Chemistry Commons^™

Advances In Cellulose Nanomaterial-Based Foams For Environmental Applications, Md Musfiqur Rahman

Electronic Theses and Dissertations

The use of metal-oxide nanoparticles adsorbents is limited to fixed-bed columns in industrial-scale water treatment applications. This limitation is commonly attributed to the tendency of nanoparticles to aggregate, the use of non-sustainable and inefficient polymeric resins as supporting materials, or a lack of adsorption capacity. Foams and aerogels derived from cellulose nanomaterials have unique characteristics, such as high porosity and low density, which enables their use in a variety of environmental applications, including water treatment. However, the overall use of cellulose nanomaterial-based foams in various environmental sectors is limited due to the high cost of production associated with time- and …

Influence Of Platinum Nanoparticles On Ionic Transport And Hydrogen Reactivity Of Yttria-Stabilized Zirconia Thin Films, Firas Mahyob

Electronic Theses and Dissertations

Yttria-stabilized zirconia (YSZ) is a widely used ceramic material in solid oxide fuel cells, oxygen sensors, and sensing applications due to its high ionic conductivity, chemical inertness, and thermal stability. YSZ is promising active coating for use in miniaturized harsh environment wireless surface acoustic sensors to monitor gases such as H₂. Adding catalytic Pt nanoparticles can enhance gas reactivity and lead to associated film conductivity changes.

In this work, thin films with an (8% Y₂O₃ - 92% ZrO₂) composition were deposited onto piezoelectric langasite substrates using RF magnetron sputtering in Ar:O₂ - …

The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels

Electronic Theses and Dissertations

The purpose of this study was to investigate and compare the corrosion mechanisms between wrought and additive-manufactured (3D-printed) copper and stainless steel. The experimental procedure consisted of measuring the open circuit potential, electrochemical impedance spectroscopy, linear sweep voltammetry, Tafel analysis, surface topology, and scanning electron microscopy for each metal within salt water, tap water, sulfuric acid, and synthetic body fluid (excluding copper in synthetic body fluid).

Overall, printed stainless steel was more corrosion-resistant than wrought stainless steel in tap water and synthetic body fluid based on OCP, LSV, and surface topology results. Additionally, printed copper was more corrosion-resistant than wrought …

Enzymatic Removal Of Diclofenac And Aceclofenac From Synthetic Wastewater By Soybean Peroxidase, Sarah Pishyar

Electronic Theses and Dissertations

Pharmaceutical medications that are a class of emerging contaminants have been detected in wastewater treatment facilities' influent and effluent, and they have reached water sources in amounts ranging from ng/L to ug/L. They threaten the environment and non-target life. Soybean peroxidase (SBP)-catalyzed process was studied to remove two non-steroidal anti-inflammatory drugs (NSAIDS) diclofenac and aceclofenac through enzymatic oxidation from synthetic wastewater. SBP can be extracted from soybean hulls, a by-product of the soybean industry. First, the experiments studied the viability of SBP-catalyzed removal on these two compounds, then the operational parameters including pH, the molar ratio between hydrogen peroxide and …

Enzymatic Removal Of Sulfa Drugs From Synthetic Wastewater By Soybean Peroxidase, Maryam Sharifzadeh

Electronic Theses and Dissertations

Sulfa drugs are a broad family of antibiotics that are widely used in the treatment of a wide range of infections, and they have been found in surface and groundwater, as well as present in sewage and effluent (treated sewage and sludge)municipal or industrial wastewater treatment plants (WWTPs). in concentrations of ng/L to >g/L. The continued presence of these so-called emerging pollutants (ECs) and their metabolites can cause adverse ecological effects, including bacterial resistance, even at very low concentrations. In this study, the first aim was to explore the feasibility of oxidation processes catalyzed by soybean peroxidase as an eco-friendly …

Intersections Of Environmentalism, Chemistry, And Racism: An Experimental Study Of Halobenzene Hydrogenolysis And Critical Communication Studies Of Equitable Learning Practices Rooted In Black Feminism, Lauren O. Babb

Electronic Theses and Dissertations

Increasing concentrations of fluorinated aromatic compounds in surface water, groundwater, and soil pose threats to the environment. Fundamental studies that elucidate mechanisms of dehalogenation for C-X compounds (where X represents a halide) are required to develop effective remediation strategies. For halogenated benzenes, previously published research has suggested that the strength of the C-X bond is not rate-determining in the overall rate of dehalogenation. Instead, the rate-determining step has been hypothesized to be adsorption of the C-X compound onto the surface of a catalyst. Building on this hypothesis, in this work, we examine the reaction kinetics of fluorobenzene conversion to benzene, …

