Physical Chemistry Commons^™

Preface-Jes Focus Issue On Electrolysis For Increased Renewable Energy Penetration, B. Pivovar, M. Carmo, K. Ayers, X. Zhang, J. O'Brien

Mechanical & Aerospace Engineering Faculty Publications

(First paragraph) Today represents a particularly exciting time, as our planet’s energy system is undergoing major changes due to dramatically decreasing renewable energy prices and increasing societal concerns over greenhouse gas emissions, criteria pollutants (arsenic, mercury, NOx, particulate matter), and climate change. These factors are pushing society toward deep decarbonization of our energy system, perhaps the most challenging issue facing the planet today. Unfortunately, wind and solar energy, while both promising generation sources, come with intermittency challenges and have limitations in their abilities to impact industrial and transportation sector demands where fossil fuel energy carriers based on chemical bonds have …

An Investigation Of The Requirements For Excimer Formation And Charge Stabilization In Model Pi-Stacked Assemblies, Brandon Uhler

Dissertations (1934 -)

Formation of -stacked excimers plays an important role in many systems, ranging from biological phenomena and polymer formation and function to photovoltaic devices and organic molecular electronics. In these systems, the geometrical reorganization of the ground state upon photoexcitation is still a subject of debate. In this work, we compare the dynamics of excimer formation and hole (charge) stabilization in fluorene and fluorene-based model systems. We use a variety of gas-phase methods to examine the spectroscopy and dynamics of these systems, including Two-Color Resonant Two-Photon Ionization (2CR2PI), Hole-Burning (HB), Laser Induced Fluorescence (LIF), and Dispersed Fluorescence (DF). In order to …

Nmr Studies Of Electrochemical Energy Storage Materials, Jing Peng

Dissertations, Theses, and Capstone Projects

Electrochemical energy storage materials constitute essential elements in the development of sustainable energy technologies. They are crucial for improving the efficiency of energy storage devices to facilitate the use of renewable resources. The increasing human demands for energy and limitation of fossil fuel stimulates the continued development of energy storage materials. Better understanding of their working mechanisms and electrochemical properties from a view of chemistry is quite necessary for improving the energy storage technology. In this work, Nuclear Magnetic Resonance (NMR) has been used as a powerful tool to characterize the solvation behavior and diffusion ability of some commonly used …

Photodynamic Killing Of Human Cancer Cells With Smart Photosensitizer Materials And An Endoscopic Implement For Singlet Oxygen Delivery, Mihaela N. Minnis

Dissertations, Theses, and Capstone Projects

The thesis describes progress on probe tips for a microoptic device for the precise delivery of the components necessary for photodynamic therapy (PDT) in a highly localized and controllable fashion. The thesis also summarizes results of a photosensitized oxidation study. The work focused on i) developing a photoactive fluoropolymer surface that will release sensitizer drug molecule for use in PDT, ii) designing new probe tips surfaces for use as sensitizer support for a microoptic PDT device, iii) exploring strategies for covalent attachment of sensitizers and model compounds to Teflon/PVA surfaces with the aim of being coupled with our microoptic device, …

Probing The Structure And Photophysics Of Porphyrinoid Systems For Functional Materials, Christopher D. Farley

Dissertations, Theses, and Capstone Projects

Porphyrins (Pors) and their many cousins, including phthalocyanines (Pcs), corroles (Cors), subphthalocyanines (SubPcs), porphyrazines (Pzs), and naphthalocyanines (NPcs), play amazingly diverse roles in biological and non-biological systems because of their unique and tunable physical and chemical properties. These compounds, collectively known as porphyrinoids, can be employed in any number of functional devices that have the potential to address the challenges of modern society. Their incorporation into such devices, however, depends on many structural factors that must be well understood and carefully controlled in order to achieve the desired behavior. Self-assembly and self-organization are key processes for developing these new technologies, …

Electrophilic Activation Of Silicon–Hydrogen Bonds In Catalytic Hydrosilations, Mark C. Lipke, Allegra L. Liberman-Martin, T. Don Tilley

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Hydrosilation reactions represent an important class of chemical transformations and there has been considerable recent interest in expanding the scope of these reactions by developing new catalysts. A major theme to emerge from these investigations is the development of catalysts with electrophilic character that transfer electrophilicity to silicon by Si-H activation. This type of mechanism has been proposed for catalysts ranging from Group 4 transition metals to Group 15 main group species. Additionally, other electrophilic silicon species, such as silylene complexes and η3-H2SiRR′ complexes, have been identified as intermediates in hydrosilation reactions. In this Review, different types of catalysts are …

Lubricants For Turbine Engines, David W. Johnson

Chemistry Faculty Publications

The lubricant systems used in turbine engine applications are discussed with respect to the particular problems associated with aircraft applications. After initially describing the relevant specifications, the typical basestocks are described along with some common degradation schemes. The additive systems, including antioxidants, anti-foaming agents, and anti-wear additives needed to achieve the typical specifications, are described along with their mechanism of action and degradation mechanisms. The methods used for the monitoring of lubricant health, including in-line and offline methods, are also discussed. Finally, future changes in specifications, basestocks, and additives are discussed with respect to new, high-performance bearing materials.

