Physical Chemistry Commons^™

Properties And Structures Of Li-N Based Hydrogen Storage Materials, Junqing Zhang

Dissertations, Master's Theses and Master's Reports - Open

Traditional transportation fuel, petroleum, is limited and nonrenewable, and it also causes pollutions. Hydrogen is considered one of the best alternative fuels for transportation. The key issue for using hydrogen as fuel for transportation is hydrogen storage. Lithium nitride (Li3N) is an important material which can be used for hydrogen storage. The decompositions of lithium amide (LiNH2) and lithium imide (Li2NH) are important steps for hydrogen storage in Li3N. The effect of anions (e.g. Cl-) on the decomposition of LiNH2 has never been studied. Li3N can react with LiBr to form lithium nitride bromide Li13N4Br which has been proposed as …

Ultrasensitive Analysis Of Binding Affinity Of Hiv Receptor And Neutralizing Antibodies Using Solution-Phase Electrochemiluminescence Assay, Xiao-Hong Nancy Xu, Zhaoyang Wen, William J. Brownlow

Chemistry & Biochemistry Faculty Publications

Binding of a few ligand molecules with its receptors on cell surface can initiate cellular signaling transduction pathways, and trigger viral infection of host cells. HIV-1 infects host T-cells by binding its viral envelope protein (gp120) with its receptor (a glycoprotein, CD4) on T cells. Primary strategies to prevent and treat HIV infection is to develop therapies (e.g., neutralizing antibodies) that can block specific binding of CD4 with gp120. The infection often leads to the lower counts of CD4 cells, which makes it an effective biomarker to monitor the AIDS progression and treatment. Despite research over decades, quantitative assays for …

Broadband Fourier Transform Rotational Spectroscopy For Structure Determination: The Water Heptamer, Cristóbal Pérez, Simon Lobsiger, Nathan A. Seifert, Daniel P. Zaleski, Berhane Temelso, George C. Shields, Zbigniew Kisiel, Brooks H. Pate

Faculty Journal Articles

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (¹³C, ¹⁵N, ¹⁸O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water …

The Relation Between Atmospheric Humidity And Temperature Trends For Stratospheric Water, S. Fueglistaler, Y. S. Liu, T. J. Flannaghan, P. H. Haynes, D. P. Dee, W. J. Read, E. E. Remsberg, L. W. Thomason, D. F. Hurst, J. R. Lanzante, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

We analyze the relation between atmospheric temperature and water vapor-a fundamental component of the global climate system-for stratospheric water vapor (SWV). We compare measurements of SWV (and methane where available) over the period 1980-2011 from NOAA balloon-borne frostpoint hygrometer (NOAA-FPH), SAGE II, Halogen Occultation Experiment (HALOE), Microwave Limb Sounder (MLS)/Aura, and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) to model predictions based on troposphere-to-stratosphere transport from ERA-Interim, and temperatures from ERA-Interim, Modern Era Retrospective- Analysis (MERRA), Climate Forecast System Reanalysis (CFSR), Radiosonde Atmospheric Temperature Products for Assessing Climate (RATPAC), HadAT2, and RICHv1.5. All model predictions are dry biased. The interannual …

Hydrocarbons In The Upper Troposphere And Lower Stratosphere Observed From Ace-Fts And Comparisons With Waccm, Mijeong Park, William J. Randel, Douglas E. Kinnison, Louisa K. Emmons, Peter F. Bernath, Kaley A. Walker, Chris D. Boone, Nathaniel J. Livesey

Chemistry & Biochemistry Faculty Publications

Satellite measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) are used to examine the global, seasonal variations of several hydrocarbons, including carbon monoxide (CO), ethane (C₂H₆), acetylene (C₂H₂), and hydrogen cyanide (HCN). We focus on quantifying large-scale seasonal behavior from the middle troposphere to the stratosphere, particularly in the tropics, and furthermore make detailed comparisons with the Whole Atmosphere Community Climate Model (WACCM) chemistry climate model (incorporating tropospheric photochemistry, time-varying hydrocarbon emissions, and meteorological fields nudged from reanalysis). Comparisons with Microwave Limb Sounder (MLS) measurements of CO are also included …

