Physical Chemistry Commons^™

Preparation And Characterization Of Titanate-Phosphate Passivation Film On Tinplate, Zi-Yu Wang, Ming-Hao Wang, De-Yu Li, Ning Li

Journal of Electrochemistry

A passivation film was prepared on tinplate surface with a composite passivating agent made of titanate and phosphate. The surface morphologies, chemical compositions and corrosion resistances of the passivation films were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), salt spray test, Tafel polarization measurement and electrochemical impedance spectroscopy (EIS). The results were compared with those films untreated and treated with titanate or phosphate passivation. It was shown that the titanate and phosphate passivation film was mainly composed of Ti₃(PO₄)₄·nH₂O and TiO₂. The finely crystallized surface could seal …

Preparation And Properties Of Nanocrystalline Nickel By Pulse Electrodeposition On Glassy Carbon, Ya-Li Zhang, Ming-Xian Zhang, Teng-Da Guo, Yan-Jie Zhao, Sheng-Xue Yu

Journal of Electrochemistry

Nanocrystalline nickel exhibits electrocatalytic activity for methanol. In this work, nanocrystalline nickel coating has been obtained by using the double pulse method on glassy carbon materials surface. The influence of pulse conditions on the grain size of nanocrystalline nicke was studied. The concentrations and compositions of the plating bath were  300 g·L^-1 NiSO₄·6H₂O,45 g·L^-1 NiCl₂·6H₂O,40 g·L^-1 H₃BO₃,5 g·L^-1 C₇H₅NO₃S,and 0.05 g·L^-1 C₁₂H₂₅NaO₄S. The optimal pulse process parameters including the average pulse …

Synthesis And Electrochemical Properties Of Nickel-Rich Cathode Material Lini0.6Co0.2Mn0.2O2 With High Initial Coulombic Efficiency, Xiao-Yun Guan, Chao-Yu Hong, Jian-Ping Zhu, Wei-Li Wang, Yi-Xiao Li, Yong Yang

Journal of Electrochemistry

Nickel-rich cathode materials LiNi_0.6Co_0.2Mn_0.2O₂(NCM622)were synthesized by a co-precipitation-solid state sintering method at different temperatures. The structure, morphology and electrochemical performance of the as-prepared materials were investigated by X-ray powder diffraction (XRD) /Rietveld refinement, scanning electron microscope (SEM) and electrochemical experiments. It is found that NCM622 calcined at 800 ℃ showed the lowest degree of cation disorder (~1.97%) with a high initial Coulombic effiency of 92.2% and the capacity retention of 81.4% after 100 cycles.

Electrodeposition Of Cigs Thin Film With Special Structure Using Laser Etching Template, Jin-Zhi Yu, Ye Lian, Jin-Qiu Zhang, Pei-Xia Yang, Mao-Zhong An

Journal of Electrochemistry

Copper indium gallium selenide (Cu_1.00In_xGa_1-xSe_2.00, CIGS) thin film solar cells have a wide application in semiconductor thin film batteries. The CIGS absorbing layer is the key of the thin film solar cell material. Therefore, it is of theoretical and practical significance to carry out researches in CIGS thin films. In this work, the CIGS thin films with special structures were prepared by using laser etching template. The copper thin film was firstly electrodeposited in aqueous solution with Laser etching template. The influences of temperature, current and concentration of copper sulfate on morphology …

An Electrochemical Investigation In The Anticorrosive Properties Of Silver Nanoparticles For The Acidic Corrosion Of Aluminium, H. A. Fetouh, B. A. Abd-El-Nabey, Y. M. Goher, M. S. Karam

Journal of Electrochemistry

The mass loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used for the determinations of the corrosion rates for aluminium in 1.0 mol·L^-1 hydrochloric acid (HCl) solutions both in the absence and presence of silver nanoparticles (SNPs) at 30 ℃. The protection efficiency was evaluated to be 96.4% for 0.014 g·L^-1 of the SNPs. It has been found that the capacity of the electrical double layer at the aluminium/solution interface was decreased with increasing the concentration of the SNPs, indicating that the SNPs were adsorbed at the aluminium surface. The Langmuir adsorption isotherm and the kinetic-thermodynamic …

Preface For Special Issue On Electroplating And Surface Finishing, Mao-Zhong An

Journal of Electrochemistry

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Superhydrophobic Surface On Aluminum Alloy By Hydrothermal Method And Its Electrochemical Performance, Xiao-Hang Chen, Mo-Jing Chen, Yu-Lin Min, Qun-Jie Xu

