Physical Chemistry Commons^™

Morphology-Property Relationship For Binary Organic Thin Films, Alyssa Lynn Griffin

Master's Theses

Organic thin films can be readily mass-produced through solution-based fabrication methods including ink-printing and solution-casting because their light weight, flexibility, and inexpensive sources. Their applications range from organic field-effect transistors (OFET), organic solar cells (OSC), to organic light emitting diodes (OLEDs). Compared with pure component films, binary organic thin films (BOTF) allows for novel characteristics and specialized features to handle more demanding tasks. Due to the complex intermolecular interactions in BOTF, various microscopic phases with different morphological and electronic properties may be formed and this information is difficult to extract through conventional bulk measurements.

Organic thin films can be readily …

Nanostructured Cerium Oxide Based Catalysts: Synthesis, Physical Properties, And Catalytic Performance, Yunyun Zhou

Department of Chemistry: Dissertations, Theses, and Student Research

Cerium oxide is an extensively used industrial catalyst with applications as diverse as catalysts for automobile exhaust, petroleum cracking and organic chemicals synthesis. The catalytic activity of cerium oxide is dependent upon its structural properties, especially the oxygen vacancy defects. While recent advances in characterization techniques have dramatically improved our understanding of cerium oxide functionality, many atomic features in cerium oxide contributing to the overall catalytic reactivity are not yet well-understood. This dissertation focuses on the structural studies of catalytically active cerium oxides with different compositions, phases and morphologies, and their utilizations to establish fundamental understandings of cerium oxide based …

Gas-Phase Electron Diffraction From Laser-Aligned Molecules, Jie Yang, Martin Centurion

Martin Centurion Publications

Electron diffraction is a valuable tool to capture structural information from molecules in the gas phase. However, the information contained in the diffraction patterns is limited due to the random orientation of the molecules. Additional structural information can be retrieved if the molecules are aligned. Molecules can be impulsively aligned with femtosecond laser pulses, producing a transient alignment. The alignment persists only for a time on the order of a picosecond, so a pulsed electron gun is needed to record the diffraction patterns. In this manuscript, we describe the alignment process and show the changes in the diffraction pattern as …

Transition Metal-Olefin Bonding Interactions: A Density Functional Theory Study [ M ( Co ) X ( Æ? 2-C 2 H 3-C 6 H 4-Y) ], Michael John Berninger

Theses and Dissertations

Metal-olefin equilibrium geometries, bond formation energies (Î?E), enthalpies (Î?H), and free energies (Î?G) for a select series of transition (M = Ni, Fe, Cr, Mo and W) metal-olefin carbonyl complexes [M(CO)x(Æ?2-C2H3-C6H4-Y)] have been calculated and compared using density functional theory (DFT), with the BP86 functional under standard state conditions (1 atm, 298.15 K) for the general gas phase formation reaction:

M(CO)x + (C2H3-C6H4-Y) â?? [M(CO)x(Æ?2-C2H3-C6H4-Y)] (1)

Y = NO2, CN, COOH, H, OH, NH2, N(CH3)2

In regards to the electronic modification of the substituent (Y) on styrene at the para position, this study quantitatively investigated the effect of electron-withdrawing and …

Thz-Pulse-Induced Selective Catalytic Co Oxidation On Ru, Jerry L. Larue, Tetsuo Katayama, Aaron Lindenberg, Alan S. Fisher, Henrik Öström, Anders Nilsson, Hirohito Ogasawara

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We demonstrate the use of intense, quasi-half-cycle THz pulses, with an associated electric field component comparable to intramolecular electric fields, to direct the reaction coordinate of a chemical reaction by stimulating the nuclear motions of the reactants. Using a strong electric field from a THz pulse generated via coherent transition radiation from an ultrashort electron bunch, we present evidence that CO oxidation on Ru(0001) is selectively induced, while not promoting the thermally induced CO desorption process. The reaction is initiated by the motion of the O atoms on the surface driven by the electric field component of the THz pulse, …

The Quantum Efficiency Of Cdse Semiconducting Nanocrystals, Charles Bledsoe

Undergraduate Theses

CdSe molecules are semiconducting nanocrystals that absorb visible light and emit broad wavelengths of light in response. They utilize electromagnetic radiation not only for emitting broad wavelengths of visible light, but for fluorescence, conducting electricity, and vibrational relaxation. The Thermal Lensing technique (TL) can be used to study the lifetimes of the excited state transitions and the various nonradiative processes molecules can undergo in order to better understand the excited state dynamics of semiconducting nanocrystals, and in turn, better understand how these molecules may be applied in solar cells, lasers, and fluorescence labeling. Using known methods, four samples of CdSe …

Plotting The Van Der Waals Fluid In Pseudo-3d And The Maxwell Construction, Carl W. David

Chemistry Education Materials

The van der Waals (from his thesis of 1873) equation is a cubic in the molar volume. Plotting the equation in pseudo 3 dimensions is quite simple to do, but including tie lines is quite difficult. Employing the solutions to the cubic van der Waals equation, the tie lines are readily available and can be easily incorporated into the aforementioned 3D plots.