Organic Photovoltaics: A Charge Transfer Perspective In The Study Of Donor-Acceptor Systems, Marco Olguin

Open Access Theses & Dissertations

The present research involves the study of donor-acceptor (D/A) dyad complexes from a charge transfer energy perspective. The aim is to provide insight and predictive understanding into the charge transfer processes of the molecular-level components in donor-acceptor based organic solar cells using computational methods to describe photochemical processes at the quantum mechanical level within the Density Functional Theory (DFT) approximation. Predictive understanding is anchored in reproducing experimental results, wherein the present work a perturbative excited-state DFT method is described in detail and shown to give Charge Transfer (CT) energies in excellent agreement with benchmark experimental data. With an accurate excited …

Self-Assembling Of Gold Nanoparticles Array For Electro-Sensing Applications, Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

A colloidal solution of citrate-stabilized gold nanoparticles (AuNPs) with an average size of ca. 2.6 nm has been prepared, characterized and further implemented in electro-sensing applications. This colloidal solution of AuNPs has been prepared via the reduction of NaAuCl4 with sodium tetrahydroborate (NaBH4) using trisodium citrate as a stabilizer. The optical properties of this solution have been studied with UV–Vis spectroscopy. Next, these AuNPs have been immobilized onto a polycrystalline Au (poly-Au) electrode with the assistance of benzenedimethanethiol (BDMT), which served as a binder. Attention has been taken to ensure the formation of a compact impermeable layer of BDMT on …

Homogeneous Connectivity Of Potential Energy Network In A Solidlike State Of Water Cluster, Takuma Akimoto, Toshihiro Kaneko, Kenji Yasuoka, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A novel route to the exponential trapping-time distribution within a solidlike state in water clusters is described. We propose a simple homogeneous network (SHN) model to investigate dynamics on the potential energy networks of water clusters. In this model, it is shown that the trappingtime distribution in a solidlike state follows the exponential distribution, whereas the trapping-time distribution in local potential minima within the solidlike state is not exponential. To confirm the exponential trapping-time distribution in a solidlike state, we investigate water clusters, (H₂O)₆ and (H₂O)12, by molecular dynamics simulations. These clusters change dynamically from …

Structure And Thermodynamics Of H3o+(H2o)8 Clusters: A Combined Molecular Dynamics And Quantum Mechanics Approach, Berhane Temelso, Thorsten Koddermann, Karl K. Kirschner, Katurah L. Klein, George C. Shields

Faculty Journal Articles

We have studied the structure and stability of (H₃O⁺)(H₂O)₈ clusters using a combination of molecular dynamics sampling and high-level ab initio calculations. 20 distinct oxygen frameworks are found within 2 kcal/mol of the electronic or standard Gibbs free energy minimum. The impact of quantum zero-point vibrational corrections on the relative stability of these isomers is quite significant. The box-like isomers are favored in terms of electronic energy, but with the inclusion of zero-point vibrational corrections and entropic effects tree-like isomers are favored at higher temperatures. Under conditions from 0 to 298.15 K, the …

Structures And Reactions Of Biomolecules At Interfaces, Xiaoning Zhang

Theses and Dissertations--Chemistry

This dissertation serves to study a protein's conformation-function relationship since immobilized proteins often behave differently from their solution-state counterparts. Therefore, this study is important to the application of protein-based biodevices. Another aim of this dissertation is to explore a new approach to realize low voltage electrowetting without the help of oil bath. Utilizing this approach, a protein micro-separation was realized. Additionally, the interfacial properties of ionic liquid (IL) solid-like layer, which played a key role in electrowetting, was studied for further developments of IL-based applications.