Revisiting The Fenceplot For The Maxwell Construction Of A Van Der Waals Fluid, Carl W. David

Chemistry Education Materials

An earlier published plot intended to better explain the Maxwell construction of the vapor pressure construct for van der Waals fluids is improved using Inkscape.

Theoretical Study Of Photoelectrochemical Reactions And Ec-Sers On Spr Metallic Electrodes Of Silver And Gold, Yuan-Fei Wu, Ran Pang, Meng Zhang, Jian-Zhang Zhou, Bin Ren, Zhong-Qun Tian, De-Yin Wu

Journal of Electrochemistry

At present photoelectrochemistry has received much concern back to nanostructures of noble metals from semiconductor electrodes. This is due to the surface plasmon resonance (SPR) effect of metallic nanostructures, which can effectively convert the far-field light to the near-field light and concentrate the photonic energy to the local surface area with high energy density. Thus, the different enhancement mechanisms, such as the local optical field enhancement, the formation of light generated hot carriers (hot electron-hole pairs), or the photothermal effect, have been proposed in literatures. On the basis of the SPR enhancement effect, the surface-enhanced Raman spectroscopy (SERS) can be …

Photoelectrochemical Water Splitting Cells: Methods For Improving Performance Of Electrodes And Recent Progress On Photocathodes, Kai-Jian Zhu, Wen-Jun Luo, Zhong-Jie Guan, Xin Wen, Zhi-Gang Zou, Wei Huang

Journal of Electrochemistry

Photoelectrochemical water splitting can convert solar energy into hydrogen which is an ideal way to utilize and store solar energy. A p-n tandem cell is considered as the most promising solar water splitting cell due to its high theory conversion efficiency, low cost and photoelectrode material flexibility. However, solar conversion efficiency of a tandem cell is still low in the experiment because of poor performance in a single photoelectrode. In this review, we have introduced some effective approaches to improve the performances of photoelectrodes by reducing recombination of photogenerated carriers in the bulk or on the surface, and suppressing back …

Preparations And Photoelectrochemical Properties Of Phosphate Modified Rgo-Biobr Nanocomposites, Shuang-Ying Chen, Zhi-Jun Li, Xu-Liang Zhang, Kang Hu, Rui Yan, Li-Qiang Jing

Journal of Electrochemistry

The RGO-BiOBr nanocomposites have been successfully synthesized by a hydrothermal process, and then modified with phosphorous acids. The photoelectrochemical properties of the fabricated RGO-BiOBr nanocomposite films were studied. The results indicate that the photocurrent densities of RGO-BiOBr were much larger compared with those of the bare BiOBr, and interestingly, the photocurrent densities were further improved after phosphate modification. Based on the analyses of the produced hydroxyl radical amounts, the enhanced photocurrent densities could be attributed to the introduction of RGO and to the formed negative fields of modified phosphate groups, which are favorable for electrons to be transferred and for …

Solvent Effect On The Anticorrosive Properties And Active Coating Area Of A Long Alkyd Varnish, Saadawy M., Abd-El-Nabey B.A., Gomaa A.Z., Ashour M.

Journal of Electrochemistry

The effects of solvent nature and composition on the anticorrosive properties of a long alkyd varnish after different days of immersion in 0.5 mol•L^-1 NaCl were studied using electrochemical impedance spectroscopy. The protection efficiencies of the long alkyd varnishes containing different solvents increased with increasing the volatility of solvent or the composition of a given volatile solvent, which was confirmed with the observations using scanning electron microscopy and energy-dispersive X-Ray spectroscopy. The delaminated area, the area where the organic coating is detached from the metal surface leaving it unprotected, was found to decrease by increasing the volatility of solvent.