A Ph Switchable Responsive Surface For The Trapping And Release Of A Hydrophobic Substance, Ali Esmail Karim

Masters Theses & Specialist Projects

Solid phase extraction is one of the most widely used techniques to trap and release compounds in a solution. A hydrophobic substance will stick efficiently to a hydrophobic surface (the “like dissolves like” principle). With an introduced response (i.e. pH change), a responsive surface can change from hydrophobic to hydrophilic, weakening the hydrophobic substance’s attraction and thus facilitate in an easy removal. A surface has been prepared having a terminal anthranilic acid (AA) moiety on silica gel particles, microscope slides, and TLC plates in three steps. First, a vinyl group was attached to the surface. Then, this vinyl group was …

Fundamental Studies Of Magnetoconvective Forces And Density Gradients In A Microfluidic Environment, Adam James Kreidermacher

Graduate Theses and Dissertations

Magnetoconvection is a promising phenomenon for developing new electrochemical-based microfluidic flow devices with unique capabilities, such as easily switching flow direction and adjusting flow speeds and flow patterns as well as avoiding bubble formation. In order to develop these devices it is necessary to study the underlying forces. Four contributions toward fluid flow were considered. The first and foremost is the magnetohydrodynamic force, which is the magnetic component of the Lorentz force and governed by the right hand rule. It generates the majority of the convention, and is the most well-known. The second is the gravitational force, which causes convection …

Surface Modification Of Noble Metal Nanostructures Toward Biomedical Applications, Samir V. Jenkins

Graduate Theses and Dissertations

Noble metal nanostructures have seen a steady increase in biomedical application over the last several decades; new diagnostic and therapeutic modalities are under intense investigation. Many of these applications are possible because of post-synthetic modifications to the particle surface. These modifications take a variety of forms and can significantly affect the pharmacokinetics of these particles. In this work, various surface modifications were investigated. Particle agglomeration, which occurs when particle surfaces remain in contact, can significantly affect the toxicity and efficacy of a nanomedicine. Darkfield microscopy and single-particle ICP-MS were developed as complementary methods to detect agglomeration in blood, with the …

A Lego® Brewster Angle Microscope For Quantitative Monolayer Film Analysis, Nicholas Benz

Physics

In order to study single-molecule thick films and their phase behavior we built a Brewster Angle Microscope (BAM). BAM’s are inherently expensive due to their accuracy and precision. We built a fully functional BAM using Lego® Mindstorm® kits for the fraction of the price of a commercial BAM. And by utilizing the 10µm patented Lego® tolerance, comparable accuracy was attained. The BAM was mounted to a Langmuir-trough and will be used for laboratory experiments for optics and physical chemistry along with research on lung surfactant and on liquid crystals.

Fret Study Of Ligand Binding And Exchange Kinetics On The Surface Of Cdse/Zns Quantum Dots, Randee Jean Mcbride

Graduate Theses and Dissertations

Quantum dots are a valuable tool in many research applications and commercial development. Their applications are far reaching and as such have become a topic of great interest. One of their greatest assets is the ability to utilize them as water soluble fluorescent labels. Rendering the nanocrystals water soluble can be accomplished in several ways, but one very popular method is by capping them with water-soluble multi-functional organic ligands. However, these ligands, when attached to the quantum dot surface, are labile and can be exchanged which can be problematic when using the quantum dots in research applications. This projects investigates …

Current Status And Prospect Of Cathode Materials For Lithium Sulfur Batteries, Lan Zhou, Ai-Shui Yu

Journal of Electrochemistry

Elemental sulfur has been extensively investigated as a promising candidate of cathode material for next generation lithium secondary batteries. However, some troublesome issues, such as the low electric conductivity of sulfur (5×10^-30 S·cm^-1) and the high solubility of lithium polysulfide intermediates in organic electrolytes, resulting in a low utilization of active material and a redox shuttling of dissolved polysulfide ions between the sulfur cathode and the lithium anode, which eventually leads to a deposition of insoluble and insulating Li₂S₂/Li₂S on the electrode surface and a fast reduction in the specific capacity. …

