Physical Chemistry Commons^™

Progress And Perspective Of Fuel Cell Technology, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Fuel cell, a clean and high-efficiency electrochemical power source, has being paid much attention worldwide recent years. In this paper, the progress and perspective of fuel cell technology are elucidated in detail. Fuel cells have been applied in some special fields such as spacecraft, shuttle and submarines. However, in the areas of transportation, stationary station and portable power source, fuel cells are still under demonstration due to the durability and cost problems. The reliability and surrounding survivability of fuel cells should be enhanced in the special application. Meanwhile, the durability and cost of fuel cells are the main issues to …

Preparation And Electrochemical Performance Of Lifepo4/C By Spray Drying Method Assisted With Organic Template, Quan-Bing Liu, Yang-Mei Jiang, Hui-Yu Song, Shi-Jun Liao

Journal of Electrochemistry

In this work, the LiFePO₄/C composites were prepared by the spray drying and carbothermal method, and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge measurements. The effects of the organic assisted templates on the morphologies and electrochemical properties of the LiFePO₄/C composites were investigated. The results showed that the morphology and microstructure of the composites could be tuned by incorporating with the different templates. The morphology of the composite appeared to be solid microspheres if no organic template was added, while porous microspheres, nest-like …

Synthesis And Electrochemical Performance Of Xlifepo4·Yli3V2(Po4)3 Composites, Ping-Ping Ma, Zhi-Jian Liu, Jian-Hua Xia, Yu Chen, Pu Hu, Zhi-Chao Lu, Ding-Guo Xia

Journal of Electrochemistry

A series of xLiFePO₄·yLi₃V₂(PO₄)₃ composites were systematically synthesized through solid state reactions by variations in the proportions of LiFePO₄ and Li₃V₂(PO₄)₃. The properties of the prepared compounds were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The capacity of 162.7 mAh/g at 0.2 C rate was obtained with the relatively good cycle stability and good conductivity for 0.95LiFePO₄·0.05Li₃V₂(PO₄)₃ due to more uniformed distributed and smaller particle sizes.

Preparation And Characterization Of Mno/Tin Anode For Lithium Ion Batteries, Gao-Jie Xu, Hai-Yan Yang, Peng-Xian Han, Li-Xue Zhang, Ke-Jun Zhang, Chuan-Jian Zhang, Yu-Hua Fan, Cai-Feng Bi, Guang-Lei Cui

Journal of Electrochemistry

Manganese titanate (MnTiO₃) powder was prepared via a sol-gel method using manganese acetate and tetrabutyl titanate as raw materials, and citric acid as a chelating agent. Through high temperature nitridation of MnTiO₃ powder in ammonia, the MnO/TiN composite was obtained. The phase structure, composition and morphology of the composites were characterized by XRD, SEM and EDS. The electrochemical properties of the composite electrodes were studied by performing cyclic voltammetry, galvanostatic charge and discharge, and electrochemical impedance spectroscopy tests. The MnO/TiN electrode delivered specific capacities of 394 mAh·g^-1 and 146 mAh·g^-1 at the current density of …

Temperature Effects On The Electron-Transfer Reactions Of Fe(Cn)63-/4- And Cytochrome C, Jing Tang, Lin Du, Xiao-Jian Xiao, Ning Zhang

Journal of Electrochemistry

Cyclic voltammetric and chronoamperometric techniques were employed to study the temperature effects on the electrochemical reaction of Fe(CN)₆^3-/4- by self-made thermostatic water bath electrochemical cell. The diffusion coefficient D and the formal heterogeneous electron-transfer rate constant k0 were calculated at different temperatures from 25 °C to 75 °C. In the Fe(CN)₆^3-/4- system, the DO values of Fe(CN)₆^3- were directly proportional to temperature, while DR of Fe(CN)₆^4- inversely proportional to temperature. The values of k^₀ decreased with the increase of temperature due possibly to the electrode passivation resulted from the decomposition of …

