Chemistry Commons^™

High-Purity Gallium Analysis By Inductively Coupled Plasma Mass Spectrometry, Kyungjean Min

Open Access Theses

The mobility of Two-dimensional Electron Gas in AlGaAs/GaAs heterostructures that are grown in the Molecular Beam Epitaxy (MBE) can be increased by purification of the gallium used to grow the films. To attain 200 million cm2/Vs mobility, the impurity concentration of gallium should be reduced to below 1 ppb. The commercial 7N (99.99999%) gallium with 100 ppb total impurity is currently used in the MBE at Purdue University and is being purified by zone refining. To evaluate the commercial 7N gallium and establish the methodology for the impurity measurement after zone refining, germanium, iron, and zinc in 6N and 7N …

Electrochemically Active Biofilm Assisted Synthesis Of Ag@Ceo2 Nanocomposites For Antimicrobial Activity, Photocatalysis And Photoelectrodes, Mohammad Mansoob Khan Dr, S. A. Ansari, J. H. Lee, M. O. Ansari, J Lee, M. H. Cho

Dr. Mohammad Mansoob Khan

Ag@CeO2 nanocomposites were synthesized by a biogenic and green approach using electrochemically active biofilms (EABs) as a reducing tool. The as-synthesized Ag@CeO2 nanocomposites were characterized and used in antimicrobial, visible light photocatalytic and photoelectrode studies. The Ag@CeO2 nanocomposites showed effective and efficient bactericidal activities and survival test against Escherichia coli O157:H7, and Pseudomonas aeruginosa. The as-synthesized Ag@CeO2 nanocomposites also exhibited enhanced visible light photocatalytic degradation of 4-nitrophenol and methylene blue than pure CeO2. A photocatalytic investigation showed that the Ag@CeO2 nanocomposites possessed excellent visible light photocatalytic activities compared to pure CeO2. Electrochemical impedance spectroscopy and photocurrent measurements showed that the …

Molecular Engineering Strategies For The Design And Synthesis Of New Organic Photovoltaic Materials, Paul J. Homnick

Doctoral Dissertations

Dramatic improvements in organic photovoltaic device efficiency can be obtained by optimizing spectral absorbance and frontier molecular orbital (FMO) energies, increasing solid state exciton/charge mobility, and utilizing p-/n-type nanoarchitecture. Combining all of these properties into a new material presents a considerable synthetic challenge because potential commercial applications require materials that are high-performance and inexpensive. Thus, it is advantageous to design new materials using a versatile, modular synthetic approach that allows each design criterion to be engineered individually, in a synthetically efficient manner. Several strategies were successfully pursued using simple interchangeable electron donor and acceptor components as functional modules, which …

Creasing Instability Of Hydrogels And Elastomers, Dayong Chen

Doctoral Dissertations

CREASING INSTABILITY OF HYDROGELS AND ELASTOMERS MAY 2014 DAYONG CHEN, B.S., TIANJIN UNIVERISTY M.S., TIANJIN UNIVERSITY M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Ryan C. Hayward Soft polymers placed under compressive stress can undergo an elastic creasing instability in which sharp folds spontaneously form on the free surfaces. This process may play an important role in contexts as diverse as brain morphogenesis, failure of tires, and electrical breakdown of soft polymer actuators. While the creasing instability has been used for collotype printing since as early as the 1850s, the scientific appreciation of this instability …

Preparation And Lithium Storage Performance Of Sn-Snsb Nanoparticles, Yao Xiao, Jiao-Hong Wu, Qi Wang, Ling Huang, Jun-Tao Li, Shi-Gang Sun

Journal of Electrochemistry

Tin was widely studied as alternative anode material to carbon for lithium-ion batteries thanks to its much higher theoretical capacity. However, a pure tin electrode suffers severely from its poor cycleability due to mechanical fatigue caused by volume change during lithium insertion and extraction processes. Tin-based alloy may improve the cycleability property of tin electrode. In this article, we report facile synthesis of spherical Sn-SnSb nanopartciles using a simple solvent-thermal approach. It is amazing to find that the spherical Sn-SnSb nanoparticles can circumvent volume changes effectively during charge-discharge process. Electrochemical discharge/charge results show that the spherical Sn-SnSb nanoparticles electrode exhibits …

