry, cathodic polarization and current transient methods. The results revealed that the addition of ATU inhibited nickel deposition, which was enhanced with an increase in ATU concentration from 5 to 50 mg•L^-1. The initial deposition kinetics corresponded to a model including instantaneous nucleation and diffusion controlled growth. In the presence of ATU, the initial nucleation of nickel electrocrystallisation remained unchanged. …

Preparation Of Nis2 Nanosheet And Its Application In Asymmetric Supercapacitor, Yuan-You Wang, Ya-Nan Liu, Dang-Qin Jin

Journal of Electrochemistry

In this work, the NiS₂ nanosheets have been synthesized using Ni(OH)₂ as a precursor through a sacrificial template method. The microstructure and chemical composition of as-prepared NiS₂ were characterized by XRD, EDS, BET, SEM and TEM techniques. The results showed that both Ni(OH)₂ and NiS₂ were composed of nanoplates. The electrochemical tests revealed that NiS₂ exhibited the high specific capacitance of 1067.3 F•g^-1 at a current density of 1 A•g^-1 and excellent rate performance. Furthermore, in order to evaluate the practical application of NiS₂, an asymmetric supercapacitor, NiS₂ as …

Applications Of N-Methyl-N-Butyl-Pyrrolidinium Bromide And N-Methyl-N-Ethyl-Pyrrolidinium Bromide In Zn-Br Flow Batteries, Zhang Qi, Miao-Miao Zhang, Meng Lin

Journal of Electrochemistry

It is extremely important for battery performance and safety in Zn-Br flow battery to use quaternary ammonium salts as complex agents for bromine. In this work, the effects of electrolyte compositions and concentrations on the electrode reactions and battery performances were studied in the absence and presences of N-methyl-N-ethyl-pyrrolidinium bromide (MEP) or N-methyl-N-butyl-pyrrolidinium bromide (MBP). The conductivities in the electrolytes containing different constitutions and concentrations were measured by EIS method. The charge-discharge performance for the battery and the complex ability for bromine in different electrolytes were also investigated. The results showed that the electrolyte containing MBP was better than that …

Quantum Chemical Studies Of Noncovalent Interactions And Multicenter Bonds Utilizing Local Vibrational Modes, Vytor Oliveira

Chemistry Theses and Dissertations

Noncovalent interactions play an important role for the design of novel drugs, better catalysts, synthesis of complex supramolecular structures, and so on. To develop new materials, a well-founded knowledge of how to control the strength of these interactions is desirable. Despite the many investigations done so far, a quantitative assessment of the intrinsic strength of most types of noncovalent interactions is still missing. Recently and for the first time, the Konkoli-Cremer local modes analysis was successfully used to probe the intrinsic strength of hydrogen and pnicogen bonds. We extended these investigations to more than 300 halogen and chalcogen bonds. A …

Synthesis, Characterization, And Spectroscopy Of Donor-Acceptor Charge Transfer Complexes, Dominic K. Kersi

Chemistry and Chemical Biology ETDs

A series of square-planar metal (diimine)(dichalcogenolene) chromophoric complexes have been synthesized, characterized and studied spectroscopically. Studies conducted on diimineplatinum(II) dichalcogenolene complexes (LPtL’) using time resolved spectroscopic techniques such as transient absorption and emission, reveal a charge-separated excited state of the type dichalcogenolene → diimine charge-transfer (LL’CT) [(dichalcogenolene^•+)Pt(diimine^•-) with an open shell donor-acceptor biradical character. Long-live excited state lifetimes were observed for these complexes upon visible photoexcitation of the LL’CT or MMLL’CT band. A direct linear relationship is observed to exist between photoluminescence rates, calculated SOC matrix elements, and ¹³C-NMR chemical shifts.

A series of …

Studying Metal-Organic Frameworks Via Solid-State Nmr: Gas Dynamics, Structure Determination, And Phase Transition, Yue Zhang

Electronic Thesis and Dissertation Repository

Metal-organic frameworks (MOFs) are a class of microporous materials constructed from virtually endless combinations of metal centres and organic linkers. MOFs have attracted intense research interest in recent decades, since MOFs have outstanding properties such as extremely high surface area, tuneable pore topology, good stability, and many others. MOFs are also promising candidates for gas storage. In this work, solid-state NMR (SSNMR) spectroscopy has been investigated to study MOFs and their guest molecules, since SSNMR can provide information on the short-range environment about target nuclei and can also reveal the dynamics of guest molecules.