Journal of Electrochemistry

Superhydrophobic film formed on a metal surface is an effective way for corrosion protection. In this paper, the superhydrophobic film was prepared on the surfaces of aluminum alloy by hydrothermally treating with a solution containing CeCl₃·7H₂O and CO(NH₂)₂ , and a self-assemble process. The electrochemical measurements and surface morphology results confirmed that the best superhydrophobicity and electrochemical performance could be achieved with the contact angle of 155.5^o after six hours of hydrothermal reaction. Furthermore, the inhibition efficiency of 99.6% was obtained in 3.5 wt% NaCl aqueous solution, indicating the excellent corrosion resistance …

Intrinsic Kinetic Properties Of Ternary Material For Lithium Ion Batteries Assessed By Single Particle Microelectrode, Yi-Min Wei

Journal of Electrochemistry

Electrochemical performances such as capacity, rate, cycle and thermal stability of the nickel (Ni), cobalt (Co) and manganese (Mn) ternary cathode material, LiNi_xCo_yMn_zO₂ (x + y + z = 1), are significantly influenced by the proportion of Ni, Co, and Mn elements. To obtain higher specific capacity, LiNi_0.6Co_0.2Mn _0.2O₂ (NCM622) and LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) with high amounts of Ni element were employed for the lithium ion batteries. By now, many studies have been focusing on the thermal and cycling stabilities of …

Preparation And Electrocatalytic Activity Of Nitrogen-Doping Tungsten Carbide Catalyst, Pian-Pian Yang, Li-Zhen Huang, Ying-Ying Li, Mei-Qin Shi, Chun-An Ma

Journal of Electrochemistry

Tungsten carbide (WC) is a promising electrocatalyst, however, its electrocatalytic activity is far inferior to Pt and Pt-group metal. In this work, nitrogen-doping tungsten carbide (WN|WC) catalysts with a nanoplate morphology were prepared via the tungsten nitride (WN) as the precursor and sodium tungstate as the tungsten source. The SEM and TEM results indicated that carbon atoms entered into the WN lattice to form the hexagonal close packed WC phase. In this way, an atomic scale heterostructure involving the closely linked interfaces between WN and WC was created . The XRD data confirmed that the cubic crystal structure of WN …

Deposition Mechanism And Coating Characterization For The Trivalent Chromium Electrodeposition In Sulphate Electrolyte, Hui Yan, Shuai-Shuai Huang, Fang-Zu Yang, Zhong-Qun Tian, Shao-Min Zhou

Journal of Electrochemistry

Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) were used to study the electrodeposition mechanism of trivalent chromium on a copper electrode in the novel sulphate electrolyte for thick trivalent chromium plating. The thickness, morphology, composition, microhardness, and structure, as well as the corrosion resistance in 3.5wt% NaCl solution of the trivalent chromium coatings were investigated by X-ray fluorescence gage, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), microhardness tester, X-ray diffraction (XRD) and Tafel curve measurements. The results showed that the electrodeposition of trivalent chromium involved two consecutive one electron reduction steps. The first step, Cr³⁺ + e …

Surface Ehancement Of Nickel Ions On Cyanide Free Immersion Gold Deposited From A Chloroauric Acid-Choline Chloride Solution On Medium-Phosphorus Nickel, Tian-Yu Xu, Shi-Ying Wang, Wen-Chang Wang, Zhi-Dong Chen

Journal of Electrochemistry

The nickel ions (Ni²⁺) were introduced into choline chloride (ChCl) cyanide free immersion gold solution to improve the surface quality of electrodeposition on medium-phosphorus nickel substrate. The addition of Ni²⁺ had no significant impact on the plating speed. However, the hyperactive corrosion of nickel substrate could be effectively alleviated by the addition of 500 mg·L^-1 NiCl₂·6H₂O, and the surface morphology of gold coating could be greatly improved. The choline chloride bath has great potential for industrial production due to its high Ni²⁺ carrying capacity (2000 mg·L^-1) and superior applicability …

Effects Of Carboxylic Acids On Structure And Performance Of 10% Vanadium Modified Li2Fesio4/C Composites, Xue-Xia Wei, Jia-Qi Huang, Shi-Yang Liu, Xuan Cheng, Ying Zhang