Electrochemical Fabrication Of Two-Dimensional Flower-Like Pt Nanostructures For Methanol Electrocatalytic Oxidation, Xia Wang, Jun Hu, Yong-Jun Li

Journal of Electrochemistry

Two-dimensional flower-like Pt nanostructures (2D FPNs) were fabricated on glassy carbon substrates by galvanostatical electrochemical technique. The electrolyte was the HAuCl₄ + HClO₄ aqueous solution without addition of any structure-directing organic reagent, which made as-prepared Pt nanostructures cleaner, exhibiting much higher reactivity. Scanning electron microscopic images revealed that 2D FPNs were spherical Pt nano-flowers constructed by the smallest building blocks, nano-leaves. The number density of spherical Pt nano-flowers can be tuned by controlling the electrodeposition time. High resolution transmission electron microscopic images indicated that each nano-leaf was formed by growing along Pt(111) direction. Electrocatalytic activities of as-prepared 2D …

High Sensitive Detection Of Cd(Ii) And Pb(Ii) Based On Antimony-Film Covered Pencil Core Electrodes, Shan Chen, Zhao-Yan Zheng, Yi-Min Fang, Li-Qing Zheng, Jian-Jun Sun

Journal of Electrochemistry

In this paper, a pencil core was used as the substrate for an antimony-film electrode for simultaneous detection of Cd(II) and Pb(II) by square-wave anodic stripping voltammetry (SWASV). With the deposition time of 180 s, the low limit of detection (LOD) for the electrode was determined to be 0.075 ?g?L-1 for Cd(II), while 0.13 ?g?L-1 for Pb(II) with good reproducibility in low pH solutions (pH = 2). The results show a much lower LOD than that of bismuth-film pencil core electrode. Finally, this antimony-film electrode was successfully applied to determine Cd(II) and Pb(II) in tap water.

Electrochemical Catalysis: A Dft Study, Li Li, Zi-Dong Wei

Journal of Electrochemistry

In this review, we focus on achievements in electro-catalysis based on the density function theory study. The relationships among the electrode potential, electronic structure of catalysts and electro-catalytic activity are summarized in three parts: the adsorption and desorption of species, electron transfer, and stability of catalysts. The electrode potential and the electronic structure (d-band center or Fermi (HOMO) energy) of catalysts significantly influence the formation, adsorption and desorption of surface species on electrode. The electro-catalytic activity can be improved by modulating the electrode potential and electronic structure of catalysts.

A Sensitive And Label-Free Electrochemical Aptasensor Based On Signal Amplification Of Carbon Nanotubes, Chun-Yan Deng, Hui-Min Fan, Juan Xiang, Yuan-Jian Li

Journal of Electrochemistry

A label-free electrochemical sensing electrode for highly sensitive detection of adenosine was constructed based on the signal amplification of carbon nanotubes (CNTs). The change in the interfacial feature of the modified electrode was characterized by electrochemical impedance spectroscopy. Using [Ru(NH₃)₆]³⁺ as the signaling moiety, adenosine with concentrations as low as 0.027 nmol·L^-1 can be selectively detected. Additionally, the fabrication of this present aptasensor was simple, time-saving and cost-effective. Compared with other reported aptasensors, the proposed aptasensor had advantages of excellent sensitivity, selectivity and simplicity, which plays a potential role in development of aptasensor.