Cathode Buffer Layer For Improving Photovoltaic Performance Of Planar P-I-N Perovskite Solar Cells, Xiao-Dong Liu, Yong-Fang Li

Journal of Electrochemistry

Organic/inorganic hybrid metal halide perovskite semiconductor materials have drawn great attention for the application in solar cells in recent years because of their combined superior photoelectrical properties of inorganic semiconductors (with high dielectric constant and high charge carriers mobility) and organic semiconductors (with good solution processability and high absorbance). The power conversion efficiency (PCE) of the organometal halide perovskite solar cells (pero-SCs) based on CH₃NH₃PbI₃ has been increased dramatically in a few years from 3.8% to a certified 22.1%, primarily owing to the development of new interfacial materials, careful optimization of morphology, and perovskite crystallization …

Special Issue: Photoelectrochemistry And New Types Of Solar Cells, Chang-Jian Lin, Yong-Fang Li

Journal of Electrochemistry

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Application Of Metal-Organic Frameworks In Dye-Sensitized Solar Cells, Ya-Feng Li, Qing-Qing Sun, Ming-Deng Wei

Journal of Electrochemistry

To assemble dye-sensitized solar cells (DSSCs) with high efficiencies, their photoanodes should have large specific surface area to establish a large adsorption amount of dyes and good light-harvesting ability. From this point of view, it will be an interesting topic to explore the application of metal-organic frameworks (MOFs) in the field of DSSCs due to their huge specific surface area. This paper introduces the application of MOFs in photovoltaic devices briefly, and then summaries our approaches in using MOFs in the study of DSSCs, including the pre-treatment and the post-treatment of photoanode, the preparation of photoanode materials and the light …

Prospects Of D-Π-A Structured Porphyrins And Their Photoelectrochemical Application, Shuang-Shuang Liu, Jian-Feng Lu, Ming-Kui Wang

Journal of Electrochemistry

Porphyrins and their metalloderivatives are a class of compounds exhibiting a wide variety of interesting and highly useful properties, such as chlorophyll. Porphyrins are particularly interesting in photoelectrochemical applications due to their structural similarity to chlorophylls in natural photosynthetic systems, as well as their strong and tunable absorption properties. Recently, various porphyrins have been extensively studied for their applications in solar cells, photocatalytic hydrogen production, optical information storage and others. This review will focus on the unique physical and chemical properties of D-π-A structured porphyrins, and their photovoltaic performances in dye-sensitized solar cells. A brief discussion in the future development …

Activation Effect Of Nano-Carbon Derived From Co2 On Lead Electrode In Sulfuric Aqueous Solution, Yu-Qiao Song, Hua Zhu, Guang-Jin Zhao, Wen-Long Wu, Shou-Bin Zhou, Di-Hua Wang

Journal of Electrochemistry

Serious sulfation of the negative plate is one of the most popular reasons of the early failure of lead-acid battery. Addition of nano-carbon was proved to be effective for recovering the sulfated electrode and the property of the carbon material always plays an important role. In this work, a new kind of nano-carbon material with high electrical conductivity and good adsorption capability for heavy metal cations, which is electrochemically prepared from CO₂ in molten carbonates, was tested as activation additive for the sulfated lead electrode by cyclic voltammetry and SEM measurements. The results showed that the as-prepared carbon can …

WoX/Pedot:Pss Double-Layered Hole-Transport Layers For Efficient And Stable Planar Heterojunction Perovskite Solar Cells, Wen-Yuan Qiao, Qiang Guo, Cong Li, Shuang Ma, Fu-Zhi Wang, Song-Yuan Dai, Zhan-Ao Tan

Journal of Electrochemistry

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a commonly used hole-transport material in the perovskite solar cells (PerSCs) structure of perovskite/fullerene planer heterojunction, but it also has a negative effect on the stability of device because of its acidity which will corrode metal oxide transparent electrodes. In this work, a WO_x hole-transport layer with high work function was inserted into the PEDOT: PSS and FTO to enhance the stability and photovoltaic performance. The inserted WO_x layer not only can avoid direct contact between PEDOT:PSS and FTO, but also can further reduce the contact barrier between the electrode interface. We studied the effect …

A Novel Flexible Dye-Sensitized Solar Cell Based On Pt Networks Counter Electrode, Zi-Jie Xu, Fa-Yin Zhang, Xiao-Dan Hong, Wen-Xi Guo, Xiang-Yang Liu, Chang-Jian Lin

Journal of Electrochemistry

Flexible dye-sensitized solar cells (DSSCs) have received widespread attentions in recent years because of their ease of fabrication, low production cost, relatively high chemical stability and flexibility. We report the fabrication of ZnO DSSCs based on the highly flexible, conducting, catalytic and transparent Pt networks counter electrode, and the performance of this solar cell was characterized by SEM, XRD, polarized fluorescence microscope, motor, I-V test station and electrochemical workstation. Compared to Pt nanofiber arrays (NFs), Pt networks not only show a better conductivity, but also exhibit superior transparency and catalytic activity. Furthermore, Pt networks electrode could be constructed on arbitrary …