Journal of Electrochemistry

The carbon coated 10% vanadium modified lithium iron silicate (Li₂Fe_0.9V_0.1SiO₄/C) composites were prepared by sol-gel method to form precursor and followed by solid state reaction. Effects of different carboxylic acids, namely, citric acid, acetic acid and oxalic acid, on the crystal structures, surface morphologies, interfacial characteristics and electrochemical properties of the composites were systematically investigated. It was found that a mixed P2₁ and Pmn2₁ phase was formed with the major impure phase of iron (Fe) and minor impurity of lithium silicate (Li₂SiO₃). The initial discharge capacities …

Applications Of Electrospinning In Lithium-Air Batteries, Yue Fu, Jin Wang, Hai-Yang Yu, Jing-Hua Tian, Rui-Zhi Yang

Journal of Electrochemistry

Lithium-air batteries have received increasing attention as the “ultimate batteries” due to their extremely high theoretical capacity and environment friendly. However, there are still many obstacles hindering the wide applications of the lithium-air batteries owing to the limitations of large charge-discharge over-potentials, poor Columbic efficiency and cycling performance. Exploring of high-efficiency, low-cost and eco-friendly catalysts is one of the vital issues for lithium-air batteries. Meanwhile, electrospinning techniques have been under substantial developments due to its simple fabrication process, high efficiency and production. This paper reviews the recent progresses in fabrications of various novel catalysts for lithium-air batteries with electrospinning techniques, …

Innovative Monte Carlo Methods For Sampling Molecular Conformations, Aliasghar Sepehri

LSU Doctoral Dissertations

Sampling molecular conformations is an important step in evaluating physical, mechanical, hydrodynamic, and optical properties of flexible molecules especially polymers. One powerful method for this purpose is configurational-bias Monte Carlo in which one random segment of a molecule is chosen, all segments toward one random end are removed, and then regrown segment by segment to produce a new geometry to be accepted/rejected according to probability laws. The advantage of this method is the ability to generate acceptable conformations that are favorable for intra- and intermolecular energies to save computational costs. However, when there are several interdependent energetic terms, trial generation …

Undergraduate Research In Petrology Approached Through Computer Modeling Of Fabric Evolution In Igneous Rocks, Michael C. Leopold, M. J. Bonder, C. W. Holyoke, T. G.M. Krohn, R. V. Amenta

Chemistry Faculty Publications

Undergraduate research is an important part of the curriculum in many geology departments but, in recent years, it has become more difficult to attract students into projects dealing with solid-earth studies due to the limited employment prospects in these areas compared to those in environmental geology. This report describes how petrologic research can be made more attractive to students by an approach using C programming to model crystal growth and fabric development in poly crystalline solids. This topic has broad appeal to students in the other sciences as well as geology, and the computer skills learned have wide practical utility …

Investigation Of Novel Electrolytes For Use In Lithium-Ion Batteries And Direct Methanol Fuel Cells, Kartik Pilar

Dissertations, Theses, and Capstone Projects

Energy storage and conversion plays a critical role in the efficient use of available energy and is crucial for the utilization of renewable energy sources. To achieve maximum efficiency of renewable energy sources, improvements to energy storage materials must be developed. In this work, novel electrolytes for secondary batteries and fuel cells have been studied using nuclear magnetic resonance and high pressure x-ray scattering techniques to form a better understanding of dynamic and structural properties of these materials. Ionic liquids have been studied due to their potential as a safer alternative to organic solvent-based electrolytes in lithium-ion batteries and composite …

Organic Photochemistry: Remote Delivery Of Reactive Oxygen Intermediates Via A Heterogeneous Approach, Niluksha Walalawela Abeykoon

Dissertations, Theses, and Capstone Projects

Photosensitized oxidation reactions produce a number of intermediates species, which are generated in varying amounts over time. This complexity presents major challenges in the study of oxidation processes. Mechanistic efforts to separate and deliver reactive oxygen intermediates enable their controlled use in processes such as bacterial inactivation. This thesis describes a heterogeneous reaction approach taken to control the generation and delivery of reactive oxygen intermediates. The mechanistic details of photosensitized reactions were elucidated via synthetic, materials, and physical organic techniques to optimize the delivery of reactive oxygen intermediates. This thesis contains six chapters as described below.

Chapter 1 gives a …

The Van Der Waals Fluid's Liquid Vapor Coexistence Locus, Carl W. David

Chemistry Education Materials

The liquid vapor coexistence locus is plotted from the analytical solution to the Maxwell construction for the van der Waals fluid.