Cyclic Voltammetric Studies In Adsorption Of Cetyltrimethylammonium Bromide (Ctab) On Au(111) Electrode, Ling Chen, Chang-Deng Xu, Jin-Yu Ye, Chun-Hua Zhen, Shi-Gang Sun

Journal of Electrochemistry

Adsorption of cetyltrimethylammonium bromide (CTAB) on Au(111) electrode was investigated by cyclic voltammetry (CV). The results demonstrate that the adsorption of CTAB on Au(111) yields particular CV features. Both the adsorption of CTA⁺ and the phase change of the surfactant film are surface structure selective. Two pairs of stable sharp peaks that depend on halide species appear upon the adsorption of cationic surfactant on Au(111) electrode. The relationship between the peak current density and the scan rate indicates that the electron transfer reaction was controlled by diffusion process. These CV features are observed for the first time, and reflect …

Investigation Of The Dynamics Of Photocarriers During Photoelectrochemical Water Splitting By Combination Of Photoelectrochemistry And Transient Absorption Spectroscopy, Wen-Hua Leng

Journal of Electrochemistry

Semiconductor photoelectrochemical hydrogen production is an important and promising technology for utilizing solar energy. The efficiency of hydrogen production depends on the efficiencies of separation and transport of photo-generated carriers. A deep understanding of the behavior of these processes has guiding significance for designing efficient solar hydrogen device. photoelectrochemical and transient absorption spectroscopy methods are powerful tool for studying the microscopic dynamics and mechanism of photocatalytic reaction. This review describes the part of the latest results of the author regarding the semiconductor photoelectrochemical hydrogen production obtained by these methods，and the problems and future research priorities in this field are proposed.

Recent Progress In The Mechanistic Understanding Of Formic Acid Oxidation On Pt Electrode, Jie Xu, Dao-Chuan Jiang, Dong Mei, Zheng-Da He, Yan-Xia Chen

Journal of Electrochemistry

This article reviews the recent progress in understanding of the mechanisms for formic acid oxidation on Pt electrode. There are two pathways for formic acid oxidation on Pt electrode: (1) Indirect Pathway through which HCOOH is oxidized to CO₂ through CO_ad intermediate. This pathway contributes only 1% of the total current; (2) Direct Pathway where HCOOH is oxidized directly to CO₂. The results from IR Spectroscopy, single-crystal electrochemistry and DFT calculation all support that the bridge-bonded formate is neither the intermediate of direct pathway nor the precursor for CO_ad formation in indirect pathway. Possible mechanism …

Electrocatalytic Oxidation Of Formate On Pd-Cu/C - Effect Of Dealloying Pretreatment, Jiang Kun, Wang Ye, Lin Tao, Cai Wen-Bin

Journal of Electrochemistry

Carbon supported highly dispersed Pd-Cu nanoalloy catalyst toward formate electrooxidation is prepared via one-pot synthesis by using ethylene glycol as the reducing agent and sodium citrate as the stabilizer. The as-prepared catalyst is structurally characterized by TEM and XRD. The Cu dealloyment is carried out through repetitive potential cycling of the Pd-Cu/C catalyst in an acidic solution. The dealloying effect on the performance of the Pd-Cu/C is investigated by using cyclic voltammetry and chronoamperometry, and the surface structural change of Pd-Cu/C is probed by in situ ATR-IR measurement. The results show that the as-prepared Pd-Cu/C processes a better long-term stability …

Electrochemical And Surface Enhanced Raman Spectroscopic Studies Of Benzimidazole On Nickel Electrode, Ping-Jie Wei, Ya-Xian Yuan, Min-Min Xu, Jian-Lin Yao, Ren-Ao Gu

Journal of Electrochemistry

By measuring cyclic voltammograms and polarization curves, the inhibition effects of benzimidazole (BMIH) concentration in acetonitrile system on a nickel electrode were investigated. It was found that the oxidation and the corrosion potentials shifted positively, and the oxidation current decreased with the increase in the concentration of BIMH. Potential dependent adsorption and film formation behavior of BMIH on the nickel electrode were investigated by in situ SERS spectroscopy. With the potential moving from negative direction to positive direction, the complexes made of BIMH and nickel were formed, preventing the nickel electrode from corrosion. In addition, the 0.001 mol·L^-1 of …

Synthesis Of Silver Nanoparticles Supported On Graphene Quantum Dots For Oxygen Reduction Reaction, Jian Ju, Wei Chen

