Physical Sciences and Mathematics Commons^™

Photoluminescence Mechanism And Applications Of Graphene Quantum Dots, Yiyang Liu

Theses and Dissertations--Chemistry

Graphene quantum dots (GQDs) are small pieces of graphene oxide whose physical dimensions are so confined (a few to a few tens nm) that they have a finite bandgap due to a quantum confinement effect. The finite bandgap of GQDs grants them pronounced absorption bands and a substantial photoluminescence. These optical properties are rarely observed in traditional carbon materials, since most of carbon materials are metallic with a near-zero bandgap and thus have broad absorption spectra with no photoluminescence. The unique optical properties of GQDs, along with GQDs’ inherited advantages from carbon material family (cheap, abundant, non-toxic), make GQDs an …

Acenes, Heteroacenes And Analogous Molecules For Organic Photovoltaic And Field Effect Transistor Applications, Devin B. Granger

Theses and Dissertations--Chemistry

Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have …

Exploring The Structure And Properties Of Nanomaterials Using Advanced Electron Microscopy Techniques, Yao-Jen Chang

Theses and Dissertations--Chemistry

Nowadays people are relying on all kinds of electronic devices in their daily life. All these devices are getting smaller and lighter with longer battery life due to the improvement of nanotechnology and materials sciences. Electron microscopy (EM) plays a vital role in the evolution of materials characterization which shapes the technology in today’s life. In electron microscopy, electron beam is used as the illumination source instead of visible light used in traditional optical microscopy, the wavelength of an electron is about 10⁵ times shorter than visible light. By taking this advantage, the resolving power and magnification are greatly …

Energetic Effects Of Hole Transporting Materials On The Performance Of Organometal Halide Perovskite Photovoltaic Cells, So Min Park

Theses and Dissertations--Chemistry

Efficient, inexpensive, lightweight and flexible solar cells are desired to help meet the world’s growing energy needs. Organometal halide perovskite (OMHP) photovoltaic (PV) cells have shown dramatic increases in solar cell efficiencies increase over the last 5 years. OMHP PV cells have attracted significant attention due to their broad absorption spectra, high electron and hole mobility, and low production cost. The interface between hole transporting layer (HTL) and perovskite thin films have a significant influence on charge transfer and overall solar cell performance. 2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)9,9’-spirobifluorene (Spiro-OMeTAD) is a small molecule largely used as HTL in perovskite solar cells. However, this material …

Heterogeneous Base Metal Catalyzed Oxidative Depolymerization Of Lignin And Lignin Model Compounds, John Adam Jennings

Theses and Dissertations--Chemistry

With the dwindling availability of petroleum, focus has shifted to renewable energy sources such as lignocellulosic biomass. Lignocellulosic biomass is composed of three main constituents, lignin, cellulose and hemicellulose. Due to the low value of cellulosic ethanol, utilization of the lignin component is necessary for the realization of an economically sustainable biorefinery model. Once depolymerized, lignin has the potential to replace petroleum-derived molecules used as bulk and specialty aromatic chemicals. Numerous lignin depolymerization strategies focus on cleavage of β-aryl ether linkages, usually at high temperatures and under reductive conditions.

Alternatively, selective benzylic oxidation strategies have recently been explored for …

Arsenic Removal With A Dithiol Ligand Supported On Magnetic Nanoparticles, John Hamilton Walrod Ii

Theses and Dissertations--Chemistry

Exposure to arsenic (As) in water, the ubiquitous toxin that poses adverse health risks to tens of millions, is the result of both anthropogenic and geochemical mobilization. Despite recent publicity and an increased public awareness, the dangers associated with arsenic exposure rank among the top priorities of public health agencies globally. Existing sequestration applications mainly include reductions and adsorption with zero-valent metals and their oxides. The performance of adsorption media is known to preferentially favor aqueous As(V) over As(III) due to the charge of the dissolved oxyanion. Magnetic nanoparticles (MNP) have been the focus of multidisciplinary research efforts for the …

Deconvolving The Steps To Control Morphology, Composition, And Structure, In The Synthesis Of High-Aspect-Ratio Metal Oxide Nanomaterials, Lei Yu