Structural Evolution Of Gold-Doped Bismuth Clusters AubiN– (N = 4−8), Seema Pande, Tian Jian, Navneet S. Khetrapal, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The structures of gold-doped bismuth clusters, AuBi_n⁻ (n = 4−8), are investigated through a joint photoelectron spectroscopy and density functional theory (DFT) study. Well-resolved photoelectron spectra are obtained at several photon energies. Global minimum searches coupled with DFT calculations yield low-lying structures, whose relative energies are further evaluated by single-point energy calculations at the CCSD(T) level of theory. Vertical detachment energies are calculated with the inclusion of spin−orbit effects to compare with the experimental data. Three-dimensional structures are found to be dominant in this size range, while a planar low-lying isomer is observed only for AuBi_{4 …}

X-Ray Spectroscopy Of Nio And Nanodiamond At Ssrl, Jackson Earl

STAR Program Research Presentations

The first aspect of this research project focuses on investigating the surface chemistry of high pressure high temperature (HPHT) nanodiamond by using X-ray spectroscopy techniques at the Stanford Synchrotron Radiation Lightsource (SSRL). HPHT nanodiamond is being examined as a biosensing tool for electric field detection based on the fluorescent nitrogen vacancy center hosted within diamond. With use of the transition edge spectrometer (TES), a state-of-the-art X-ray fluorescence detector, we are able to probe the surface and bulk properties of diamond. Preliminary work using density functional theory (DFT) has been done, offering insight into ground state energies and electronic structure. DFT …

Probing The Surface Of Nanodiamonds At Stanford Synchrotron Radiation Lightsource And San Jose State University, Jocelyn Valenzuela, Jackson Earl, Cynthia Melendrez, Grace Jeanpierre, Dennis Nordlund, Abraham Wolcott

STAR Program Research Presentations

The nitrogen-vacancy center in diamond is a promising tool in oncology, electric field sensing, and quantum cryptography. High-pressure high-temperature (HPHT) nanodiamonds (NDs) are prime contenders for these fields because they host nitrogen-vacancy centers (NVCs) which are applicable towards cancer detection and electric and magnetic field sensing. However, to apply HPHT NDs to these fields, the surface must first be functionalized—a difficult process because of the inert nature of the surface. The project at hand focuses on surface modification of HPHT NDs with amines to allow for further bioconjugation of small molecules and plasmonic shells. This is done via liquid-phase chemistry …

Radical Chemistry In A Femtosecond Laser Plasma: Photochemical Reduction Of Ag+ In Liquid Ammonia Solution, Victoria K. Meader, Mallory G. John, Laysa M. Frias Batista, Syeda Ahsan, Katharine M. Tibbetts

Chemistry Publications

Plasmas with dense concentrations of reactive species such as hydrated electrons and hydroxyl radicals are generated from focusing intense femtosecond laser pulses into aqueous media. These radical species can reduce metal ions such as Au3+ to form metal nanoparticles (NPs). However, the formation of H2O2 by the recombination of hydroxyl radicals inhibits the reduction of Ag+ through back-oxidation. This work has explored the control of hydroxyl radical chemistry in a femtosecond laser-generated plasma through the addition of liquid ammonia. The irradiation of liquid ammonia solutions resulted in a reaction between NH3 and OH·, forming peroxynitrite and ONOO−, and significantly reducing …

Applications Of Molecular And Quantum Mechanical Methods For Studying The Chemical Reactions Of Inorganic And Organic Systems, Yi-Jung Tu

Wayne State University Dissertations

Computational studies can assist chemists to interpret experimental observations and to predict the properties and behaviors of molecules. The work presented in this dissertation applies different computational methods to study the molecular properties and reaction paths for various inorganic and organic systems. The second and third chapters discuss the force field development using “Gaussian Electrostatic Model (GEM)” and its amenability for use in the AMOEBA force field. The forth and fifth chapters discuss the density functional theory (DFT) studies of photodissociation behaviors for inorganic molecules. The sixth chapter explores the oxidation mechanisms of ascorbic acid and its antioxidant properties in …

Computational Study Of Transition Metal Complexes For Solar Energy Conversion And Molecular Interaction With Strong Laser Fields, Xuetao Shi

Wayne State University Dissertations

There are two topics in this dissertation: ground state and excited state modeling of a few series of transition metal complexes that facilitate solar energy conversion, and Born-Oppenheimer Molecular Dynamics (BOMD) simulations of molecular cations interacting with intense mid-infrared laser light.