Electrochemical Fabrication Of The Ordered Polyaniline Nanowires Array, Yan-Xin Gao, Li-Chao Sun, Su-Yuan Xie, Kang Shi

Journal of Electrochemistry

The effects of electrochemical fabrication methods in different aniline concentrations on the morphologies of polyaniline, which was polymerized on the aligned-multi-walled carbon nanotubes electrode in H₂SO₄ or HClO₄ electrolyte solution, were investigated. It was demonstrated that the polyaniline nanowires would not be prepared by cyclic voltammotry, whereas the nanowires could be obtained by the potentiostatic method without forming the ordered array. Only when the aniline concentration in HClO₄ solution was high enough, the ordered polyaniline nanowires array could be fabricated by the constant current method.

Preparation And Hydrogen Evolution Properties Of Ni/Ag2O/Ruo2-Pt Cathodes, Shu Huang, Xue-Ming Li, Wu-Lin Li, Wen Wang

Journal of Electrochemistry

The Ni/Ag₂O/RuO₂-Pt composite cathode was prepared by sol-gel method using RuCl₃ and H₂PtCl₆ as raw materials. The effects of heat treatment conditions and AgNO₃ concentrations on hydrogen evolution properties were investigated. The morphology and composition of Ni/Ag₂O/RuO₂-Pt composite cathode have been characterized by XRD, XPS and SEM-EDS. It is demonstrated that the surface structure of Ni/Ag₂O/RuO₂-Pt composite cathode is more compact, with fewer cracks and larger surface roughness than pure nickel. At the conditions of 0.3 A·cm^-2, 90 ^oC, and …

Ag Nanoparticles Self-Assembled Films On Iron Surface And Their Inhibition Properties, Zhe Zhang, Ming-Zi Jia, Le Ruan

Journal of Electrochemistry

The Ag nanoparticles were prepared in aqueous solutions through a chemical reduction method and transferred from water phase to toluene phase with the protection of 1-dodecanethiol (DDT). The polished iron electrode was immersed in the DDT-protected metal nanoparticles toluene solutions to form DDT/Ag nanoparticles self-assembled mixed films. Electrochemical methods such as electrochemical impedance spectroscopy and polarization curve measurement were used to study the inhibition properties of the self-assembled films in the 0.5 mol·L^-1 H₂SO₄ solution. The appearance of elements such as S and Ag from the XPS data identified the presences of DDT and Ag nanoparticles.

Function Assignment Within The Haloacid Dehalogenase Superfamily, Hua Huang

Chemistry and Chemical Biology ETDs

The HaloacidDehalogenase Enzyme Superfamily (HADSF) is a ubiquitous family of enzymes. Presently, more than 45,000 deposited gene sequences encode proteins of the HADSF, and only a fraction of these have defined structure and/or function. The work described in this thesis focuses on function determination in several members of the HADSF. An integrated bioinformatic-protein structure-enzyme mechanism approach was used to differentiate and track D-glycero-D-manno-heptose-1,7-bisphosphate phosphatase (GHMB) and histidinol phosphatephosphatase (HisB)orthologues; 2-keto-3-deoxynononic acid 9-phosphatephosphatase (KDN9PP) and 2-keto-3-deoxy-D-manno-octulosonic acid 8-phosphatephosphatase (KDO8PP)orthologues; inorganic pyrophosphatase and β-phosphoglucomutase(β-PGM) orthologues. In addition, a structure-function/bioinformatic analysis was carried-out on the bifunctional 1,3-diposphoglycerate acyltransferase/Cys-S-glyceryl-3-phosphate phosphatase (FKBH). Each study began …

Evolution Of Structure And Function Among Hotdog-Fold Thioesterases And Had Family Phosphatases, Wang Min