Theses and Dissertations--Chemistry

Metal oxides are of interest not only because of their huge abundance but also for their many applications such as for electrocatalysts, gas sensors, diodes, solar cells and lithium ion batteries (LIBs). Nano-sized metal oxides are especially desirable since they have larger surface-to-volume ratios advantageous for catalytic properties, and can display size and shape confinement properties such as magnetism. Thus, it is very important to explore the synthetic methods for these materials. It is essential, therefore, to understand the reaction mechanisms to create these materials, both on the nanoscale, and in real-time, to have design control of materials with desired …

Interactions Of Compounds Containing Group 12 And 16 Elements, Daniel Burriss

Theses and Dissertations--Chemistry

The focus of this dissertation is on the interactions of compounds containing group 12 and 16 elements. This work is presented in three major parts. First, the interaction of the synthetic dithiol N,N’-bis(2-mercaptoethyl)isophthalamide), abbreviated BDTH₂, with selenite. Second, the interaction of cysteine with Cd(II) and the biologically relevant Cd-Cysteine crystal structure. Third, the green synthesis of CdSe quantum dots (QDs).

The interaction of BDTH₂ with selenite is different from the interactions with other metals and metalloids previously studied. Under ambient conditions, BDTH₂ is oxidized to the disulfide, BDT(S-S), while selenite is reduced to elemental selenium. However, …

Characterization And Application Of Hybrid Nanostructures For Enhanced Biological Imaging Using Fluorescence Microscopy Techniques, William E. Martin

Theses and Dissertations--Chemistry

Fluorescence microscopy is a powerful tool for interpreting the structure and function of biomolecules, and their interactions with one another. Understanding fundamental biological mechanisms is important to the development of improved treatments for a variety of diseases. Fluorescent tags are used to track the motion and longevity of such events, with the ability to monitor several biomolecules at once. Currently, many of these studies are conducted using bulk measurements, or several biological events at the same time, because the added light from several emitters can more easily overcome the high fluorescence background inherent to biological systems. Although important in their …

Organometallic Materials: Ferroceno[C]Thiophenes And 1,2-Bisthienylmetallocenes, Surya R. Banks

Theses and Dissertations--Chemistry

Development of synthetic routes toward two general organometallic frameworks was undertaken. The first project involved synthetic attempts of substituted and unsubstituted ferroceno[c]thiophene while the second one was the synthesis of 1,2-dithienylmetallocenes. The long-term goal of this work is to lay the foundations for study of electronic, electrochromic, redox, and optical properties of thiophene-based materials integrated with organometallic systems such as ferrocene, ruthenocene and cymantrene. The synthetic pathway for the target molecule in the first project involved converting 1,2-bis(hydroxymethyl)ferrocene to 1,2-bis(thiouroniummethyl)ferrocene with thiourea under acidic conditions. Refluxing the salt in base followed by acidification resulted in 1,2-bis(mercaptomethyl)ferrocene, which is …

Using Conventional And In Situ Transmission Electron Microscopy Techniques To Understand Nanoscale Crystallography, Bethany M. Hudak

Theses and Dissertations--Chemistry

Transmission electron microscopy (TEM) is a powerful tool for studying solidstate crystalline systems. With the advances in aberration correction, monochromation, and in situ capabilities, these microscopes are now more useful for addressing fundamental materials chemistry problems than ever before. This dissertation will illustrate the ways in which I have been using high-resolution imaging and in situ heating in the TEM during my Ph.D. research to investigate unique solid state chemistry questions.

This dissertation will focus on four unique crystal systems: thermoelectric skutterudite crystals, vapor-liquid-solid (VLS) grown nanowires, and hafnium dioxide nanorods. Although these systems are very different from one another, …

The Optimization Of The Synthesis And Characterization Of Vapor-Liquid-Solid Grown Zno Nanowires, Silas R. Fiefhaus

Theses and Dissertations--Chemistry

ZnO nanowires are a promising material with great semiconductor properties. ZnO nanowires were prepared by carbothermal reduction and vapor-liquid-solid growth mechanism. Altering a variety of parameters ranging from mole to mole ratio of ZnO to C all the way to gas flow rate was examined. The nanowires were then characterized and their morphology examined under a SEM to observe what effect the parameter had on the morphology of the nanowires. From the experiments and the parameters tested it was observed that in order to produce the highest quality straight nanowires one should use a mole to mole ratio of ZnO …