In Chapter 2 and 3, a few series of transition metal complexes that facilitate solar energy conversion are studied computationally. Metal-to-ligand charge-transfer (MLCT) excited states of several (ruthenium) (monodentate aromatic ligand, MDA) chromophore complexes are modeled by using time-dependent density function theory (TD-DFT). The calculated MLCT states correlate closely with the heretofore unknown emission properties that were observed experimentally. …

3d Momentum Imaging Spectroscopy Probing Of Strong-Field Molecular And Surface Dynamics, Lin Fan

Wayne State University Dissertations

Electron-ion coincidence measurements in combination with 3-dimensional (3D) momentum imaging can provide comprehensive 3D-momentum information to unravel multichannel photoionization/dissociation processes, and thus is an effective tool to investigate atomic/molecular dynamics. A camera-based 3D coincidence momentum imaging system and the velocity mapping imaging (VMI) based machine were introduced in Chapter 2. Studies of strong field dissociative single and double ionization of relatively large molecules camphor and 2-phenylethyl-N, N-dimethylamine (PENNA) were carried out and illustrated in Chapter 3. We demonstrated the main products of double ionization of PENNA were singlet diradicals. In Chapter 4, a novel angle resolved-photoemission spectroscopy based on VMI …

Physical Chemistry Of Gas-Liquid Interfaces: Foreword, Jennifer Faust

All Faculty Articles

Physical Chemistry of Gas-Liquid Interfaces, the first volume in the Developments in Physical & Theoretical Chemistry series, addresses the physical chemistry of gas transport and reactions across liquid surfaces. Gas-liquid interfaces are all around us, especially within atmospheric systems such as sea spray aerosols, cloud droplets, and the surface of the ocean. Because the reaction environment at liquid surfaces is completely unlike bulk gas or bulk liquid, chemists must readjust their conceptual framework when entering this field. This book provides the necessary background in thermodynamics and computational and experimental techniques for scientists to obtain a thorough understanding of the …

Mechanistic Studies Of Proton-Coupled Electron Transfer Reactions Involving Antioxidants, Kejie Meng

Theses and Dissertations

The objective of the research was to investigate proton-coupled electron transfer (PCET) reactions involving antioxidants to gain insight into the detailed mechanisms of glutathione (GSH), Trolox, and α-tocopherol (α-TOH). PCET reactions are complex redox reactions that transfer electrons and protons sequentially or in concert. These reactions are ubiquitous in natural or artificial processes that produce electrochemical energy that is extractable as electricity or as chemical fuels of high energy content. Examples of processes based on PCET are photosynthesis, respiration, nitrogen fixation, carbon dioxide reduction, redox fuel cells, and artificial photosynthesis. Antioxidants were selected as a PCET model to understand the …

Gas-Phase Studies Of Nucleophilic Substitution Reactions: Halogenating And Dehalogenating Aromatic Heterocycles, Leah L. Donham

Theses and Dissertations

Halogenated heterocycles are common in pharmaceutical and natural products and there is a need to develop a better understanding of processes used to synthesize them. Although the halogenation of simple aromatic molecules is well understood, the mechanisms behind the halogenation of aromatic heterocycles have been more problematic to elucidate because multiple pathways are possible. Recently, new, radical-based mechanisms have been proposed for heterocycle halogenation. In this study, we examine and test the viability of possible nucleophilic substitution, S_N2@X, mechanisms in the halogenation of anions derived from the deprotonation of aromatic heterocycles. All the experiments were done in a …

Solvent And Concentration Effects Governing The Hierarchical Organization Of Asphaltenes: A Small-Angle X-Ray Scattering Study, Hasan Rejoanur Rahman

Open Access Theses & Dissertations

Asphaltenes are a group of planar molecules found in crude oil and are prone to aggregation which often causes blockage of pipes along the oil production stream resulting a huge economic downside. In an effort to understand the hierarchical organization of asphaltene in different solvents and concentrations, the solution structure of various asphaltene solutions were studied using small-angle x-ray scattering (SAXS). Solvents were chosen based on miscibility maps. Such maps are generated on the critical value of the solubility parameter difference between asphaltenes or asphaltene components, and a range of solvents. The critical factors that affect asphaltene and asphaltene component …

Characterization Of Coacervate Systems Using Redox Sensitive Dyes, Caleb Kaiser

All Master's Theses

Coacervates are systems that spontaneously form when two oppositely charged polyelectrolytes are mixed in a concentrated salt solution. When coacervates form, a biphasic equilibrium occurs in the sample with two phases present in the solution. The two phases are described as the dense phase and the lean phase, named after the amount of polyelectrolyte material in each phase. Coacervates have been topics of interest to researchers in a variety of fields including biomedical applications, drug delivery devices, and more. This thesis worked towards the characterization of coacervate systems on the molecular level by investigating the interaction of the polyelectrolytes and …