An introduction to MOFs and SSNMR …

Multiscale Modeling Approach To Understand Active Sites In Non-Conventional Catalyst Layers For Fuel Cell Applications, Diana Constanza Orozco Gallo

Doctoral Dissertations

Fuel cells development required stable, active and more abundant catalytic materials. Oxygen reduction reaction (ORR) is the key process to enhance better activity and reduce the fabrication costs. Pt-based has proven to be the best catalyst for ORR and greater efforts has been made in terms of reducing the Pt content in the electrodes, reduce electrode thickness and enhance better catalytic activities. To overcome many of the challenges present, the catalyst layer studies are the great importance in the fuel cell community. Understanding catalyst layer with new catalytic materials, and configurations requires the development of methodological approach to relate structure, …

Analysis Of Primary Stripper Foils At The Spallation Neutron Source By An Electron Beam Foil Test Stand, Eric Paul Barrowclough

Doctoral Dissertations

Diamond films are used at the Spallation Neutron Source (SNS) as the primary charge exchange foils (i.e., stripper foils) of the accelerated 1 GeV (Gigaelectron volts) hydride ions. The most common type of film used is a nanocrystalline diamond film, typically 17 mm x 45 mm (millimeter) with an aerial density of 350 μg/cm² (microgram per square centimeter). The diamond film is deposited on a corrugated silicon substrate using plasma-assisted chemical vapor deposition. After the growth of the diamond film, 30 mm of the silicon substrate is etched away, leaving a freestanding diamond foil with a silicon handle that …

Eigenstate–Specific Temperatures In Two–Level Paramagnetic Spin Lattices, Mark Masthay, Calley N. Eads, Amber N. Johnson, R. Gerald Keil, Phillip Miller, Ross E. Jones, Joe D. Mashburn, Harry B. Fannin

Chemistry Faculty Publications

Increasing interest in the thermodynamics of small and/or isolated systems, in combination with recent observations of negative temperatures of atoms in ultracold optical lattices, has stimulated the need for estimating the conventional, canonical temperature Tconvc of systems in equilibrium with heat baths using eigenstate-specific temperatures (ESTs). Four distinct ESTs—continuous canonical, discrete canonical, continuous microcanonical, and discrete microcanonical—are accordingly derived for two-level paramagnetic spin lattices (PSLs) in external magnetic fields. At large N, the four ESTs are intensive, equal to Tconvc, and obey all four laws of thermodynamics. In contrast, for N < 1000, the ESTs of most PSL eigenstates are non-intensive, differ from Tconvc, and violate each of the thermodynamic laws. Hence, in spite of their similarities to Tconvc at large N, the ESTs …

Study Of 2,5-Diaminoimidazolone, A Mutagenic Product Of Oxidation Of Guanine In Dna, Hannah Catherine J. Pollard

Electronic Theses and Dissertations

2,5-diaminoimidazolone (Iz) is an important product of a 4-electron oxidation of guanine. The present research focuses on the mechanisms of formation of Iz via pathways initiated by guanine oxidation by one-electron oxidants (OEOs) generated by X-ray radiolysis in aqueous solutions. The kinetics of formation and yields of Iz in reactions of native highly polymerized DNA with different OEOs have been compared using an HPLC-based quantitative analysis of low-molecular products generated from the reaction of DNA-bound Iz with primary amines. Mechanisms of Iz formation in DNA have been investigated including oxygen and superoxide dependence as well as the hypothesis that 8-oxo-G, …

Investigation Of Tribochemical Reactions Using The Model System Of Methyl Thiolate On Copper Foil In Ultrahigh Vacuum And Ab-Initio Calculations, Heather Loren Adams

Theses and Dissertations

Advancement in the understanding of tribochemical systems suffers from several obstacles that hinder the progress in advancing an understanding of the fundamental processes involved in the evolution of friction and wear. Characterizing ephemeral chemical states within a buried interface is an experimental challenge and work in this dissertation uses a model system, methyl thiolate on copper foil, that undergoes tribo-activated decomposition to investigate the rate of change of the chemical components in the interface. The elementary steps in the tribochemical reaction were identified and consist of a shear-induced decomposition of methyl thiolate species to produce gas-phase hydrocarbons and form surface …

Artificial Olfactory System For Multi-Component Analysis Of Gas Mixtures., Alexander Aleksandrovich Larin

Electronic Theses and Dissertations

Gas analysis is an important part of our world and gas sensing technology is becoming more essential for various aspects of our life. A novel approach for gas mixture analysis by using portable gas chromatography in combination with an array of highly integrated and selective metal oxide (MOX) sensors has been studied. We developed a system with small size (7 x 13 x 16 inches), low power consumption (~10 W) and absence of special carrier gases designed for portable field analysis (assuming apriori calibration). Low ppb and even sub-ppb level of detection for some VOCs was achieved during the analysis …

The Electrochemical Deposition Of Samarium And Europium Dissolved In Ionic Liquid Solvent, Bea Martinez

UNLV Theses, Dissertations, Professional Papers, and Capstones

Rare-earth elements include the lanthanide series in the periodic table with the addition of scandium and yttrium. China produces approximately 95% of the world’s rare-earths supply and is the largest consumer of the world’s rare earth supply. Domestic production of rare-earth metals is a priority in the US. The domestic demand for rare-earth elements is largely based on their use in electronic devices, catalytic converters, and more importantly defense applications. Therefore, China’s monopoly of rare-earth elements is viewed as a threat to national security. Although capital investments have resulted in an increase in domestic mining and refining of rare-earth materials, …