Surface-Functionalized Chemiresistive Films That Exploit H-Bonding, Cation-Pi, And Metal-Halide Interactions., Prasadanie Karunarathna Adhihetty

Electronic Theses and Dissertations

The development of gas sensors for detection of volatile organic compounds (VOCs) has been of interest in the sensing field for decades. To date, the use of metal nanoparticle-based chemiresistors for trace VOC detection, particularly gold nanoparticle-based sensors, is of great interest due to their high chemical stability, ease of synthesis, unique optical properties, large surface to volume ratio, and high level of conductivity. Much effort has been devoted towards gold monolayer protected clusters (Au MPCs) as chemiresistors to detect harmful VOCs. The present thesis documents the results of our efforts to exploit the advantages of functionalized Au MPCs chemiresistors …

Structural, Charge Transport, Gas Sensing, Magnetic, Pseudocapacitive, And Electrocatalytic Properties Of Perovskite Oxides., Surendra Bahadur Karki

Electronic Theses and Dissertations

Perovskites are functional materials with the general formula ABO₃ (A = alkali, alkaline earth or lanthanoid cations and B = transition metal or main group cations). These materials are marked by a variety of crystal structures and interesting properties such as colossal magnetoresistance, ferroelectricity, multiferroicity, superconductivity, pseudocapacitance, gas sensing, charge transport, and electrocatalytic properties. The formula of perovskite can be written as AA’BB’O₆, when there is ordering between two cations over A and B-sites. Such compounds are called double perovskite oxides. Some amount of oxygen could be lost from crystal structure without decomposition of the phase. Such …

Charged-Particle Interactions To Generate Novel Coatings And Materials, Pradnya D. Rao

Electronic Theses and Dissertations

A typical paper coating formulation contains anionically charged pigments and latex to provide a high-quality surface for printing. However, during application and drying, the latex can migrate to the surface or deep into the paper, resulting in weak coating layers or the need to use a high latex content to obtain the same strength properties. In this thesis, we have explored the introduction of cationically charged particles into the suspension as a way to reduce the amount of binder in the coatings, improve coating strength and reduce binder migration. With these aims in mind, we have generated cationic precipitated calcium …

Characterization Of A Three-Way Catalyst For High Efficiency Spark Ignition Engines, Cavin Hesketh

Electronic Theses and Dissertations

The push for environmental protection and sustainability has led to strict emission regulations for automotive manufacturers as evident in EURO VII and 2026 EPA requirements set to take effect in the coming years. The modern gasoline spark ignition (SI) engine typically employs various in-cylinder emission reduction techniques along with an exhaust after-treatment system to comply with emission standards. The three-way catalyst (TWC) is wholly responsible for removing the engine-out emissions including hydrocarbons (HC), carbon monoxide (CO) and nitrogen oxides (NOx). The main objective of this thesis is to investigate the impact of extensive exhaust gas recirculation (EGR) on …

Gradient Generating Microfluidic Coculture System For Disease Modeling And Neural Development, Phaneendra Chennampally

Electronic Theses and Dissertations

Cellular microenvironment or cell niche plays an important role in developmental biology and disease pathophysiology. Physical or chemical signals in microenvironment drive the cellular activity. These signaling molecules are generated from the surrounding cells/tissues as part of intercellular communication; a fundamental property of a cell. Dynamic profile of these signaling molecules in the microenvironment plays a pivotal role in transfer of molecular information from cell to cell in disease proliferation or fate determination. Recapitulating these signaling cues in an in vitro study is difficult to achieve using standard cell culture techniques. However microfluidic systems are capable of addressing these issues, …

Synthesis, Crystal Structure And Ionic Conductivity Of Ruddlesden-Popper Oxide Materials: Effects Of Ionic Radii And Defects On Lithium-Ionic Conductivity., Selorm Joy Fanah