Research Status And Application Prospects Of Limnpo4 As A New Generation Cathode Material For Lithium-Ion Batteries, Lai-Fen Qin, Yong-Gao Xia, Li-Peng Chen, Hua-Sheng Hu, Feng Xiao, Zhao-Ping Liu

Journal of Electrochemistry

Olivine-structured lithium manganese phosphate (LiMnPO₄) has the following advantages: excellent thermal stability, low cost, high safety and environmental benignity. Importantly, the theoretical energy density of LiMnPO₄ is about 20% higher than that of commercialized LiFePO₄ due to its higher Li⁺ intercalation potential of 4.1 V (vs. Li⁺/Li). Moreover, the high operating voltage of LiMnPO₄ is compatible with present non-aqueous organic electrolytes of lithium-ion batteries. Therefore, LiMnPO₄ is considered as a next generation cathode material for lithium-ion batteries. However, LiMnPO₄ suffers from poor electronic conductivity and low lithium diffusivity, resulting in …

Preparations And Applications Of Layered Carbon And Layered Carbon-Pbso4 Composite, Shu-Kai Zhang, Hao Zhang, Wei-Hua Xue, Jie Cheng, Wen-Feng Zhang, Gao-Ping Cao, Hai-Lei Zhao, Yu-Sheng Yang

Journal of Electrochemistry

The layered carbon materials (similar to graphene) have been synthesized by chemical vapor deposition (CVD) on the cheap catalyst (potassium or sodium carbonate substrate). The layered-carbon- lead sulfate (PbSO₄) composite could be prepared by in situ chemical deposition based on the layered carbon. The XRD, SEM and TEM results showed that the layered carbon materials was amorphous carbon layer, and the composite was a compound made of fine lead sulfate grains and layered carbon. Thermogravimetric analysis determined the carbon content in the composite. Adding a certain amount of layered carbon or layered-carbon-PbSO₄ composite into negative active materials …

Preparation Of Zro2-Doped Nb/Pbo2 Electrode And Electrocatalytic Performance Of Methyl Orange Degradation, Li Zhang, Wen-Yan Dong, Tai-Lai Yang, Zhen-Hai Liang

Journal of Electrochemistry

The zirconium oxide (ZrO₂)-doped niobium based lead oxide (Nb/PbO₂) electrode was prepared by electrodeposition. The microstructures and electrochemical properties of Nb/ZrO₂+PbO₂ electrode were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), linear sweep voltammetry, electrochemical impedance spectroscopy and cyclic voltammotry. In addition, the Nb/PbO₂ electrode was used as an anode for the electrochemical degradation of methyl orange (MO). Results revealed that the ZrO₂ doping made the Nb/PbO2 electrode surface denser and rougher with smaller sized crystal particles, which increased the specific surface area and enhanced the electrocatalytic activity of the …

Electrochemical Mass Spectrometric Study Of Lithium-Oxygen Batteries, Xin-Xiu Yan, Li-Po Ma, Zhang-Quan Peng

Journal of Electrochemistry

Mass Spectrometry, coupled with electrochemistry, is a powerful research tool to study mechanisms for a broad range of electrode reactions by identifying and quantifying reaction products and intermediates. In this review, we summarize the recent advances in the Li-O₂ battery researches offered by electrochemical mass spectrometry based on our group investigations. These include the research progresses in electrolytes, cathode materials (electrocatalysts), and parasitic reactions, i.e., the key issues associated with Li-O₂ research. In addition, we also discuss the effects of irreversible side reactions involved in battery systems on charge and discharge processes.

Synthesis Of Graphene Wrapped Li-Rich Layered Metal Oxide And Its Electrochemical Performance, Meng-Yan Hou, Ke Wang, Xiao-Li Dong, Yong-Yao Xia

Journal of Electrochemistry

In present work, lithium-rich layered transition metal oxide (LLO) was synthesized by a co-precipitation method in combination with a solid-state reaction. The graphene wrapped Li-rich layered oxide composite (LLO/Gra) was obtained by sintering the LLO/GO composite at 300 ^oC for 30 min in an air. The morphologies and the electrochemical performances were characterized by means of SEM, TEM, XRD, XPS, EIS and charge/discharge tests. The results indicated that the LLOe particles were uniformly wrapped with graphene. The resulting material exhibited better rate capability than that of pristine LLO since the wrapped graphene demonstrated the enhanced electronic conductivity. Accordingly, the …

