Chemistry Commons^™

Study On The Electrochemical Enhanced Self-Assembled Cobalt-Porphyrin Monolayer, Bei Zhang, Rong Wang, Guo-Yang Zhu, Xiaowei Cao, Xia-Qin Wu, Zong-Rang Zhang, Takeo Ohsaka

Journal of Electrochemistry

According to the different coordination ability between Cobalt(II) porphyrin and Cobalt(Ⅲ) porphyrin,an electrochemical modulated self-assembling process was developed to prepare the CoTMPP/MP/Au(E) modified electrode.The O2 reduction catalytic activity and the Raman spectrum of the CoTMPP/MP/Au(E) modified electrode were found to be similar to those of the CoTMPP/MP/Au(I) modified electrode obtained by the immersion method,which was suggested that both modified electrodes have the similar well oriented structure and electrochemical behavior.Compared with CoTMPP/Au modified electrode,the modified electrodes with mercaptopyridine ligand were showed better electrocatalytic activity and stability.

Effects Of Direct Current Bias Potentials On Lipid Membranes Forming On A Glassy Carbon Electrode, Yu-Hui Li, Hong-Wei Zhang, Gui-Lan Song, Zhan-Jun Zhang, Sheng-Min Cai

Journal of Electrochemistry

The effects of direct current(DC) bias voltage on the structure of lipid membranes forming on a glassy carbon electrode(GCE) was investigated by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS).The experiment showed that the lipid membranes can be formed with either positive or negative bias potential exerted.When bias voltage was exerted,bilayer lipid membranes tended to form due to the electrostatic interaction between the superficial positive charges on the polarized electrode and the negative charged part of PC.When the positive bias voltage overrun the range,the lacunas on s-BLMs would increase,and the BLMs would be broken.A proper equivalent circuit was nonlinearly fitted,based on the …

Polarization Properties Of The Cu/Paa Composite Films, Li-Chun Zhang, Qing-Shan Li, Meng-Meng Zheng, Fu-Quan Wu

Journal of Electrochemistry

Porous alumina templates with different apertures were fabricated by the pore widening and increase of the anodic oxidation voltage,and then Cu nanowires were synthesized in porous alumina templates by alternating electro-deposition method.The transmission spectrum and polarization spectrum of Cu/PAA composite films were measured.Experiment have indicated that both the pore widening and increase the anodic oxidation voltage can make the transmittance drop,but the pore widening cannot enhance the polarization performance of the micropolarizer.The extinction ratio can be improved with increase of the template oxidation voltage or the Cu nanowires' diameter.

Investigations On Edlcs Using Pmma-Based Gel Polymer Electrolytes, Xiang-Li Meng, Jin-Ling Yin, Juan Ren, Bao-Hong Zhang

Journal of Electrochemistry

Polymethyl methacrylate(PMMA) based gel polymer electrolytes electrochemical double layer capacitors(GPE-EDLCs) were fabricated by an in situ polymerisatonal method with actived carbon electrodes,using propylene carbonate(PC) and ethylene carbonate(EC) as plasticizer,lithion perchlorate as surporting electrolytes.The ion conductivity values of GPEs were evaluated by AC impedance.The properties of PMMA-based GPEs capacitors were researched by impedance spectrum,cyclic voltammetry,galvanostatic charge-discharge.It showed that the ion conductivities of the PMMA-based gel polymer electrolytes reached to 3.7 mS·cm-1 at ambient tempreture.The working voltage of the capacitors reached to 3.0 V.The specific capacitance of the capacitor was obtained as high as 41.6 F·g-1(I=1 mA·cm-2).The equivalent serial resistance of the …

Variable Frequence Switching Power Supply Used To Aluminum Foil Corrosion, Xiang-Dong Zhuo, Lan Sun, Guo-Qing Qian, Chang-Jian Lin

Journal of Electrochemistry

A new variable frequence and multi-wave power supply used to aluminum foil corrosion is introduced.The switching supply power supply controlled by the microcontroller and Variable Frequence in low band and multi-wave、big power supply controlled by the electronic switch bridge for changing phase were designed.This power supply does not need bulky and cumbersome transformer,and the frequency at lower limit is not limited,even lower than 1Hz.

Fragmentation Of Methyl Chloride Studied By Partial Positive And Negative Ion Yield Spectroscopy, D. Ceolin, Maria Novella Piancastelli, Renaud Guillemin, Wayne C. Stolte, S-W Yu, Oliver Hemmers, Dennis W. Lindle

Environmental Studies Faculty Publications

The authors present partial-ion-yield experiments on the methyl chloride molecule excited in the vicinity of the Cl2p and C1s inner shells. A large number of fragments, cations produced by dissociation or recombination processes, as well as anionic species, have been detected. Although the spectra exhibit different intensity distributions depending on the core-excited atom, general observations include strong site-selective fragmentation along the C–Cl bond axis and a strong intensity dependence of transitions involving Rydberg series on fragment size.