Fabrications Of Three Copper Sulfide Counter Electrodes And Their Influences On Photovoltaic Properties In Qdsscs, Xiao-Dan Hong, Zi-Jie Xu, Fa-Yin Zhang, Yu-Peng Li, Mei-Dan Ye, Chang-Jian Lin, Wen-Xi Guo

Journal of Electrochemistry

Quantum dot-sensitized solar cells (QDSSCs) have attracted intensive attention in scientific and industrial fields due to their high molar extinction coefficient, spectral tunability by particle size, ease of fabrication, and low cost. In the past years, semiconductor metal sulfides have attracted extensive attention because of their attractive physical and chemical properties for potential applications in many fields,such as PbS, CuS, CoS and CdS. In particular, copper sulfides have become a promising candidate for counter electrode materials in QDSSCs for their outstanding electrochemical and catalytic properties. In order to explore more stable and efficient copper sulfide counter electrode materials, in this …

Hydrothermal One-Step Synthesis Of Layered Nickel/Cobalt Double Hydroxide With Using Shape-Directing Agent And Homogeneous Precipitating Agent, Li-Wei Zhu, Yun-Hai Yan, Hui Jia, Run-Fen Liang

Journal of Electrochemistry

Nickel/cobalt double hydroxide (Ni/Co-DH) has been prepared by facile hydrothermal one-step synthesis method using hexamethylene tetramine (HMT) as a homogeneous precipitating agent and cetyltrimethylammonium bromide (CTAB) as a shape-directing agent. With the hydrolysis of HMT and the use of CTAB, the Ni/Co-DH could be synthesized without additional alkali source, and in the meantime, the Ni/Co-DH exhibited a controlled mesopore size of 13.4 nm and a large BET surface area of 93.6 m² •g^-1 . The X-ray diffraction (XRD) pattern displays that the Ni/Co-DH existed as a mixture of α-Ni(OH)₂-β-Co(OH)₂. The scanning electron microscope (SEM) …

Stability And Kinetics Of Dna Pseudoknots: Formation Of T∗A•T Base-Triplets And Their Targeting Reactions, Calliste Steffensmeier

Theses & Dissertations

Pseudoknots have been found to play important roles in the biology of RNA. These stem-loop motifs are considered to be very compact and the targeting of their loops with complementary strands is accompanied with lower favorable free energy terms. We used a combination of spectroscopic (UV, CD and fluorescence), calorimetric (DSC, PPC and ITC) and kinetic (SPR) techniques to investigate: 1) Local base-triplet formation in pseudoknots; 2) energetic contributions for the association of pseudoknots with their complementary strands; and 3) the kinetic rates as a function of targeting strand length.

We investigated a set of DNA pseudoknots with sequence: d(TCTCT …

Verwiebe's "3-D" Ice Phase Diagram Reworked, Carl W. David

Chemistry Education Materials

The two dimensional phase diagrams of the various forms of ice are difficult to read and understand. A ``3D'' versions appearing ~80 years ago helps understanding of the phases and their inter-conversion into other phases.

Using In Situ Liquid Single Photon Ionization Mass Spectrometry (Spi-Ms) To Probe Lithium Polysulfide Electrolyte In Motion, Aala M. Al Hasan, Jiachao Yu, Juan Yao, Vijayakumar Murugesan, Manjula Nandasiri, Xiao-Ying Yu

STAR Program Research Presentations

The solid-liquid (s-l) interface is the most common interface encountered in electrochemical systems. The s-l interface has wide applications in energy storage, catalysis, and material sciences. In situ studies of chemical reactions taking place on the s-l interfaces can further our understanding of electron transfer and link to real-world device functions under challenging conditions. Direct probing of the solid electrode and liquid electrolyte interface has been realized using a vacuum compatible electrochemical microfluidic reactor, system for analysis at the liquid vacuum interface (SALVI) with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Most recently, the electrochemical version of SALVI was integrated to …

Comparative Analysis Of In Situ Fibronectin Using Tof-Sims, Spi-Ms, And Dropdesi-Ms In A Microfluidic Reactor, Shannon Fasing, Xiao-Ying Yu, Juan Yao, Jiachao Yu