Unhindered Triangulene Salt Pairs: Substitution-Dependent Contact Ion Pairing And Complex Solvent-Separated Discotic Ions In Solution, Subrahmanyam Modekrutti

Theses and Dissertations--Chemistry

This work sought to enforce aromatic interactions between compatible π-molecular orbital systems with ionic bonding. In this case the interacting partners are oppositely charged discotic triangulene derivatives. The observed properties of the heterodimeric ion-pairs likely arise due to a hypothetical synergy between electrostatics and π-interactions. The work presented here describes investigation of putative covalency arising from this hypothetical synergy in the electrostatics driven π-stacking. In order to probe this, various hypotheses were made and experiments were designed to test their validity. The results from the experiments show existence of contact ion-pairs and complex solvent-separated discotic ions in solution. The formation …

Plasma Treated Mesoporous Tio2 Thin Films For Energy Storage Applications, Allen D. Reed

Theses and Dissertations--Chemistry

Mesoporous TiO₂ films treated with N₂/argon plasma or H₂ plasma were studied for use in photoelectrochemical water splitting and electrochemical supercapacitors, respectively. Cubic-ordered mesoporous thin films were prepared by a templated sol-gel method. UV-Vis absorbance spectra indicated that nitrogen plasma treatment significantly reduced the band gap of the TiO₂. XPS analysis showed that nitrogen atoms are incorporated into substitutional sites, rather than interstitial. Photocatalytic activity of nitrogen-doped TiO₂ films was evaluated by chronoamperometry and linear sweep voltammetry. Compared to pristine TiO₂, plasma-treated films showed remarkable photocurrent enhancement (up to 240 times) …

Ferrocene-Fused Derivatives Of Acenes, Tropones And Thiepins, Bidhya L. Maharjan

Theses and Dissertations--Chemistry

This research project is concentrated on tuning the properties of small organic molecules, namely polyacenes, tropones and thiepins, by incorporating redox-active transition metal centers π-bonded to terminal cyclopentadienyl ligands. Organometallic-fused acenequinones, tropones, thiepins and cyclopentadiene-capped polyacenes were synthesized and characterized. This work was divided into three parts: first, the synthesis of ferrocene-fused acenequinones, cyclopentadiene-capped acenequinones and their subsequent aromatization to polyacenes; second, the synthesis of ferrocene-fused tropones, thiotropones and tropone oxime; and third, the synthesis of ferrocene-fused thiepins. Ferrocene-fused quinones are the precursors to our target complexes. Our synthetic route to ferrocenequinones involved two-fold aldol condensation between 1,2-diformylferrocene and naphthalene-1,4-diol …

Electrode And Electrolyte Additives For Lifetime Extension In Lithium-Ion Batteries, Kishore Anand Narayana

Theses and Dissertations--Chemistry

Lithium-ion batteries (LIBs) are the most commonly used type of rechargeable batteries with a global market estimated at $11 billion, which is predicted to grow to $60 billion by 2020. The global commercialization of Li-ion batteries is impeded by issues such as poor cycle life (5000 cycles achieved in some LIBs) in high energy and power density applications because of the rising internal resistance due to aging and safety concerns such as overcharge which ultimately leads to thermal runaway and explosions. A battery’s performance mainly depends on external factors such as electrode thickness and degree of compacting, and the type …

Addressing Public Health Risks Of Persistent Pollutants Through Nutritional Modulation And Biomimetic Nanocomposite Remediation Platforms, Bradley J. Newsome

Theses and Dissertations--Chemistry

Due to their relative chemical stability and ubiquity in the environment, chlorinated organic contaminants such as polychlorinated biphenyls (PCBs) pose significant health risks and enduring remediation challenges. Engineered nanoparticles (NPs) provide a novel platform for sensing/remediation of these toxicants, in addition to the growing use of NPs in many industrial and biomedical applications, but there remains concern for their potential long-term health effects. Research highlighted herein also represents a transdisciplinary approach to address human health challenges associated with exposure to PCBs and NPs. The objectives of this dissertation research are two-fold, 1) to develop effective methods for capture/sensing and remediation …

N-Doped Multiwalled Carbon Nanotubes: Functionalization, Characterization And Application In Li Ion Batteries, Aman Preet Kaur