High-Resolution Structure Of A Beta-Peptide Bundle, Douglas S. Daniels, E. James Petersson, Jade X. Qiu, Alanna S. Schepartz

Chemistry Faculty Publications

We recently reported that β-peptides can form discrete hetero-oligomers in aqueous solution. Here we describe the structure of such an oligomer as determined by X-ray crystallography. The structure of Zwit-1F reveals a homo-octamer of two cupped “hands” composed of both parallel and antiparallel 314-helices. The core of the assembly is composed entirely of solvent-excluded β3-homoleucine residues. The Zwit-1F assembly shares many of the physical characteristics of natural proteins.

Thermochemistry Of 2- And 3-Acetylthiophenes: Calorimetric And Computational Study., María Victoria Roux, Manuel Temprado, And Pilar Jiménez, Rafael Notario, James S. Chickos, Ana Filipa L. O. M. Santos And, Manuel A. V. Ribeiro Da Silva

James Chickos

No abstract provided.

Calorimetric And Computational Study Of Indanones, M. Agostinha R. Matos, Margarida S. Miranda, Manuel J. S. Monte, Luis M. N. B. F. Santos, Victor M. F. Morais, James S. Chickos, Patamaporn Umnahanant, Joel F. Liebman

James Chickos

No abstract provided.

Photochemical Production Of Micromolarsuperoxidestandards In Aqueous Solutiont, T. C. Ong, D. W. King

Undergraduate Research Symposium (UGRS)

Superoxide(O2-) is a reactive free radical that rapidly undergoes disproportionation to hydrogen peroxide and oxygen. This property makes preparation of superoxide standard for instrument calibration difficult. McDowell et al. (1983) showed photolysis of ketone and alcohol as a convenient method to generate superoxide through triplet and radical intermediates reacting with molecular oxygen. This study expands on this past work and investigates detailed mechanism of the reaction.

Thermal Effects On Mechanical Grinding-Induced Surface Texture In Tetragonal Piezoelectrics, Wonyoung Chang, Alexander H. King, Keith J. Bowman

Alexander H. King

The effect of temperature on grinding-induced texture in tetragonal lead zirconate titanate (PZT) and lead titanate (PT) has been investigated using in situ x-ray diffraction (XRD) with an area detector. In contrast with previous results on electrical poling, mechanically-ground PT and soft PZT materials retain strong ferroelastic textures during thermal cycling, even after excursions to temperatures slightly above the Curie temperature. The relationship between the residual stresses in the surface region, caused by grinding, and those resulting from domain wall motion is elucidated by in situ texture measurements obtained during thermal cycling.

How Surface Stresses Lead To Size-Dependent Mechanics Of Tensile Deformation In Nanowires, M. Ravi Shankar, Alexander H. King

Alexander H. King

It has been proposed that surface and interface stresses can modify the elastic behavior in nanomaterials such as nanowires. The authors show that surface stresses modify the tensile response of nanowires only when nonlinear elastic effects become important leading to cross terms between the applied stress and the surface stress. These effects are only significant when the radius of the nanowire is of the order of a few nanometers. The resulting alteration of tensile stiffness, though effected in part by the nonlinear elastic modulus, is particularly wrought by a modification of the stress state in the deformed nanowire.

Effect Of The Lattice Crystallinity On The Electron−Phonon Relaxation Rates In Gold Nanoparticles, Wenyu Huang, Wei Qian, Mostafa El-Sayed

Wenyu Huang

In order to study the importance of surface phonons on the electron−phonon relaxation in plasmonic nanoparticles, the effect of size, shape, and materials have recently been studied. Gold and silver nanoparticles have shown no dependence on size and shape while copper nanoparticles have shown some size dependence. This suggests that the bulk phonons, which are sensitive to the bulk-phase structure, are solely responsible for the relaxation of the hot electron in gold and silver plasmonic nanoparticles. The importance of bulk phonons should depend on the degree of crystallinity. In the present study, we have found that the electron−phonon relaxation rate …

On The Universal Scaling Behavior Of The Distance Decay Of Plasmon Coupling In Metal Nanoparticle Pairs: A Plasmon Ruler Equation, Prashant K. Jain, Wenyu Huang, Mostafa A. El-Sayed