Chemistry and Chemical Biology ETDs

My doctoral research began with the function assignment to two domains of fusion protein BT4699, from Bacteriodes thetaiotaomicron, BF1314 from Bacteriodes fragilis and PG1653 from Porphyromonas gingivalis. BT4699, however, is insoluble, so its orthologue BF1314 and PG1653 were prepared and studied. The fusion proteins consist of a domain that belong to a large family of phosphatases known as Haloacid Dehalogenase (HAD) superfamily, and a domain belong to the hotdog-fold thioesterase superfamily. The genes encoding the fusion proteins located at an operon that encoding enzymes involved in the menaquinone biosynthetic pathway. So we assumed that the thioesterase domain is connected to …

Horizontally-Aligned Carbon Nanotubes Arrays And Their Interactions With Liquid Crystal Molecules: Physical Characteristics And Display Applications, Frederick Roussel, Jean-Francois Brun, Alexandre Allart, Limin Huang, Stephen O'Brien

Publications and Research

We report on the physical characteristics of horizonthally-grown Single-Walled Carbon Nanotubes (h-al-SWNT) arrays and their potential use as transparent and conducting alignment layer for liquid crystals display devices. Microscopy (SEM and AFM), spectroscopic (Raman) and electrical investigations demonstrate the strong anisotropy of h-al-SWNT arrays. Optical measurements show that h-al-SWNTs are efficient alignment layers for Liquid Crystal (LC) molecules allowing the fabrication of optical wave plates. Interactions between h-al-SWNT arrays and LC molecules are also investigated evidencing the weak azimuthal anchoring energy at the interface, which, in turn, leads to LC devices with a high pretilt angle. The electro-optical reponses of …

Applications Of Electronic Structure Theory To Problems In Strong-Field Chemistry, Inorganic Chemistry, And Nanomaterial Systems, Jason Anthony Sonk

Wayne State University Dissertations

This dissertation covers research performed on applications of electronic structure theory to various fields of chemistry and is divided into eight chapters. Chapters 2 through 4 describe a series of related works which explore applications of excited state electronic structure methods to problems in strong field chemistry. Chapters 5, 6, and 7 discuss the application of electronic structure theory methods to solving problems in inorganic chemistry. Finally, Chapter 8 looks at an application of electronic structure theory to nanomaterials.

Chapter 2 covers the modeling of electron dynamics of butadiene interacting with a short, intense laser pulse in the absence of …

State-Resolved Slice Imaging Of Photochemical Dynamics, Herath Mudiyans Nuradhika Herath

Wayne State University Dissertations

This dissertation focuses on the understanding the unimolecular photochemistry and dynamics

utilizing state-resolved slice imaging approach combined with the quantum-state selective

spectroscopy technique called resonance enhanced multi photon ionization (REMPI)

method. This powerful technique allows selecting the initial quantum states of the reactants

and determining the nal quantum states, energy, the orientation and alignments of

the products. In the investigations of photodissociation dynamics of acetone at 230 nm,

a bimodal distribution for the resulting CO photoproduct is identied. This observation

indicated the presence of unimolecular dissociation mechanism analogues to the roaming

dynamics reported in formaldehyde photodissociation. Moreover, another type of …

Water Diffusion In And Out Of The Β-Barrel Of Gfp And The Fast Maturing Fluorescent Protein, Turbogfp, Marc Zimmer, Binsen Li, Ramza Shahid, Paola Peshkepija

Chemistry Faculty Publications

The chromophore of fluorescent proteins is formed by an internal cyclization of the tripeptide 65SYG67 fragment and a subsequent oxidation. The oxidation is slow – the kinetics of this step is presumably improved in fast maturing GFPs. Water molecules can aid in the chromophore formation. We have used 50ns molecular dynamics simulations of the mature and immature forms of avGFP and TurboGFP to examine the diffusion of water molecules in-and-out of the protein β-barrel. Most crystal structures of GFPs have well-structured waters within hydrogen-bonding distance of Glu222 and Arg96. It has been proposed that they have an important role in …

Toward A Regional Radiocarbon Model For The East Texas Woodland Period, Robert Z. Selden Jr., Timothy K. Perttula