Electronic Theses and Dissertations

Layered perovskite oxides of the Ruddlesden-Popper (RP) type structure can be good lithium-ion conductors for solid electrolyte applications in all-solid-state batteries, due to the large gap separating octahedral layers which can be useful pathways for Li-ion conduction. However, little work has been done on their lithium-ion transport properties in these materials despite their interesting structural properties. This work highlights the synthesis and study of the ionic conductivities in a series of n = 2 and 3 Ruddlesden-Popper oxides, as part of an ongoing investigation in search of alternative solid electrolyte materials. Several different strategies were employed for the enhancement of …

Understanding Biomass Upgrading Through Hydrogenolysis Reactions: Kinetics And Mechanism, Jalal Tavana

Electronic Theses and Dissertations

This dissertation involves several hydrogenolysis reactions but is mainly focused on hydrodechlorination (HDC) of chlorobenzene (PhCl) and hydrodeoxygenation (HDO) of 2-furancarboxylic acid (FCA). Hydrodechlorination of PhCl has been the subject of research for some time. Here, we used a Pd/C catalyst to study this reaction though rigorous kinetics and mechanistic analyses in a CSTR reactor. The H₂/D₂ kinetic isotope effect (KIE) experiment revealed that H₂ is not involved in a rate controlling step. The kinetics data are in agreement with similar systems reported before and follow a first-order dependence on chlorobenzene, half order for hydrogen and …

Instrument And Application Development In Saturation Recovery And Rapid Scan Electron Paramagnetic Resonance, Joseph E. Mcpeak

Electronic Theses and Dissertations

Enhanced signal sensitivity by the use of Rapid Scan (RS) electron paramagnetic resonance (EPR), a technique that allows for much faster magnetic field scans than traditional field-swept techniques, has facilitated improved data acquisition for many types of samples. For example, irradiated fingernails for radiation dosimetry have been studied using RS-EPR, which resulted in substantial decreases in detection limits. Samarium-mediated reduction mechanisms in organic synthesis have been investigated by RS-EPR providing evidence for a radical intermediate. Spectra of organic radicals exhibiting both narrow lines and closely spaced hyperfine interactions have been recorded via RS-EPR. Well-resolved spectra can be recorded at a …

Controls On Phosphorus Export From An Agricultural Watershed: Amsden Brook, Fort Fairfield, Maine Usa., Gregory J. Mcdonald

Electronic Theses and Dissertations

This study explores the sources and mechanisms of phosphorus (P) mobilization during base flow within the Amsden Brook watershed, Fort Fairfield, Maine, USA. Amsden Brook is an agriculturally dominated watershed drained by a spring-fed and perennial first- to second-order stream. We characterized the P concentrations within the watershed to investigate connections between soils, stream sediment, surface water, and groundwater. Waters were monitored monthly during the 2017 snow-free period for temperature, pH, dissolved oxygen, conductivity, soluble reactive P (SRP), total P, strong acid anions, strong base cations, dissolved organic carbon (DOC), Al, Fe, and Mn. Phosphorus speciation within soils and sediment …

Mechanistic Studies Of Reducible Metal Oxides As Hydrodeoxygenation Catalysts, Akbar Mahdavi Shakib

Electronic Theses and Dissertations

Hydrodeoxygenation of phenol to benzene using ruthenium supported titania catalysts strongly varies depending on the support crystal structure and preparation conditions. Here, we performed spectroscopic characterization of titania supports to identify the surface impurities common to commercial and synthesized titania samples using a variety of spectroscopic methods. Sulfate impurities were detected for the commercial anatase samples and a procedure for their elimination was proposed so that inactive catalysts gained reactivity. Surface hydroxyls of different TiO2 samples (anatase, rutile, and pyrogenic) were identified using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed on vigorously cleaned surfaces and a facet-specific assignment …

Developing A Risk Assessment Protocol To Quantify Distribution And Uptake Of Persistent Organic Pollutants In Glacial Outflows, Kimberley Rain Miner

Electronic Theses and Dissertations

Pollutants released by industrialized nations between 1960 and 2004 have been transported northward through atmospheric processes and deposited into glaciated alpine ecosystems. Many of these chemicals retain their original structure and are absorbed into the biota thousands of miles away from where they were originally utilized. With a warming climate increasing the melt of alpine glaciers, these glaciers may be introducing growing amounts of toxins into the watershed. While studies have demonstrated the existence of resident pollutants within glaciated ecosystems, no one has developed a risk assessment to identify sources and quantity of risk posed by these compounds when released …

Surface Reaction And Diffusion Kinetics In Semiconducting Metal Oxide Film Gas Sensors, Aravind Reghu

