Materials Chemistry Commons^™

Laser Ablation In Liquid For The Controlled Production Of Photoluminescent Graphene Quantum Dots And Upconverting Nanoparticles, Rosemary Lynn Calabro

Theses and Dissertations--Chemistry

Photoluminescent­ (PL) nanomaterials play an important role in areas including displays, sensing, solar, photocatalysis, and bio applications. Traditional methods to prepare PL materials suffer many drawbacks such as harsh chemical precursors, complicated synthetic steps, and production of many byproducts. Laser ablation in liquid (LAL) has emerged as a promising alternative to prepare materials that is single-step, fast, uses fewer precursors, produces fewer side products, and has simple purification steps. During LAL, a solid target is irradiated with a pulsed laser source. The laser pulses cause plasma plumes of the target material to form which are cooled, condensed, and can react …

Uncovering Structure-Property Relationships Of Inorganic Nanomaterials Via Transmission Electron Microscopy, Melonie Thomas

Theses and Dissertations--Chemistry

The rapid increase of research in nanoscale devices and nanotechnology in the past few decades has revealed that nanomaterials may possess exceptional properties that are significantly different from the bulk counterpart, due to local rearrangements of the atoms at surfaces and defects. Transmission electron microscopy (TEM) is an indispensable tool when it comes to the characterization of nanomaterials, primarily due to its ability to resolve the local-structure of materials at the atomic-scale. To study dynamic processes, however, regular TEM experiments are inadequate, as they provide only before and after information rather than the real-time data essential to understanding a reaction …

Synthesis Of Metal Oxide Surface And Interface Arrays By A Combined Solid-Liquid- Vapor/Vapor-Liquid-Solid Approach, Alexandra J. Riddle

Theses and Dissertations--Chemistry

This project was motivated by an in situ heating experiment in the transmission electron microscope (TEM) in which gold (Au) nanoparticles were observed to dissolve tin dioxide (SnO2) nanowires (NWs) under vacuum. The explanation for this observation was that the high-temperature and low-pressure environment of the TEM caused the reverse reaction of the well-known vapor-liquid-solid (VLS) method commonly used to grow NWs. In the VLS process, a metal catalyst absorbs reactant vapor until it becomes supersaturated. The precipitation of the NW occurs at the liquid-solid interface, which ceases when there is no longer reactant vapor, and the diameter of the …

Interfaces In Lead-Free Tin Perovskite Photovoltaics: An Investigation Of Energetics, Ion Mobility, Surface Modification, And Performance, Alex Boehm

Theses and Dissertations--Chemistry

Halide perovskites have generated tremendous interest as low-cost semiconductors for optoelectronics, such as photovoltaics, lasers, and light emitting diodes due to their extraordinary optical and transport properties. Perovskite photovoltaics in particular have demonstrated a meteoric rise in power conversion efficiencies and drawn considerable interest as a next-generation solar energy technology. The rapid development has centered around lead-based derivatives, and concerns regarding the toxicity of lead has sparked interest in low toxicity and more environmentally friendly perovskite derivatives. In this regime tin (Sn) is regarded as a prominent alternative owing to the ideal bandgap and reduced toxicity exhibited by Sn-halide perovskites. …

Towards The Rational Design Of Organic Semiconductors Through Computational Approaches, Qianxiang Ai

Theses and Dissertations--Chemistry

Though organic semiconductors have illustrated potential as industry-relevant materials for electronics applications, there are few guidelines that can take one from molecular design to functional materials. This limitation is, in part, due to incomplete understanding as to how the atomic-scale construction of the π-conjugated molecules that comprise the organic semiconductors determines the nature and strength of both the noncovalent intramolecular interactions that govern molecular conformation and noncovalent intermolecular interactions that regulate the energetic preference for solid-state packing. Hence, there remain several fundamental questions that need to be resolved in order to design organic semiconductors from a priori knowledge, including: What …

Designing Metal-Halide Perovskites With Enhanced Optical Properties And Stability Using Surface Ligands, Md Aslam Uddin