Atomic Force Microscopy (AFM) was utilized in the study and played multiple roles in this …

Studies Of Organic Compounds Spreading Over High Energy Surfaces, Lingbo Lu

Theses and Dissertations--Chemistry

Spreading plays an important role in coating, lubrication, printing and etc. During the spreading process, a liquid thin film forms prior to the expansion of a liquid drop. This thin film is called a precursor film. It not only changes the spreading mechanism, but impacts the wettability of a liquid. Early studies on the precursor films showed the films were stacked in a terraced structure, and the radius of each layer of the films was proportional to the square root of time. Optical techniques such as ellipsometry, X-ray diffraction and X-ray reflectivity solved the conformations of liquid molecules at the …

Efficient Electrochemical Functionalization Of Carbon Nanotubes And Carbon Nanotube Membranes For Energy, Drug Delivery And Potential Catalysis Applications, Xin Zhan

Theses and Dissertations--Chemistry

Electrochemical diazonium grafting offers versatile functionalization of chemically inert graphite under mild condition, which is particularly suitable for CNT composite modification. Tetrafluorinated carboxylphenyl diazonium grafting provides the most controllable functionalization chemistry allowing near monolayer levels of functionality on carbon nanotubes. The functional density was successfully quantified by anion selective dye-assay and X-ray photoelectron spectroscopy (XPS) of thiol-Au self-assembled monolayers (SAM) as a calibration reference. This technique enables monolayer functionality at the tips of carbon nanotube membranes for biomimetic pumps and valves as well as thin conductive layers for CNT-based high area electrochemical support electrodes.

Double-walled carbon nanotube (DWCNT) membranes were …

Reaction Enthalpy And Volume Profiles For Excited State Reactions Involving Electron Transfer And Proton-Coupled Electron Transfer, William Antonio Maza

USF Tampa Graduate Theses and Dissertations

Electron transfer, ET, and proton-coupled electron transfer, PCET, reactions are central to biological reactions involving catalysis, energy conversion and energy storage. The movement of electrons and protons in either a sequential or concerted manner are coupled in a series of elementary reaction steps in respiration and photosynthesis to harvest and convert energy consumed in foodstuffs or by absorption of light into high energy chemi-cal bonds in the form of ATP. These electron transfer processes may be modulated by conformational dynamics within the protein matrix or at the protein-protein interface, the energetics of which are still not well understood. Photoacoustic calorimetry …

Controlled Transformation Of Nanoparticles With Tunable Surface Plasmon Resonance, Nimer Murshid

Theses and Dissertations (Comprehensive)

This thesis reports key findings in the synthesis and transformation of silver nanoparticles (AgNPs) with pentagonal symmetries. The main focus of the thesis work is on the synthesis of silver decahedral nanoparticles (AgDeNPs) and their transformation into larger AgDeNPs and silver pentagonal rod nanoparticles (AgPRNPs). In another direction, produced AgNPs were stabilized by gold plating. In a one-stage photochemical synthesis of AgDeNPs (pentagonal bipyramid, J₁₃ solid), oxidative etching by hydrogen peroxide was implemented to achieve complete conversion of the small silver platelet precursor NPs. For convenient laboratory synthesis of high-purity size-selected AgDeNPs, we have also adapted LEDs as a …

Electrocatalytic Oxidation Of Formic Acid On Pd/Ni Heterostructured Catalyst, Mingjun Ren, Liangliang Zou, Ju Chen, Ting Yuan, Qinghong Huang, Haifeng Zhang, Hui Yang, Songlin Feng

Journal of Electrochemistry

A Pd/Ni bimetallic nanostructured electrocatalyst was fabricated via a two-step reduction route. Owing to an epitaxial growth of Pd atoms on the surface of Ni nanoparticles, heterostructured Pd/Ni nanocomposites were formed and verified by high resolution transmission electron microscopy combined with energy-dispersion X-ray spectroscopy. X-ray diffraction confirmed that the as-prepared Pd/Ni nanocomposites possessed a single face-centered-cubic (fcc) Pd structure, probably due to a weaker diffraction intensity of metallic Ni and/or overlapping by that of Pd. The intrinsic catalytic activity on the Pd/Ni is higher than that on the Pd. Moreover, the durability of formic acid oxidation on the Pd/Ni was …

Electrochemical Performance Of Screen-Printed Composite Coatings Of Conducting Polymers And Carbon Nanotubes On Titanium Bipolar Plates In Aqueous Asymmetrical Supercapacitors, Xiaohang Zhou, George Z. Chen