Journal of Electrochemistry

Silver-based catalysts have been extensively investigated as the platinum substituted catalysts due to their high catalytic efficiency, low cost and long-term durability. In this study, the surfactant-free silver nanoparticles supported on graphene quantum dots were synthesized through a facile approach without addition of any other protecting ligands and reducing agents. The “surface-clean” silver nanoparticles had remarkable electrocatalytic performance towards oxygen reduction reaction (ORR) with the most efficient four-electron transfer process. Compared with commercial Pt/C catalyst, the hybrid nanoparticles showed comparable catalytic performance for ORR but much higher tolerance to methanol. Such silver nanoparticles supported on graphene quantum dots may have …

Preparation Of Pt-Tio2/Graphene Composites With High Catalytic Activity Towards Methanol Oxidation And Oxygen Reduction Reaction, Li Qi, Ying Yin, Wen-Guang Tu, Bing-Bing Wu, Zhao-Sheng Wang, Jian-Guo Liu, Jun Gu, Zhi-Gang Zou

Journal of Electrochemistry

A series of graphene-supported TiO₂ nanoparticles (TiO₂/G) with different TiO₂ contents were prepared by a facile hydrothermal method, and then the Pt-TiO₂/G catalysts were successfully prepared by reducing Pt-precursor with microwave technique. Compared with Pt-G catalysts, the catalytic performance toward oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) of Pt-TiO₂/G catalysts was improved due to the addition of TiO₂. However, the excessive TiO₂ would lead to a poor catalytic performance of Pt-TiO₂/G catalysts because of the low electrical conductivity of TiO₂.

Effecting Of Dissolved Oxygen On Microbial Fuel Cells Based On Pseudomonas Aeruginosa, Chang-Li Cao, Li-Xiang Chen, Ran-Ran Wu, Ken-Lin Chang, Feng Zhao

Journal of Electrochemistry

In this work, the reaction between the electron shuttle secreted by Pseudomonas aeruginosa and anode was studied by measuring cyclic voltammogram and open circuit potential. The effect of dissolved oxygen on the oxidation reaction of anode was explored. It was demonstrated that the reaction was a diffusion-controlled and reversible process. The anode was a little affected when the dissolved oxygen of inocula was low (0 ~ 1.6 mg·L^-1). The polarization curves showed that the current output of microbial fuel cells decreased 7% with the impact of dissolved oxygen.

Surgical Adhesive From Mussel Mimetic Polymer, Jenna Desousa, Cori Jenkins, Jonathan Wilker

The Summer Undergraduate Research Fellowship (SURF) Symposium

Injuries involving damaged tissues are currently repaired through an invasive technique involving the use of screws, plates and sutures as support, which can damage these tissues. The biomedical field currently lacks an adhesive that can replace harmful implants. A surgical adhesive can provide a quick and easy alternative, which will minimize the risk of damaging healthy tissue in surgery. Inspiration for such materials can be found by looking at marine mussels as they are able to stick to nearly any surface, even in wet environments. Marine mussels affix themselves to different surfaces using adhesive plaques consisting of various proteins. Polymer …

Structural Dynamics And Charge Transport In Room Temperature Ionic Liquids, Philip James Griffin

Doctoral Dissertations

Room temperature ionic liquids are an important class of materials due to their chemical tunability and numerous advantageous physicochemical properties. As a result, ionic liquids are currently being investigated for use in a wide array of chemical and electrochemical applications. Despite their great potential, however, the relationship between the chemical structure and physicochemical properties of ionic liquids is not well understood.

To this end, this dissertation presents experimental studies of the reorientational structural dynamics and charge transport properties of a variety of room temperature ionic liquids using quasielastic light scattering spectroscopy and broadband dielectric spectroscopy.

Studies of a series of …

56th Annual Rocky Mountain Conference On Magnetic Resonance

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 56th annual meeting of the Rocky Mountain Conference on Magnetic Resonance, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Copper Mountain, Colorado, July 13-17, 2014.