Surface And Interface Characterization Of Solution-Processed Metal Oxides And Pedot:Pss Using Photoelectron Spectroscopy, Lynette M. Kogler

UNLV Theses, Dissertations, Professional Papers, and Capstones

Solution-processed materials are appealing for use in printable electronics as a means to lower production costs, but precise control of the process is crucial for achieving the desired properties in the final materials and their interfaces. Electronic interface properties depend on both the involved materials and their fabrication processes, impacting the development and commercialization of these materials. Analyzing the chemical and electronic structure of these materials, particularly at the surfaces and interfaces, is important not only for insuring that the materials have the desired properties, but also for understanding the effects of the fabrication process and how to modify properties …

The Autophagy-Related Beclin-1 Protein Requires The Coiled-Coil And Bara Domains To Form A Homodimer With Submicromolar Affinity, Matthew J. Ranaghan, Michael A. Durney, Michael F. Mesleh, Patrick R. Mccarren, Colin W. Garvie, Douglas S. Daniels, Kimberly L. Carey, Adam P. Skepner, Beth Levine, Jose R. Perez

Chemistry Faculty Publications

Beclin-1 (BECN1) is an essential component of macroautophagy. This process is a highly conserved survival mechanism that recycles damaged cellular components or pathogens by encasing them in a bilayer vesicle that fuses with a lysosome to allow degradation of the vesicular contents. Mutations or altered expression profiles of BECN1 have been linked to various cancers and neurodegenerative diseases. Viruses, including HIV and herpes simplex virus 1 (HSV-1), are also known to specifically target BECN1 as a means of evading host defense mechanisms. Autophagy is regulated by the interaction between BECN1 and Bcl-2, a pro-survival protein in the apoptotic pathway that …

Gamma-Radiation Induced Corrosion Of Alloy 800, Mojtaba Momeni

Electronic Thesis and Dissertation Repository

This thesis presents a newly developed mechanism and predictive model for the corrosion of Alloy 800. The Fe-Cr-Ni Alloy (Incoloy 800) is mainly used for steam generator (SG) tubing in CANDU and PWR reactors and is a candidate material for the proposed Canadian Supercritical Water Reactor (SCWR) in which it will be exposed to extreme conditions of high radiation flux and large temperature gradients. The influence of gamma radiation and water chemistry conditions on the corrosion behaviour of Alloy 800 are studied in this work. Ionizing radiation creates reducing (•e_aq^–, •H, •O₂^-) and oxidizing …

Coupled Plasmon/Molecule Dynamics Near Core-Shell Nanoparticles: Synthesis, Ultrafast Characterization, And Quantum/Classical Modeling, Holden Tyler Smith

LSU Doctoral Dissertations

In this dissertation, the resonance coupling of chromaphoric dyes adsorbed on the surface of plasmonic nanoparticles (NPs) are investigated using a combined theoretical and experi- mental approach. Colloidal gold, gold-silver core-shell, silver-gold core-shell, and gold-silver- gold core-shell-shell NPs are considered. These NPs are thiolated with mercaptosuccinic acid, and malachite green dyes are adsorbed to the surface of the nanoparticle (NP) via elec- trostatic interactions. Second harmonic generation is used to determine the surface to the isotherm of the molecular dyes to the colloidal nanoparticle surface. Adsorption isotherms show that the SHG intensity increases as the concentration of dye increases, reaching …

Spectroscopic Studies Of Gas-Phase Transition Metal Complexes Of Cations And Cluster Ions With Methane And Water, Christopher Copeland

Doctoral Dissertations

The study of the non-covalent interactions between metals ions and ligands such as water and methane are key to understanding many processes including solvation, homogeneous catalysis and metals in biology. Similarly, the study of interactions between transition metal ions and cluster ions with hydrocarbons is of great importance in the understanding of C-H activation reactions which are involved in generation of fuels. Gas-phase metal complexes are good models for understanding the intrinsic interactions between the metal and the ligand. Understanding the mechanisms behind these interactions can be done by characterizing the structure and bonding in the molecular reactants, products, and …

Dendritic Plasmonics For Mid-Infrared Spectroscopy, Francois Lagugne-Labarthet, Gregory Q. Wallace, Hayden C. Foy, Scott M. Rosendahl

Chemistry Publications

Metallic nanostructures that exhibit tailored optical resonances spanning from the near to mid-infrared spectral range are of particular interest for spectroscopic and optical measurements in these spectral domains that can benefit from localized surface-enhancement effects. Plasmon resonances shifted in the near or mid-infrared range could be used to further enhance the excitation and/or the emission of an optical process. Surface-enhanced infrared absorption (SEIRA) is one of such processes and can particularly benefit from plasmon-enhanced local fields yielding an increase in sensitivity towards the detection of an analyte. Herein, we have fabricated a series of gold dendritic nanostructures, prepared by electron-beam …