Electronic Theses and Dissertations

Chemiresistive metal oxide gas sensors based on materials such as SnO₂, ZnO, and TiO₂, have been investigated extensively by many researchers for a wide range of applications. The band bending model, based on the surface chemistry of highly reactive ionosorbed species (O₂^- or O^-) and the semiconducting material properties of SnO₂, TiO₂ and ZnO, adequately predicts the dependence of the change in sensor conductivity (Δσ) as a function of target gas pressure and temperature. However, the band bending model is not applicable to gas sensors based on reducible oxides …

Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders

Electronic Theses and Dissertations

The purpose of this research was to investigate the use of cellulose nanofibers (CNF) compounded into an impact modified polypropylene (IMPP) matrix. A IMPP was used because it shrinks less than a PP homopolymer during FLM processing. An assessment of material properties from fused layer modeling (FLM), an additive manufacturing (AM) method, and injection molding (IM) was conducted. Results showed that material property measurements in neat PP were statistically similar between IM and FLM for density, strain at yield and flexural stiffness. Additionally, PP plus the coupling agent maleic anhydride (MA) showed statistically similar results in comparison of IM and …

Water Chemistry Dynamics In Four Vernal Pools In Maine, Usa, Lydia H. Kifner

Electronic Theses and Dissertations

Vernal pools are small seasonal wetlands that are a common landscape feature that contribute to biodiversity in northeastern North American forests. However, even basic information about their biogeochemical functions, such as carbon cycling, is limited. Dissolved gas concentrations (CH₄, CO₂) and other water chemistry parameters were monitored weekly at the bottom and surface of four vernal pools in central and eastern Maine, USA, from April to August 2016. The vernal pools were supersaturated with respect to CH₄ and CO₂ at all sampling dates and locations. Concentrations of dissolved CH₄ and CO₂ ranged …

Artificial Olfactory System For Multi-Component Analysis Of Gas Mixtures., Alexander Aleksandrovich Larin

Electronic Theses and Dissertations

Gas analysis is an important part of our world and gas sensing technology is becoming more essential for various aspects of our life. A novel approach for gas mixture analysis by using portable gas chromatography in combination with an array of highly integrated and selective metal oxide (MOX) sensors has been studied. We developed a system with small size (7 x 13 x 16 inches), low power consumption (~10 W) and absence of special carrier gases designed for portable field analysis (assuming apriori calibration). Low ppb and even sub-ppb level of detection for some VOCs was achieved during the analysis …

Creating Renewable Tunable Polymers From Hydroxymethylfurfural, Meredith C. Allen

Electronic Theses and Dissertations

The research here deals with the conversion of 5-hydroxymethylfurfural (HMF) into a tunable polymer. HMF is a known derivative that can be acquired from biomass via hydrolysis of cellulose followed by isomerization and finally selective dehydration. The process considered here is being developed to create tunable polymers from HMF and involves several different steps, three of which are covered here. The first step, an etherification, is the reaction of HMF with an alcohol. This step is significant because in this step the R-group from the alcohol is added to HMF and the branching portion formed is carried over to the …

Direct Band Gap Gallium Antimonide Phosphide (Gasbxp1-X) For Solar Fuels., Harry Benjamin Russell

Electronic Theses and Dissertations

Photoelectrochemical water splitting has been identified as a promising route for achieving sustainable energy future. However, semiconductor materials with the appropriate optical, electrical and electrochemical properties have yet to be discovered. In search of an appropriate semiconductor to fill this gap, GaSbP, a semiconductor never tested for PEC performance is proposed here and investigated. Density functional theory (DFT+U) techniques were utilized to predict band gap and band edge energetics for GaSbP alloys with low amount of antimony. The overall objective of this dissertation is to understand the suitability of GaSb_xP_1-x alloys for photoelectrochemical water splitting application. Specifically, …

Degradation Of High Voltage Glass Fiber-Reinforced Polymer Matrix Composites By Aggressive Environmental Conditions, Tianyi Lu

Electronic Theses and Dissertations

Polymer matrix composites reinforced with either E glass or ECR glass fibers-reinforced are used in a variety of high voltage electrical applications because of their advantages like lower weight and cost. However, they can be damaged by aggressive in-service conditions such as high temperature, ultraviolet radiation, moisture, ozone and corrosive environments. Different degradation mechanisms can develop in high voltage PMCs under those extreme environments, which, in turn, can affect the long term structural durability of the composites. A set of PMCs reinforced with ECR-glass and E-glass fibers embedded in four different resins has been investigated in this study. In addition, …