Wenyu Huang

Localized surface plasmon resonances (LSPR) in lithographically fabricated gold (Au) nanodisc pairs are investigated using microabsorption spectroscopy and electrodynamic simulations. In agreement with previous work, we find that the fractional plasmon wavelength shift for polarization along the interparticle axis decays nearly exponentially with the interparticle gap. In addition, we find that the decay length is roughly about 0.2 in units of the particle size for different nanoparticle size, shape, metal type, or medium dielectric constant. The near-exponential distance decay and the interesting “universal” scaling behavior of interparticle plasmon coupling can be qualitatively explained on the basis of a dipolar-coupling model …

The Effect Of Plasmon Field On The Coherent Lattice Phonon Oscillation In Electron-Beam Fabricated Gold Nanoparticle Pairs, Wenyu Huang, Wei Qian, Prashant K. Jain, Mostafa El-Sayed

Wenyu Huang

By using electron beam lithography, we fabricated pairs of gold nanoparticles with varying interparticle separation. Double-beam femtosecond transient absorption spectroscopy was used to determine the coherent lattice oscillation frequency as a function of the interparticle separation in the presence of the plasmon field excited by the monitoring probe light. We found that the fractional shift in the coherent lattice phonon oscillation frequency follows an exponential decay with respect to the interparticle gap scaled by the disc diameter with the same decay constant as that previously observed for the fractional shift in the surface plasmon electronic oscillation resonance frequency. This strongly …

Carbazolyl Nitrenium Ion:  Electron Configuration And Antiaromaticity Assessed By Laser Flash Photolysis, Trapping Rate Constants, Product Analysis, And Computational Studies, Arthur Winter, Harry H. Gibson, Daniel E. Falvey

Arthur Winter

Laser flash photolysis of 1-(carbazol-9-yl)-2,4,6-trimethylpyridinium tetrafluoroborate generates the carbazolyl nitrenium ion (τ = 333 ns, kobs = 3.0 × 106 M-1s-1) having absorption bands at 570 and 620 nm in CH3CN. The nitrenium ion is found to have reactivity comparable to structurally similar closed-shell diarylnitrenium ions, but spectroscopic evidence favors an open-shell singlet diradical assignment for the observed nitrenium ion. The carbazolyl nitrenium ion is also more reactive than diarylnitrenium ions as a likely result of antiaromatic character. Ab initio and hybrid DFT calculations were performed to address the degree of antiaromaticity in this and similar nitrenium ions through analysis …

Benzylic Cations With Triplet Ground States:  Computational Studies Of Aryl Carbenium Ions, Silylenium Ions, Nitrenium Ions, And Oxenium Ions Substituted With Meta Π Donors, Arthur Winter, Daniel E. Falvey, Christopher J. Cramer, Benjamin F. Gherman

Arthur Winter

Density functional theory (B3LYP/6-31G(d,p)) was used to predict the effect of meta substitution on aryl cationic (Ar−X+) species, including aryloxenium ions, arylsilylenium ions, arylnitrenium ions, and arylcarbenium ions. Multireference second-order perturbation theory (CASPT2) calculations were used to benchmark the quantitative accuracy of the DFT calculations for representative systems. Substituting the meta positions on these species with π donors stabilizes a π,π* diradical state analogous to the well-known m-xylylene diradical. Notably, the 3,5-bis(N,N-dimethylamino)benzyl cation is predicted to have a triplet ground state by 1.9 kcal/mol by DFT and to have essentially degenerate singlet−triplet states at the CASPT2(10,9) level of theory. Adding …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

The stability of the association of iodine with FCC and NOM products were studied. Product distributions for the various matrices under various reaction conditions were examined in order to maximize the binding of iodine. The recovery of the iodine from the sequestration matrices was also examined, along with the conversion of the iodine to matrices more suitable for geological storage and/or use as transmutation targets.

The following are the specific research objectives and goals:

• Develop bench-scale experimental set-up and procedures for simulating plutonium extraction process (PUREX) head-end vapor phase.
• Develop experimental procedures for evaluating iodine sequestering methods using bench-scale procedures. …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process, or FLEX. The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objectives of this project are to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solution, and to use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborator, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species, enhancing the ability to selectively target and sequester individual species from mixtures. This project is in its third year and has successfully completed phases 1 and 2. Phase 3 has been partially completed. The tasks have been expanded …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are …