Research Progress In Carbon Coating On Lifepo4 Cathode Materials For Lithium Ion Batteries, Ning Zhang, Yong-Chang Liu, Cheng-Cheng Chen, Zhi-Qiang Zhu, Zhan-Liang Tao, Jun Chen

Journal of Electrochemistry

Olivine-structured LiFePO₄ has been received much attention because of its flat voltage profile, low cost, abundant material supply and better environmental compatibility. However, the poor electronic and ionic conductivities have limited its application in industry. One of the best methods to improve the electrochemical performance is carbon coating. In this review, we summarize the recent developments of LiFePO₄/C cathode. Moreover, the different effects caused by coating methods and carbon sources, as well as the mechanism of carbon coating on the properties of LiFePO₄/C are reviewed.

Enhancing Stability Of Pem Fuel Cell Catalysts Via Support Changing, Xiao-Hong Xie, Zi-Dong Wei

Journal of Electrochemistry

The Pt/C catalyst with highly dispersed Pt nanoparticles supported on carbon has been widely used as the state-of the-art catalyst in proton exchange membrane fuel cells (PEMFCs), while the durability of Pt/C is one of the major barriers for large-scale applications of PEMFCs. Thus, enhancing the stability of Pt/C has been a hot issue in this field. In this review, we summarize the recent progress in enhancing the catalyst stability in the view of support material. The future prospects of the PEMFCs catalyst should focus on adopting more stable supports or strengthening the interactions between Pt and supports.

Lithium Air Batteries: Non-Aqueous And Hybrid Systems, Sheng-Fu Tong, Ping He, Xue-Ping Zhang, Shi-Yong Zhao, Hao-Shen Zhou

Journal of Electrochemistry

Developing energy storage devices and new materials, which match the requirements in electric vehicles (EVs) and hybrid electric vehicles (HEVs), is an effective way to balance the contradiction between the social development and the shortage of fossil energy and environment pollution. Rechargeable lithium-air (Li-air) batteries consisting of Li and oxygen as the anodic and cathodic reactants, respectively, have attracted much attention during the past decade due to their high theoretical specific energy. According to work conditions, the most studied types of Li-air batteries are non-aqueous, hybrid, and solid state electrolyte Li-air batteries. Challenges still exist in cathodes, anodes, electrolytes and …

Pt/C Modified Proton Exchange Membrane For Improved Fuel Cell Performance, Zhi Cui, Chao Wang, Shui-Yun Shen, Feng-Jing Jiang, Jun-Liang Zhang

Journal of Electrochemistry

The property of proton exchange membrane greatly affects the performance of proton exchange membrane fuel cells (PEMFC). During the operation of a PEMFC, the water produced at the cathode, the water vapor from the humidified feed gas and the water migrated by electro-dragging will reach a balance in the membrane and determine the resistance of PEMFC, and thus affect the performance of PEMFC. Normally, the PEMFC performance strongly depends on the relative humidity of the feed gas, and the performance decreases at lower humidity as a result of lower proton conductivity of the membrane. In this paper, we proposed to …

Electrolytes For Lithium And Lithium-Ion Batteries, Zong-Rang Zhang

Journal of Electrochemistry

This is an up-to-date book published by Springer last year and focuses on the field of the electrolytes for lithium and lithium-ion batteries. A brief introduction and review of this book are given in this paper. The main contents of this book are introduced briefly in the order of ten different chapters along with a short review of recent progress in those fields.

The Electronic Structure Of The Pyranopterin Dithiolene Cofactor And Radical Reporters Of Excited State Interactions, Benjamin William Stein

Chemistry and Chemical Biology ETDs

Crystal structures of multiple molybdenum enzymes clearly demonstrate interesting structural distortions involving the pyranopterin dithiolene. These distortions can be correlated with pyranopterin oxidation state through the use of DFT geometry optimized structures of the possible oxidation states, and these are correlated with enzyme family. The potential role of the pyranopterin dithiolene in electron transfer in the varied enzyme familes has been explored through the use of non-equilibrium Green's function (NEGF) electron transport calculations. These calculations demonstrate clear differences in electron transport behavior as a function of pyranopterin oxidation state. The Jahn-Teller effect can strongly impact the geometric and electronic structures …

Electrochemical Investigation Of Homogenous Species At An Electrode Interface, Christopher Alan Larsen Iii