Theses and Dissertations--Chemistry

Metal-halide perovskites (MHPs), with formula ABX₃ (A = methylammonium, formamidinium, or Cs⁺; B = Sn²⁺ or Pb²⁺; and X = Cl^-, Br^-, or I^-) are versatile and attractive materials because of their tunable optical and electronic properties. These optical and electronic properties include tunable direct band gaps, high absorption coefficients, low exciton binding energies, relatively high electron and hole mobilities, narrow emission line-widths, and high photoluminescence (PL) quantum yields (Φ_PL). Much of the initial excitement around organic metal-halide perovskites focused on their application in photovoltaics (PVs) …

Developing And Testing Redox Active Organic Molecules For Nonaqueous Redox Flow Battery Applications, Nuwan Harsha Attanayake

Theses and Dissertations--Chemistry

Non-emissive, sustainable energy sources such as solar, wind, and geothermal power have continued to provide an increasing amount of electricity to support electrical grids. Due to the intermittent nature of renewable energy sources like wind and solar, grid energy storage systems must adjust for variations in and mismatches between electricity production and consumption. Among the available energy storage technologies, redox flow batteries (RFBs) are expected to play a critical role in the grid energy storage due to their decoupled energy and power, long service life, and simple manufacturing. However, the worldwide market penetration of RFB systems is still limited due …

Identification Of Adsorbate Ft-Ir Bands Using In-Situ Techniques: Pd Speciation And Adsorption Chemistry Of Pd-Zeolites For Passive Nox Adsorption, Robert Bruce Pace Iii

Theses and Dissertations--Chemistry

To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NO_x) once the catalyst reaches operational temperature (~200 °C). NO_x emitted at lower catalyst temperatures now comprises most of the NO_x released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NO_x adsorbers present an appealing solution to the cold start problem, …

Oxidative Degradation Of Lignin And Investigation Of Utilization Of Lignin-Derived Materials As Building Blocks For Epoxy Resins, Zhen Fang

Theses and Dissertations--Chemistry

Lignin, the second most abundant biopolymer on earth, is potentially a replaceable source for bulky fuels and chemical feedstocks. There have been numerous reports on methods for the oxidative cleavage of β-O-4 linkages but relatively few reports of how those methods affect other linkages that are present in lignin. We investigated how the β-1 and β-5 linkages respond under oxidative conditions proposed for lignin deconstruction based on their effect on β-O-4 linkages. Mechanochemical treatment of lignin can greatly improve the yield of monomer products and we applied a mechanochemical approach, using powerful ring-and-puck milling to promote lignin degradation. Along with …

Synthesis And Characterization Of Carbonaceous Particles From Xylose And Soybean Residuals, Shanshan Wang

Theses and Dissertations--Chemistry

Carbonaceous materials, especially in micro and nanoscale, are useful in optical, energy storage, electronic, and biomedical devices or technologies. Techniques have been developed for preparation and modification of the carbonaceous materials, while it is still challenging to tailor the properties of carbonaceous materials effectively and economically. Laser is a powerful tool in academic and industrial laboratories, which also plays important roles in the preparation and modification of high-performance carbonaceous nanomaterials.

In this study low-cost hydrothermal synthesis, high-temperature annealing, and Laser ablation (LAL) methods are developed to prepare functionalized carbon nanomaterials and modify their electrochemical and optical properties.