F-Element Electrochemistry In Room Temperature Ionic Liquids, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This proposal focuses on f-element electrochemistry in room temperature ionic liquids (RTILs). The ultimate goal is to fully characterize the oxidation/reduction of elements in RTILs to establish the baseline thermodynamic and kinetic data for these systems. The data will be used to critically evaluate the ability to use electrochemical methods for controlled, potential mediated, separation off-elements by electroplating on electrodes surfaces. Factors that will influence the ability to measure the redox processes in f-elements in RTIL solutions and electroplating on electrode surfaces include the structure, solubility, and stability of the target species in these solutions. These factors will be addressed …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU–includes Np, Pu, Am, and Cm) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership. In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in this new …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the UREX separation scheme, providing data useful to modeling. The areas to be examined include the speciation of U and Pu with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK system. The complexation constants of U and Pu with tributylphosphate will be evaluated. In the TALSPEAK system, …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic methods, intermediate chemical phases at the interface, intermixing/ diffusion behavior, and the electronic interface structure as a function of material (metal and coating materials) and temperature are examined.

In the past year, emphasis was placed on a detailed analysis and description of the Cs/SiC interface formation process.

Design And Performance Of A Curved-Crystal X-Ray Emission Spectrometer, A. C. Hudson, Wayne C. Stolte, Dennis W. Lindle, Renaud Guillemin

Chemistry and Biochemistry Faculty Research

A curved-crystal x-ray emission spectrometer has been designed and built to measure 2–5 keV x-ray fluorescence resulting from a core-level excitation of gas phase species. The spectrometer can rotate 180°, allowing detection of emitted x rays with variable polarization angles, and is capable of collecting spectra over a wide energy range (20 eV wide with 0.5 eV resolution at the Cl K edge) simultaneously. In addition, the entire experimental chamber can be rotated about the incident-radiation axis by nearly 360° while maintaining vacuum, permitting measurements of angular distributions of emitted x rays.

Formation Of In- (2×1) And In Islands On Si (100) - (2×1) By Femtosecond Pulsed Laser Deposition, M. A. Hafez, H. E. Elsayed-Ali

Electrical & Computer Engineering Faculty Publications

The growth of indium on a vicinal Si (100) - (2×1) surface at room temperature by femtosecond pulsed laser deposition (fsPLD) was investigated by in situ reflection high-energy electron diffraction (RHEED). Recovery of the RHEED intensity was observed between laser pulses and when the growth was terminated. The surface diffusion coefficient of deposited In on initial two-dimensional (2D) In- (2×1) layer was determined. As growth proceeds, three-dimensional In islands grew on the 2D In- (2×1) layer. The RHEED specular profile was analyzed during film growth, while the grown In islands were examined by ex situ atomic force microscopy. The full …

A Novel Tio2 / Pvc Layer For Use In A Photoelectrochemical Cell, Faiza Touati, John Cassidy, Kevin Mcguigan

Articles

A novel method of coating titanium dioxide on a glassy carbon electrode as a polyvinylchloride composite , is described. On illumination , there is an enhanced voltammetric current at this TiO2/PVC composite in aqueous formic acid solution. This electrode is used as the basis of a formic acid fuel cell where oxygen is reduced at a platinum cathode. The system yields 100 cm-2 for 0.01 mol dm-3 HCOOH in 0.1 mol dm-3 NaOH under illumination from a 150 W xenon lamp. The current without illumination is 0.5 cm-2.

An Experiment Using A Simple Photoassisted Fuel Cell Designed To Remediate Simulated Wastewater, John Cassidy, Faisa Touati, Kevin Mcguigan

Articles

Work in photochemistry work peaked in the 1980’s where there was the prospect of using sunlight shining on suspensions of titanium dioxide in order to catalytically cleave water into hydrogen and oxygen [1-5]. In this way a clean and efficient method of producing hydrogen as a fuel was envisaged. However, there was a requirement to use a rather high energy light to achieve the splitting and it was not as efficient with visible light[5]. Doped TiO2 layers have been used in a three electrode system for formic acid degradation[6]. In this work, the system uses an electrode coated with TiO2 …

Improved Nitrate Sensing Using Ion Selective Electrodes Based On Urea–Calixarene Ionophores, Benjamin Schazmann, Dermot Diamond

Articles

Urea–calix[4]arenes 1 and 2 were synthesised and incorporated into ISE membranes for assessment as sensors for inorganic anions in water. 1 revealed a strong response to all anions following the Hofmeister selectivity order. For ISEs of 2, the response to a portion of the anion series was suppressed, increasing the margin of selectivity of nitrate over chloride, a common interferant of nitrate in fresh and marine water samples. The performance of ISEs containing 2 was compared to commercially available alkylammonium nitrate ion-exchange salts used for nitrate sensing. Our ISEs performed favourably in terms of sensitivity, linear range and LOD performing …