CRHR: Archaeology

The East Texas Radiocarbon Database contributes to an analysis of tempo and place for Woodland era (ca. 500 B.C. - A.D. 800) archaeological sites within the region. The temporal and spatial distributions of calibrated radiocarbon (¹⁴C) ages (n=127) with a standard deviation (ΔT) of 61 from archaeological sites with Woodland components (n=51) are useful in exploring the development and geographical continuity of the peoples in East Texas, and lead to a refinement of our current chronological understanding of the period. While the analysis of the dates produces less than significant findings due to sample size, they are used …

Modeling Regional Radicarbon Trends: A Case Study From The East Texas Woodland Period, Robert Z. Selden Jr.

CRHR: Archaeology

The East Texas Radiocarbon Database contributes to an analysis of tempo and place for Woodland era (~500 BC–AD 800) archaeological sites within the region. The temporal and spatial distributions of calibrated ¹⁴C ages (n = 127) with a standard deviation (ΔT) of 61 from archaeological sites with Woodland components (n = 51) are useful in exploring the development and geographical continuity of the peoples in east Texas, and lead to a refinement of our current chronological understanding of the period. While analysis of summed probability distributions (SPDs) produces less than significant findings due to sample size, they are used …

Dynamic Light Scattering And Microelectrophoresis: Main Prospects And Limitations, Vuk Uskoković

Pharmacy Faculty Articles and Research

Microelectrophoresis based on the dynamic light scattering (DLS) effect has been a major tool for assessing and controlling the conditions for stability of colloidal systems. However, both the DLS methods for characterization of the hydrodynamic size of dispersed submicron particles and the theory behind the electrokinetic phenomena are associated with fundamental and practical approximations that limit their sensitivity and information output. Some of these fundamental limitations, including the spherical approximation of DLS measurements and an inability of microelectrophoretic analyses of colloidal systems to detect discrete charges and differ between differently charged particle surfaces due to rotational diffusion and particle orientation …

Probing The Dynamics Of Radical Reactions With Polyatomic Hydrocarbons By Crossed-Beam Dc Slice Imaging, Armando Dura Estillore

Wayne State University Dissertations

This work presents results of crossed molecular beam imaging studies on the reaction of radicals (Cl and CN) with polyatomic hydrocarbons of different functionalities such as pentane isomers, deuterated alkanes, alkenes, and alcohols. The reactively scattered alkyl radicals are probed as a function of collision energy using single photon ionization. The scattering results for pentane are quite similar for all reactants, suggesting that the nature of the abstraction site has surprisingly little influence on the dynamics studied at ~5 and ~9 kcal/mol. The angular distributions are broad with a backscattered peak at low collision energy and a sharp forward peak …

Pegylated Silicon Nanowire Coated Silica Microparticles For Drug Delivery Across Intestinal Epithelium, Vuk Uskoković, Phin-Peng Lee, Laura Walsh, Kathleen Fischer, Tejal Dasai

Pharmacy Faculty Articles and Research

Composite particles made by growing nanoscopic silicon wires from the surface of monodispersed, microsized silica beads were tested in this study for their ability to affect the integrity and permeability of an epithelial cell layer. Polyethylene glycol (PEG) is known to sterically stabilize particles and prevent protein binding; as such, it is a routine way to impart in vivo longevity to drug carriers. The effect of the silica beads, both with and without silicon nanowires and PEG, on the disruption of the tight junctions in Caco-2 cells was evaluated by means of: (a) analysis of the localization of zonula occludens-1 …

Maxwell's Equations, Part V, David W. Ball

Chemistry Faculty Publications

This is the fifth installment in a series devoted to explaining Maxwell’s equations, the four mathematical statements upon which the classical theory of electromagnetic fields – and light – is based. Previous installments can be found on Spectroscopy’s website (whose URL can be found throughout these issues). Maxwell’s equations are expressed in the language of vector calculus, so a significant part of some previous columns have been devoted to explaining vector calculus, not spectroscopy. For better or worse, that’s par for the course, and it’s my job to explain it well – I trust readers will let me know if …