Sub-micro hollow carbon …

Modeling The Condensed-Phase Behavior Of Π-Conjugated Polymers, Walker Mask

Theses and Dissertations--Chemistry

It is well established that the morphology and physical properties of an organic semiconducting (OSC) material regulate its electronic properties. However, structure-function relationships remain difficult to describe in polymer-based OSC, which are of particular interest due to their robust mechanical properties. If relationships among the molecular and bulk levels of structure can be found, they can aid in the design of improved materials. To explore and detail important structure-function relationships in polymer-based OSC, this work employs molecular dynamics (MD) simulations to study various π-conjugated polymers in different environments. Two independent investigations are discussed in this work. One investigation examines how …

Synthesis, And Structural, Electrochemical, And Magnetic Property Characterization Of Promising Electrode Materials For Lithium-Ion Batteries And Sodium-Ion Batteries, Ruixin Han

Theses and Dissertations--Chemistry

Iron oxides, have been widely studied as promising anode materials in lithium-ion batteries (LIBs) for their high capacity (≈ 1000 mA h g^-1 for Fe₂O₃ and Fe₃O_4,), non-toxicity, and low cost. In this work, β-FeOOH has been evaluated within a LIB half-cell showing an excellent capacity of ≈ 1500 mA h g^-1 , superior to Fe₂O₃ or Fe₃O_4. Reaction mechanism has been proposed with the assistance of X-ray photoelectron spectroscopy (XPS). Various magnetic properties have been suggested for β-FeOOH such as superparamagnetism, antiferromagnetism and complex …

Carbon Quantum Dots: Bridging The Gap Between Chemical Structure And Material Properties, Timothy J. Pillar-Little Jr.

Theses and Dissertations--Chemistry

Carbon quantum dots (CQDs) are the latest generation of carbon nanomaterials in applications where fullerenes, carbon nanotubes, and graphene are abundantly used. With several attractive properties such as tunable optical property, edge-functionalization, and defect-rich chemical structure, CQDs have the potential to revolutionize optoelectronics, electro- and photocatalysis, and biomedical applications. Chemical modifications through the addition of heteroatoms, chemical reduction, and surface passivation are found to alter the band gap, spectral position, and emission pathways of CQDs. Despite extensive studies, fundamental understanding of structure-property relationship remains unclear due to the inhomogeneity in chemical structure and a complex emission mechanism for CQDs.

This …

Study Of The Effect Of Steric Bulk Of Side Chains On The Properties Of Conjugated Polymers, Bei Zhang

Theses and Dissertations--Chemistry

Donor-acceptor conjugated polymers opened a new era for conjugated polymer research due to the abundant selection and combination of different conjugated units. This class of polymers function as semiconductor materials with potential application in plastic consumer electronics. The frontier molecular orbital energies of the polymers are generally determined by the selection of donor and acceptor units in the backbone structure, and their substituents. The side chains attached to the backbone not only affect the solubility of the materials, but also their self-assembly and morphological characteristics, which indirectly govern optoelectronic properties. It is important therefore to consider backbone architectures and the …

Design And Synthesis Of Functional Organic Materials, Anthony Joseph Petty Ii

Theses and Dissertations--Chemistry

Control of solid state ordering in conjugated small molecules is paramount to the continued development and implementation of organic materials in electronic devices. However, there exists no reliable method on which to predicatively determine how a change to the molecular structure will impact the solid-state packing. As such, the molecule must be synthesized before its solid-state packing can be definitively evaluated. However, once the packing structure of a material is known there exist both qualitative structure- function relationships derived from the literature, as well as quantitative computational methods that can be employed to suggest if a material will perform well …

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 …

Biomimetic Devices To Drive A Thermodynamically Uphill Reaction Using Light And To Degrade Industrial Waste Stream Components, Madison Joanne Sloan

Theses and Dissertations--Chemistry

Given the amount of industrial waste produced each year, as well as the accruing amount of greenhouse gases in our atmosphere produced by the burning of fossil fuels, it is imperative that humanity develop environmentally-sustainable sources of energy and methods of remediation. Nature achieves both of these by use of enzymes as catalysts, inspiring interest in designing biomimetic systems capable of harnessing clean energy and remediating industrial waste. This study examined the ability of enzymes in electrochemical and convective flow systems to achieve these tasks. The first portion studied the incorporation of enzymes into an electrochemical system to drive the …

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 …

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 …

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, …

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 …

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 …

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 …

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 …

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 …

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 …

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, …

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 …

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 …