Preparation & Characterization Of High Purity Cu2 Znsn(Sxse1-X)4 Nanoparticles, Bethlehem G. Negash

Open Access Theses

Research in thin film solar cells applies novel techniques to synthesize cost effective and highly efficient absorber materials in order to generate electricity directly from solar energy. Of these materials, copper zinc tin sulfoselenide (Cu₂ZnSn(S_xSe_1-x) ₄) nanoparticles have shown great promise in solar cell applications due to optimal material properties as well as low cost & relative abundance of materials.^1,2 Sulfoselenide nanoparticles have also a broader impact in other industries including electronics³, LED ⁴, and biomedical research⁵. Of the many routes of manufacturing these class of semiconductors, …

Effects Of Oxygen Coverage And Hydrated Proton Model On The Dft Calculation Of Oxygen Reduction Pathways On The Pt(111) Surface, Li-Hui Ou, Sheng-Li Chen

Journal of Electrochemistry

DFT calculation is used to study various possible steps in the oxygen reduction reaction (ORR), including the adsorption and dissociation process of O₂ and the serial protonation process of dissociated products to form H₂O on the Pt(111) surface. By using slabs of different sizes, and different numbers of pre-adsorbed oxygen atoms, the coverage effects on the pathways are investigated. The calculated results using different hydrated proton models are also compared. It is shown that the initial step of the ORR is the formation of a protonated end-on chemisorbed state of OOH*, which can transform to an unprotonated …

Surface Enhanced Raman Spectroscopic Studies Of Pyridine Adsorbed On Ti/Au@Sio2 Film Electrode, Min-Min Xu, Ke Liu, Qing-Hua Guo, Jian-Lin Yao

Journal of Electrochemistry

This study was performed based on shell-isolated nanoparticles-enhanced Raman spectroscopy (SHINERS) technology. The Au@SiO₂ nanoparticles were prepared and characterized by TEM and cyclic voltammetry. It was shown that the shell of SiO₂ was compact. The high quality signal measured by surface enhanced Raman spectroscopy (SERS) was obtained from the adsorbed pyridine on Ti/Au@SiO₂ electrode. The origin of the SERS signals was further confirmed by testing Pt and Ni electrodes. In addition, potential dependent adsorption behavior was investigated. It was found that pyridine was adsorbed parallel on the surface from -0.1 V to -0.6 V, and converted to …

The Ionic Diffusion Model For The Solid Oxide Cathode And Its Verification By The Electrolysis Of Ta2O5 In Molten Cacl2, Hua-Lin Chen, Zhi-Yong Wang, Xian-Bo Jin, George Z. Chen

Journal of Electrochemistry

The deoxidation speed of a solid oxide cathode in molten CaCl₂ can be estimated by the PRS steady diffusion model of O^2-, which correlates the deoxidation speed with the precursor porosity, P, the metal-to-oxide molar volume ratio, R, and the cathode volume shrinkage S. The PRS model indicates that the porosity of the oxide cathode has important influence on the deoxidation speed, and provides a very simple equation for the prediction of the optimal cathode porosity. For the electrolysis of Ta₂O₅, the porosity of the cathode is better to be …

Effects Of Conformational Transformations On Electronic Transport Properties Of Optical Molecular Switches: An Ab Initio Study, Yuan-Yuan He, Jian-Wei Zhao

Journal of Electrochemistry

A series of model molecules with 4 kinds of conformational transformations have been investigated as optical molecular switches by using density functional theory combined with nonequilibrium Green’s function method. The theoretical calculations show that molecules after conformational transformations have photoswitching characteristics. We find that the photochromic molecules with the same conformational transformation usually have a similar current on/off state when they are applied as photoshwitches. Among these transformations, the molecular switch with E(“trans”)/Z(“cis”)-isomerisation of the NN double bond has the highest current on-off ratio. The influences of the energy gap (HLG) between the highest occupied molecular orbital …

A New Silver Electrode Based On The Composite Silver Sulfide/Attapulgite As Ionophore, Wen-Zhuo Li, Ding-Jia Xu, Jun Wang, Jian-Long Wang