Theses and Dissertations--Chemistry

The focus of this dissertation is to utilize chemical functionalization as a probe to investigate the reactivity of N-doped multiwalled carbon nanotubes (N-MWCNTs). The surface of N-MWCNTs, being a set of potentially reactive graphene edges, provides a large number of reactive sites for chemical modification, so considerable changes in chemical and physical properties can be envisaged. We observed that both reduction (dissolving metal reduction/alkylation) and oxidation (H₂SO₄/HNO₃ and H₂SO₄/KMnO₄ mixtures) of N-MWCNTs lead to formation of interesting spiral channels and spiraled carbon nanoribbons. A variety of techniques, including TGA, SEM, …

Preparation, Characterization And Applications Of Functionalized Carbon Nano-Onions, Mahendra K. Sreeramoju

Theses and Dissertations--Chemistry

Carbon nano-onions (CNOs) discovered by Ugarte in 1992 are multi-layered fullerenes that are spherical analogs of multi-walled carbon nanotubes with diameters varying from 6 nm to 30 nm. Among the various methods of synthesis, CNOs prepared by graphitization of nanodiamonds (N-CNOs) and underwater electric arc of graphite rods (A-CNOs) are the subject of our research. N-CNOs are considered as more reactive than A-CNOs due to their smaller size, high curvature and surface defects.

This dissertation focuses on structural analysis and surface functionalization of N- CNOs with diameters ranging from 6—10 nm. Synthetic approaches such as oleum- assisted oxidation, Freidel-Crafts acylation …

Acenes And Acenequinones For Optics And Organic Electronics, Matthew Bruzek

Theses and Dissertations--Chemistry

Acenes have been explored by a number of research groups in the field of organic electronics with a particular emphasis on transistor materials. This group has been actively studying acene‐based organic semiconductors for more than a decade using a crystal engineering approach and has developed acene derivatives for applications in field‐effect transistors, light‐emitting diodes, and photovoltaics. In addition to organic electronics, crystal engineering has important applications in a number of other fields, quite notably in the design of metal‐organic frameworks. Chapters 2 and 3 of this dissertation focus on applying crystal engineering to the synthesis of acene derivatives for use …

Physicochemical Modifications And Applications Of Carbon Nano-Onions For Electrochemical Energy Storage, Rituraj Borgohain

Theses and Dissertations--Chemistry

Carbon nano-onions (CNOs), concentrically multilayered fullerenes, are prepared by several different methods. We are studying the properties of two specific CNOs: A-CNOs and N-CNOs. A-CNOs are synthesized by underwater arc discharge, and N-CNOs are synthesized by high-temperature graphitization of commercial nanodiamond. In this study the synthesis of A-CNOs are optimized by designing an arc discharge aparatus to control the arc plasma. Moreover other synthesis parameters such as arc power, duty cycles, temperature, graphitic and metal impurities are controlled for optimum production of A-CNOs. Also, a very efficient purification method is developed to screen out A-CNOs from carboneseous and metal impurities. …

Fluorinated Arene, Imide And Unsaturated Pyrrolidinone Based Donor Acceptor Conjugated Polymers: Synthesis, Structure-Property And Device Studies, Arawwawala Don T. Liyanage

Theses and Dissertations--Chemistry

FLUORINATED ARENE, IMIDE AND LACTAM-FUNCTIONALIZED DONOR ACCEPTOR CONJUGATED POLYMERS: SYNTHESIS, STRUCTURE-PROPERTY AND DEVICE STUDIES

After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control 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 …

Optimization Of The Optical And Electrochemical Properties Of Donor-Acceptor Copolymers Through Functional Group And Side Chain Modification, Mark J. Seger

Theses and Dissertations--Chemistry

Donor-acceptor copolymers have received a great deal of attention for application as organic semiconductors, in particular as the active layers in low-cost consumer electronics. The functional groups grafted to the polymer backbones generally dictate the molecular orbital energies of the final materials as well as aid in self-assembly. Additionally, the side chains attached to these functional groups not only dictate the solubility of the final materials, but also their morphological characteristics. The bulk of the research presented in this dissertation focuses on the synthesis and structure-property relationships of polymers containing novel acceptor motifs. Chapter 2 focuses on the synthesis of …