Ƴ-Selective Directed Catalytic Asymmetric Hydroboration Of 1,1-Disubstituted Alkenes, Sean M Smith, Gia L. Hoang, Rhitankar Pal, Mohammad O. Bani Khaled, Liberty S. W. Pelter, Xiao Cheng Zeng, James M. Takacs

Xiao Cheng Zeng Publications

Directed catalytic asymmetric hydroborations of 1,1-disubstituted alkenes afford ƴ

-dioxaborato amides and esters in high enantiomeric purity (90–95% ee).

On The Nature Of Weak Intermolecular Forces: A First Principles Approach To Hydrogen Bonding And Pi-Type Interactions, Kari Lorene Copeland

Electronic Theses and Dissertations

Computational quantum chemistry is a branch of chemistry that is based on quantum mechanics. In this field, chemical phenomena is represented in mathematical form and computers are used to provide numerical solutions to rigorous mathematical equations. Through this medium, the properties of atoms and molecules are calculated with high accuracy. Chapter 1 opens with a general discussion of science, the development of atomic theory and computational chemistry. Electronic structure theory is more extensively reviein Chapter 2. Hydrogen bonding and dispersion forces are defined in Chapter 3, and the procedures used to computationally study these type interactions are considered. Chapter 4 …

Synthesis And Flame Retardant Testing Of New Boronated And Phosphonated Aromatic Compounds, Vladimir Benin, Sravanthi Durganala, Alexander Morgan

Chemistry Faculty Publications

The present report describes the preparation and use of some dimethyl terephthalate derivatives in transition metal-catalyzed coupling reactions to produce new reactive flame retardants. Dimethyl iodoterephthalate and dimethyl 2,5-diiodoterephthalate were successfully employed in the preparation of phosphonic and boronic esters and acids. The latter were tested for heat release with a microcombustion calorimeter (ASTM D7309) to determine the potential for heat release reduction of these flame retardant molecules. The results showed that the addition of boronic or phosphonic acids greatly lowered the heat release, due to a condensed phase (char formation) mechanism. Adding ester groups to the boronic acids or …

A New, Simple, Green And One-Pot Four-Component Synthesis Of Bare And Poly(Α, Γ, L-Glutamic Acid) Capped Silver Nanoparticles, Magdalena Stevanović, Igor Savanović, Vuk Uskoković, Srečo D. Škapin, Ines Bračko, Uroš Jovanović, Dragan Uskoković

Pharmacy Faculty Articles and Research

A simple and green chemical method has been developed to synthesize stable bare and capped silver nanoparticles based on the reduction of silver ions by glucose and capping by poly(α,γ,Lglutamic acid) (PGA). The use of ammonia during synthesis was avoided. PGA has had a dual role in the synthesis and was used as a capping agent to make the silver nanoparticle more biocompatible and to protect the nanoparticles from agglomerating in the liquid medium. The synthesized PGA-capped silver nanoparticles in the size range 5–45 nm were stable over long periods of time, without signs of precipitation. Morphological examination has shown …

Observation Of Sulfate Aerosols And So₂ From The Sarychev Volcanic Eruption Using Data From The Atmospheric Chemistry Experiment (Ace), D. Doeringer, A. Eldering, C. D. Boone, G. González Abad, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

[1] Infrared spectra measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on the SCISAT satellite were used to analyze the Sarychev volcanic aerosol after the eruption in June 2009. Evidence of the Sarychev eruptions was first detected in July 2009 from enhanced SO₂ concentrations and atmospheric extinction. By February 2010, the atmosphere had returned to pre-Sarychev conditions. In July 2009, the volcanic plume was found between 8.5 km and 17.5 km in altitude at mid- and high latitudes (55°N–70°N). The first SO₂ and sulfate aerosol retrievals carried out using the infrared solar occultation spectra recorded with …

Applications Of Density Functional Theory In Materials Science And Engineering, Manuel Alvarado