STAR Program Research Presentations

Fibronectin is an important biomolecule due to its role in cell differentiation, growth, kinesis, and adhesion. Such biological responses are mediated through membrane recognition and signaling; where fibronectin is found. Studying the outer molecular surface of fibronectin allows deeper insight into the microbiological reactions that occur during these processes. In situ mass spectrometry analysis in aqueous solution accurately represents fibronectin’s chemical components, made possible by a vacuum compatible microfluidic reactor, SALVI (System for Analysis at the Liquid Vacuum Interface). SALVI was paired with the analytical tools: time-of-flight secondary ion mass spectrometer (ToF-SIMS), single photon ionization mass spectrometer (SPI-MS) and drop …

Catalytic Conversion Of Chlorite To Chlorine Dioxide By Non-Heme Complexes, Manasa Ramachandra

Open Access Theses

The oxyanions of chlorine (ClOx-, x=1-4) have diverse applications and are used in a variety of commercial products. They are very stable in an aqueous environment leading to water contamination, thereby posing a concern for the environment and human health. At the microbial level, the enzyme perchlorate reductase catalyzes the reduction of perchlorate (ClO4-) to chlorite (ClO2-) and chlorite dismutase further reduces chlorite to innocuous chloride (Cl -) and dioxygen (O2). Two non-heme complexes [Fe III-TAML]- (Tetraamido Macrocyclic Ligand), and [Mn II-(BnTPEN)] in the presence of peracetic acid (PAA) have been studied as catalysts for chlorite dismutation under ambient conditions. …

Ultraviolet And Infrared Spectroscopy Of Synthetic Foldamers, Aib Homopeptides, And Solvated 1,2-Diphenylethane In The Gas Phase, Joseph R. Gord

Open Access Dissertations

The work presented here implements a supersonic jet expansion source to funnel the population of model peptides and solvated-bichromophore clusters into their low lying structural minima and to collisionally cool these minima to their respective zero-point vibrational levels. Single-conformation ultraviolet and infrared spectroscopy techniques are then used to probe these systems and investigate their electronic properties and uncover their intrinsic conformational preferences in the gas phase.

Model β/γ-peptides known as synthetic foldamers and aminoisobutyric acid (Aib) homopeptides incorporate structural constraints that are designed/known to impose particular structural motifs. Here the ability of a β/γ-dipeptide to replicate the backbone length of …

Advances In Raman Hyperspectral Compressive Detection Instrumentation For Fast Label Free Classification, Quantitation And Imaging, Bharat R. Makani

Open Access Dissertations

Multiple prototypes of hyperspectral compressive detection (CD) Raman spectrometers have previously been constructed in the Ben-Amotz lab and have proven to be useful for fast, label-free chemical identification, quantitation and imaging. The CD spectrometer consists of a volume holographic grating (VHG) that linearly disperses the Raman photons into its component wavelengths and all wavelengths are focused onto a digital micromirror devise (DMD). The DMD is an optical modulator that consists of an array of programmable 10μm mirrors that can reflect photons in either +12° or -12° to the incoming light. The DMD is tilted such that the +12° photons go …

Single-Conformation Spectroscopy Of Hydrogen Bonding Networks: Solvation, Synthetic Foldamers, And Neurodegenerative Diseases, Patrick S. Walsh

Open Access Dissertations

The hydrogen bond is one of the most important interactions in natural processes ranging from protein folding to chemical reactions. Two complementary methodologies are applied to understanding this important interaction: top-down and bottom-up. Top-down methods use large molecules, such as proteins, revealing secondary structure information. Bottom-up experiments are performed on small molecules, utilizing high-resolution spectroscopy to reveal underlying quantum mechanical effects. The complexity gap is formed between these two experimental regimes; between large and small molecules; between bulk and individual solvent molecules; between classical mechanics calculations and quantum chemical calculations. This dissertation will focus on the application of gas phase, …

Determination Of Kinetic Parameters Of Equilibrium Peracetic Acid And Hydrogen Peroxide To Calculate Self-Accelerating Decomposition, Ricky Mittiga

Multidisciplinary Studies Theses

Determination of Kinetic Parameters of Equilibrium Peracetic Acid and Hydrogen Peroxide to Calculate Self-Accelerating Decomposition Temperature

Peracetic acid is a simple molecule that works as a powerful oxidant in many applications including food safety and water disinfection. The synthesis of the compound is fairly well understood due to its straightforward synthesis by mixing acetic acid and hydrogen peroxide. However, the decomposition of the compound has not been well studied. Few sources are available to provide kinetic data for the decomposition along with data that shows when the compound will undergo a self-accelerated decomposition that could lead to disastrous effects.

This …