Study Of Immobilizing Cadmium Selenide Quantum Dots In Selected Polymers For Application In Peroxyoxalate Chemiluminescence Flow Injection Analysis, Christopher S. Moore

Electronic Theses and Dissertations

Two batches of CdSe QDs with different sizes were synthesized for immobilizing in polyisoprene (PI), polymethylmethacrylate (PMMA), and low-density polyethylene (LDPE). The combinations of QDs and polymer substrates were evaluated for their analytical fit-for-use in applicable immunoassays. Hydrogen peroxide standards were injected into the flow injection analyzer (FIA) constructed to simulate enzyme-generated hydrogen peroxide reacting with bis-(2,4,6-trichlorophenyl) oxalate.

Linear correlations between hydrogen peroxide and chemilumenscent intensities yielded regression values greater than 0.9750 for hydrogen peroxide concentrations between 1.0 x 10^-4 M and 1.0 x 10^-1 M. The developed technique’s LOD was approximately 10 ppm. Variability of the prepared …

Synthesis And Characterization Of Mesoporous Silica Membranes Modified By Atomic And Molecular Layer Deposition, David Emmett Cassidy

Electronic Theses and Dissertations

Inorganic membranes offer a means for chemical separations in a variety of applications including chemical processing, drug delivery systems, battery separators and fuel cells. There is currently a “pore size gap” in silica membranes between 1-2 nanometers. Synthesizing membranes with a fine control of the pore size and distribution within that gap is a significant challenge. This thesis reports findings on using atomic and molecular layer deposition as new synthesis approaches to controlling pore size and chemical functionality of silica membranes. Mesoporous silica membranes, prepared using surfactant-templates with pore diameters ~4nm, were modified using atomic layer deposition and molecular layer …

Synthesis And Characterization Of Catalysts For The Selective Transformation Of Biomass-Derived Materials, Isaac Tyrone Ghampson

Electronic Theses and Dissertations

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silicasupported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, …

Exfoliated Graphite Nanoplatelet-Filled Impact Modified Polypropylene Nanocomposites, Alex Duguay

Electronic Theses and Dissertations

Exfoliated graphite nanoplatelets (xGnP)-filled polymer composites have demonstrated superior electrical, mechanical, physical and thermal properties and are becoming a major focus for both academic and industrial research and development (R&D) activities. The main objective of this study was to characterize the influence of xGnP particle diameter, filler loading and the addition of coupling agents on the mechanical, rheological and thermal properties of xGnP-filled impact modified polypropylene (IMPP) composites. IMPP is currently being used at the AEWC Advanced Structures and Composites Center in polymer impregnated (pre-preg) fiber reinforced polymer (FRP) tapes consisting of an IMPP matrix polymer and E-glass continuous fibers. …

Biological Conversion Of Hemicellulose Extract Into Value-Added Fuels And Chemicals, Sara Lynn Walton

Electronic Theses and Dissertations

The research presented in this thesis describes the fermentation of hemicellulose extracts to produce ethanol and lactic acid. Hardwood hemicellulose extracts made at a variety of conditions using the green liquor and hot water extraction processes were characterized and then fermented by Escherichia coli K011 and Bacillus coagulans MXL-9. Hemicellulose extracts were found to contain a dilute amount of xylo-oligosaccharides and acetic acid as the major components, and many minor components including other organic acids, lignin-derived phenolics, and sugar degradation products. In order to generate ethanol economically, the fermentation must produce at least a 4% ethanol solution, which requires a …

Nanofiltration Membrane Pilot Studies For Disinfection By-Product Control, Eric J. Lynne

Electronic Theses and Dissertations

Watertown, South Dakota currently uses conventional softening to treat ground water to remove hardness, iron and manganese, and natural organic matter. The distribution system has experienced elevated concentrations of disinfection by-products, which will require additional treatment to comply with future limits set by the Stage 2 Disinfectant/Disinfection By-Products Rule. A nanofiltration membrane system has been proposed to remove additional natural organic matter from the softened water. Removing the natural organic material disinfection by-product precursors should reduce the concentration of disinfection by-products. The use of nanofiltration membranes has been previously documented to reject total organic carbon, while allowing desirable levels of …