Journal of Electrochemistry

A novel silver ion selective electrode with its ionophore being a kind of organic/inorganic composite composed of silver sulfide and attapulgite has been prepared. Attapulgite is a type of natural inorganic polymer which has some properties similar to zeolite, such as a higher specific surface area and plenty of intercrystalline cavities. In this work, the silver ions were firstly adosrbed in the micropores of the attapulgite, then thioacetamidetiny was selected to mix with the prepared silver ions/ attapulgite composite. Owning to the existence of sulfur atoms in the structure of thioacetamide molecules, thioacetamide molecules can react with the silver ions/attapulgite …

Horseradish Peroxidase-Attapulgite Clay Nanocomposites: Fabrication And Application To Sensing The Extracellular H2O2 Released From Cells, Ping Wu, Chen-Xin Cai

Journal of Electrochemistry

The nanostructured attapulgite clay was employed as a support matrix for immobilizing horseradish peroxidase (HRP). FTIR and electrochemical methods demonstrated that HRP had been effectively assembled on attapulgite surface with the formation of HRP-attapulgite nanocomposites. The HRP-attapulgite hybrid was deposited on the glassy carbon (GC) electrode forming the HRP-attapulgite/GC electrode. Cyclic voltammetric results showed a pair of well-defined redox peaks, which were ascribed to direct electron transfer (DET) of HRP, with the formal potential E₀′ = -335 mV (vs. SCE) in the phosphate buffer solution (PBS, pH 7.0). The dependence of E₀′ on solution pH indicated …

23Na Mas Nmr Spectroscopic Study Of Na2Mnpo4F As Cathode Material For Sodium-Ion Battery, Xu Hou, Gui-Ming Zhong, Xiao-Chen Lin, Zi-Geng Liu, Xiao-Biao Wu, Yong Yang

Journal of Electrochemistry

The Na₂MnPO₄F is one of the promising cathode materials for the sodium ion batteries. In the paper, we employed the ex situ X-ray diffraction and solid state NMR techniques to study the charge and discharge processes of this material, including the crystal structure and sodium sites changes. The ex situ x-ray diffraction patterns showed that two new diffraction peaks could be observed at 31^o and 36^o indicating an intermediate phase formed with the extraction of Na+. From the ²³Na MAS NMR spectrum of the material, three peaks were seen at -209 ppm，-258 ppm …

Synthesis, Characterization And Mechanistic Studies Of Biomolecules@Mesomofs, Yao Chen

USF Tampa Graduate Theses and Dissertations

Encapsulation of biomolecules is of great interest to research advances related to biology, physiology, immunology, and biochemistry, as well as industrial and biomedical applications such as drug delivery, biocatalysis, biofuel, food and cosmetics. Encapsulation provides functional characteristics that are not fulfilled by free biomolecules and stabilizes the fragile biomolecules. In terms of biocatalysis, solid support can often enhance the stability of enzymes, as well as facilitate separation and recovery for reuse while maintaining activity and selectivity. Various kinds of materials have been used for encapsulation of biomolecules, among which, porous materials are an important group. Metal-organic frameworks (MOFs) have attracted …

Defect-Induced Band Gap Narrowed Ceo2 Nanostructures For Visible Light Activities, Mohammad Mansoob Khan Dr, S. A. Ansari, D. Pradhan, D. H. Han, J Lee, M. H. Cho

Dr. Mohammad Mansoob Khan

This work reports an electron beam irradiation (30 kGy and 90 kGy) approach to narrow the band gap of the pristine CeO2 nanostructure (p-CeO2) to enhance their visible light activity through defect engineering. This was confirmed by diffuse reflectance spectroscopy, photoluminescence, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller, electrochemical impedance spectroscopy and linear scan voltammetry. XPS revealed changes in the surface states, composition, Ce4+ to Ce3+ ratio and other defects in the modified CeO2 nanostructures (m-CeO2). The m-CeO2 exhibits excellent photocatalytic activities by degrading 4-nitrophenol and methylene blue in the presence of visible light (λ > 400 nm) compared …