Chemistry and Chemical Biology ETDs

CO₂ reduction is a pressing problem worldwide, and one obstacle in the electrochemical conversion of CO₂ to more useful C₁ products such as methanol and formic acid is the kinetic barrier known as overpotential. The overpotential of rearranging the nuclei in CO₂ to accommodate electron transfer can be lowered by pre-bending the CO₂ molecule in an adduct-mediated complex. The work presented in Part I utilizes a combination of hard and soft donors on pincer-like ligands to effect the bending of CO₂ prior to electrochemical reduction. A large majority of the work consists of using …

Theory, Multiscale Simulations, And Experiments On Mesoscale Multifunctional Systems, Lance Edward Edens

Chemistry and Chemical Biology ETDs

Computational simulations use theoretical models to reproduce, as accurately as possible, the observed real-world behavior of complex structures. Guided by experimental observations, many multiscale/coarse-grained simulations seek to explore increasingly complicated systems. Here, a multiscale/coarse-grained simulation program (called TM2) is developed with applications to 1) properties and mechanisms of DNA and DNA polymerases, and 2) adhesion between whole bacterial cells and patterned surfaces. Results from the bacterial adhesion application form a part of a larger collaborative effort aimed at creating multifunctional, controllable surfaces to capture and kill pathogenic bacteria. The application of TM2 is first demonstrated by a coarse-grained model for …

Spectroscopic And Computational Studies Of Molybdenum Enzymes And Models, Chao Dong

Chemistry and Chemical Biology ETDs

In this dissertation spectroscopic methods such as electronic absorption (EAS), resonance Raman (rRaman), electron paramagnetic resonance (EPR), and MCD spectroscopies have been used in combination with DFT calculations for the interpretation of experimental results. These methods have been used to investigate the molybdenum coordination environment in enzymes and model complexes. Xanthine oxidase (XO), one of the canonical molybdenum enzyme families, hydroxylizes heterocyclic substrates by inserting an oxygen atom from molybdenum-activated water into a substrate C-H bond. This generates reducing equivalents that pass through two iron sulfur clusters and then to FAD, where oxidation of the FAD takes place. In this …

Study Of Novel Synthetic Methodologies For Indolyl Derivatives And Beta-Fluoroenals, Xiaobei Chen

Chemistry and Chemical Biology ETDs

One of the central goals in modern organic synthesis is to develop efficient synthetic strategies for the preparation and study of complex molecules possessing interesting structural, biological, and physical properties. Toward this end, my Ph. D. work focuses on the development of novel synthetic methodologies for the facile construction of synthetically and biologically significant molecular architectures. The tert-prenylated indoles and indolines are widely present in a large collection of natural products and biologically active compounds. Although significant efforts have been made on the development of efficient methods to prepare these intriguing molecular architectures, few methods have been explored to introduce …

Corrosion Protection Of 304 Stainless Steel With Melting Gels Coatings, Mario Aparicio, Andrei Jitianu, Gabriela Rodriguez, Ahmad Dengah, Kutaiba Marzoki, Jadra Mosa, Lisa C. Klein

Publications and Research

Methyl-substituted melting gels were used to coat AISI 304 stainless steel substrates. Crack-free coatings up to 1 mm in thickness were obtained. SEM micrographs of cross-sections con fi rm good adhesion to the surface. Samples were subjected to structural characterization using FT-IR, and Raman spectroscopy. Mechanical properties were investigated by micro-scratch tests. Electrochemical analyses (anodic polarization and electrochemical impedance spectroscopy) were performed in 3.5% NaCl solutions. Electrochemical tests show excellent performance of the coatings against corrosion with no sign of degradation after several months of immersion.

Simulation Of Energetic Particle Precipitation Effects During The 2003-2004 Arctic Winter, C. E. Randall, V. L. Harvey, L. A. Holt, D. R. Marsh, D. Kinnison, B. Funke, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Energetic particle precipitation (EPP) during the 2003-2004 Arctic winter led to the production and subsequent transport of reactive odd nitrogen (NO_x=NO+NO₂) from the mesosphere and lower thermosphere (MLT) into the stratosphere. This caused NO_x enhancements in the polar upper stratosphere in April 2004 that were unprecedented in the satellite record. Simulations of the 2003-2004 Arctic winter with the Whole Atmosphere Community Climate Model using Specified Dynamics (SD-WACCM) are compared to satellite measurements to assess our understanding of the observed NO_x enhancements. The comparisons show that SD-WACCM clearly displays the descent of NO_x produced …