Open Access Theses & Dissertations

Density Functional Theory (DFT) is a powerful tool that can be used to model various systems in materials science. Our research applies DFT to two problems of interest. First, an organic/inorganic complex dye system known as a Mayan pigment is modeled to determine chemical binding sites, verifying each model with physical data such as UV/Vis spectra. Preliminary studies on palygorskite-based mayan pigments (mayacrom blue, mayacrom purple) show excellent agreement with experimental studies when using a dimer dye geometry binding with tetrahedrally-coordinated aluminum impurity sites in palygorksite. This approach is applied to a sepiolite-based organic/inorganic dye system using thioindigo attached to …

Investigations Of Noncovalent Interactions Using Raman Spectroscopy And Electronic Structure Computations, Ashley Wright

Electronic Theses and Dissertations

This dissertation research focuses on the effects of noncovalent interactions on vibrational energy levels. Vibrational spectroscopy is a powerful tool for the study of the effects of weak intermolecular interactions such as hydrogen bonding and interactions with the environment, including solvation effects. Changes in the vibrational spectra of interacting molecules allow us to ascertain exactly which atoms and bonds are affected and to what extent they are affected. Quantum mechanical methods, ab initio theory and density functional theory, are employed to model molecular geometries, properties, and subtle interactions between molecules. Much of this research centers on the comparison of these …

Multi-Configurational Investigation Of Thermolytic Pathways Of Highly Strained Ring Systems, Jeffrey Dwayne Veals

Electronic Theses and Dissertations

The isomerization pathways of model high energy structures are of interest because of their relation to high energy density fuels. Electron resonance has been found to greatly affect the relative activation barriers for several isomerization pathways, and the major goal of this research is to accurately describe its role in determining the relative barriers for strain energy release pathways. This research is centered around the potential energy surfaces (PES's) for ? bond breaking and ? bond rotation in these highly strained structures. Of particular interest was how would resonance and or electronegativity affect the allowed/disallonature of the activation barriers in …

Development Of Tailor-Designed Gold-Platinum Nanoparticles Binary Catalysts For Efficient Formic Acid Electrooxidation, Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

The modification of a glassy carbon (GC) electrode with platinum (PtNPs) and gold (AuNPs) nanoparticles is targeted to fabricate efficient anodes for the electrooxidation of formic acid (FA). A proper adjustment of the deposition sequence of PtNPs and AuNPs could eventually enhance the electrocatalytic activity of the electrode in such a way that suppresses the CO poisoning effect during FA oxidation. The highest catalytic activity is obtained at the Au/Pt/GC electrode (with PtNPs firstly deposited on the GC electrode followed by AuNPs). This superb enhancement is quantified by comparing the relative ratio of the direct vs. the indirect oxidation peaks …

Self-Assembling Subnanometer Pores With Unusual Mass-Transport Properties, Xibin Zhou, Guande Liu, Kazuhiro Yamato, Yi Shen, Ruixian Cheng, Xiaoxi Wei, Wanli Bai, Yi Gao, Hui Li, Yi Liu, Futao Liu, Daniel M. Czajkowsky, Jingfang Wang, Michael J. Dabney, Zhonghou Cai, Jun Hu, Frank V. Bright, Lan He, Xiao Cheng Zeng, Zhifeng Shao, Bing Gong

Xiao Cheng Zeng Publications

A long-standing aim in molecular self-assembly is the development of synthetic nanopores capable of mimicking the mass-transport characteristics of biological channels and pores. Here we report a strategy for enforcing the nanotubular assembly of rigid macrocycles in both the solid state and solution based on the interplay of multiple hydrogen-bonding and aromatic π − π stacking interactions. The resultant nanotubes have modifiable surfaces and inner pores of a uniform diameter defined by the constituent macrocycles. The self-assembling hydrophobic nanopores can mediate not only highly selective transmembrane ion transport, unprecedented for a synthetic nanopore, but also highly efficient transmembrane water permeability. …