Journal of Electrochemistry

Composites of conducting polymers (polypyrrole and polyaniline) with acid treated multi-walled carbon nanotubes were formulated into printable aqueous inks, with the aid of functional additives (benzethonium chloride as a surfactant with or without polyvinyl alcohol as a binder). The inks were screen-printed as fairly uniform coatings of various mass loading densities and areas (up to 75 mg cm^-2 and 100 cm²) on thin titanium plates (0.1 mm in thickness). These screen-printed plates were used to fabricate both unit cell and multi-cell stack of asymmetrical supercapacitors with screen-printed negative electrodes of activated carbon (pigment black) in aqueous electrolytes …

Ternary Alloy Electrocatalysts For Oxygen Reduction Reaction, Jin Luo, Lefu Yang, Binghui Chen, Chuanjian Zhong

Journal of Electrochemistry

Proton exchange membrane fuel cell represents an important electrochemical energy conversion device with many attractive features in terms of efficiency of energy conversion and minimization of environmental pollution. However, the large overpotential for oxygen reduction reaction at the cathode and the low activity, poor durability and high cost of platinum-based catalysts in the fuel cells constitute a focal point of major barriers to the commercialization of fuel cells. The development of nanostructured catalysts shows promises to addresses some of the challenging problems. The ability to engineer the composition and nanostructure of nanoalloy catalysts is important for developing active, robust and …

Advances And Challenges Of Intermediate Temperature Solid Oxide Fuel Cells: A Concise Review, Sanping Jiang

Journal of Electrochemistry

Fuel cell is an electrochemical energy conversion device to directly convert the chemical energy of fuels to electricity. Among all types of fuel cells, solid oxide fuel cells (SOFCs) operating at intermediate temperatures of 600~800 ^oC offer an attractive option that is much more fuel flexible than low temperature fuel cells such as proton exchange membrane fuel cells, and is suitable for a wide range of applications. However, two main challenges remain towards the commercial viability and acceptance of the SOFC technologies: the cost and durability. Both are critically dependent on the process, fabrication, performance, chemical and microstructural stability …

Electrocatalytic Activity Of Palladium Nanocatalysts Supported On Carbon Nanoparticles In Formic Acid Oxidation, Jie Huang, Zhiyou Zhou, Yang Song, Xiongwu Kang, Ke Liu, Wancheng Zhou, Shaowei Chen

Journal of Electrochemistry

Palladium nanostructures were deposited onto carbon nanoparticle surface by a chemical reduction method. Transmission electron microscopic studies showed that whereas the resulting metal-carbon (Pd-CNP) nanocomposites exhibited a diameter of 20 to 30 nm, the metal components actually showed a cauliflower-like surface morphology that consisted of numerous smaller Pd nanoparticles (3 to 8 nm). Electrochemical studies showed that the effective surface area of the Pd-CNP nanoparticles was about 40% less than that of Pd black, possibly because the Pd nanoparticles were coated with a layer of carbon nanoparticles; yet, the Pd-CNP nanocomposites exhibited marked enhancement of the electrocatalytic activity in formic …

Adsorption And Electrooxidation Of Carbon Monoxide On Platinum Surfaces Modified With Sulfur, A. Mattox Mathew, W. Henney Matthew, Johnson Adam, Zou Shouzhong

Journal of Electrochemistry

Adsorbed sulfur is commonly considered as a reaction poison. However, small amounts of sulfur on platinum significantly increase the surface reactivity toward carbon monoxide (CO) electrooxidation. For the solution CO oxidation, the onset potential was shifted up to over 300 mV negative to that on S-free surface, and the extent of the negative potential shift increases with the sulfur coverage (X_s) up to about 0.6. The enhanced CO oxidation also depends on the solution pH. For the adsorbed CO, at low sulfur coverages (X_s < 0.3), the oxidation peak potential is about 40 mV negative to that of the corresponding clean Pt. However, at higher coverages, the peak potential is about 30 mV more positive. Surface-enhanced Raman spectra show that the adsorption of sulfur significantly redshifts the Pt-CO stretching frequency. These observations are explained by the weakening of the Pt-CO bond and the hindrance of CO diffusion by Sads.