Chemistry Commons^™

Developing Consensus-Based Methods For The Examination And Interpretation Of Contemporary Vehicle, Architectural, And Portable Electronic Device Glasses By Micro-X-Ray Fluorescence Spectrometry, Zachary Bailey Andrews

Graduate Theses, Dissertations, and Problem Reports (ETD)

Glass is a trace material that is commonly encountered during investigations of violent crimes. When glass is recovered at crime scenes, it can be used to establish links between suspects, victims, and the scene itself. The most discriminatory form of analysis for glass evidence is elemental analysis, and micro-X-ray fluorescence spectrometry (µXRF) is becoming an increasingly common technique used for this purpose. Recent advances in µXRF technology, such as the introduction of silicon drift detectors (SDD) and improved polycapillary optics are promising in enhancing the capabilities for the examination of glass evidence in forensic investigations. However, along with these advances …

Individual And Collective Properties Of Tunable Photochemical Belousov-Zhabotinsky Micro-Reactors, Kudakwashe Benedict Shumba

Graduate Theses, Dissertations, and Problem Reports (ETD)

Cell-like model chemical systems are powerful tools that can be used to explore the role of intercellular coupling on population level behaviors in communities of biological cells. Firstly, we present a new method for fabricating such micro-reactors using the photosensitive Belousov–Zhabotinsky (BZ) reaction system employed in silica microparticles. These BZ micro-reactors have a tunable response to photochemical coupling, varying from a fully excitatory response to a fully inhibitory response. Their response can be tuned through variations in either the reactive mixture or, on an individual micro-reactor level, by changes in the synthesis temperature used during the fabrication of the silica …

Catalytic Deoxygenation Of Oleaginous Biomass To Renewable Diesel And Sustainable Aviation Fuel Via Decarboxylation/Decarbonylation, Chukwudalu Great Umenweke

Theses and Dissertations--Chemistry

Several technologies have been developed to produce hydrocarbon biofuels – renewable diesel (RD) and sustainable aviation fuel (SAF) – from fats, oils, and greases (FOG), with the hydroprocessing of esters and fatty acids (HEFA) representing one of the most mature pathways. In its current form, HEFA is mainly reliant on the hydrodeoxygenation (HDO) reaction, which has several drawbacks since HDO requires large amounts and pressures of hydrogen, feedstocks of high purity and cost, as well as problematic sulfided catalysts that risk contaminating the biofuel product with sulfur. A process based on decarboxylation/decarbonylation (deCO_x) offers an attractive alternative to …

Towards Automating The Study And Discovery Of Electroactive Π-Conjugated Molecules, Rebekah Ann Duke-Crockett

Theses and Dissertations--Chemistry

Chemistry is entering a new paradigm of automation and data-driven discovery. Automated discovery is grounded in well-curated “big data.” As generative and predictive models fueled by simulation data see growing success, emerging robotic automation enables the generation of unprecedented volumes of experimental data. Automation-powered, data-driven approaches hold tremendous potential for groundbreaking insights and innovations, particularly in the study and discovery of electroactive π-conjugated molecules. Realizing this potential, however, requires democratizing chemical data and the automation needed to generate and use it. There is a need to expand access to the tools for findable, accessible, interoperable, and reusable (FAIR) data management …

Machine Learning Models For Molecular-Based Functional Organic Materials, Moses Ogbaje

Theses and Dissertations--Chemistry

Organic semiconductors (OSC) are of interest for a wide range of flexible optoelectronics applications, including transistors, solar cells, and sensors, to name a few. Despite their promise, the design and optimization of OSC pose significant challenges due to the complexity of the structures of the molecular building blocks, varied packing configurations of these building blocks in the solid state, which impacts the optical and electronic response, and sensitivity of the solid-state packing to material processing conditions. Accurately predicting the solid-state properties of OSC traditionally requires high-level quantum mechanical methods. These methods, however, can be computationally demanding, particularly for large molecules …

Exploring The Relationships Between Molecular Structure And Crystal Packing In Small-Molecule Organic Semiconductor Materials, Dean A. Windemuller

Theses and Dissertations--Chemistry

Organic semiconductor materials (OSCs) are rapidly becoming a vital part of the technological landscape. They possess unique properties that make them attractive for the electronics industry. Relatively low-temperature and low-cost processing are a large part of the promise of OSCs. Perhaps more importantly, organic materials can be modified in a relatively straightforward manner, presenting an opportunity for them to be tuned and adapted to a variety of purposes and applications. Polycyclic aromatic hydrocarbons (PAHs) form a large group within the field of OSC research. Some of the most promising high-performance materials in this category to-date are acenes and heteroacenes. This …

Effects Of A-Site Cation Structure And B-Site Metal On Optical And Electronic Properties Of 2d Ruddlesden-Popper Phase Tin-Based Hybrid Perovskites, Henry Pruett

Theses and Dissertations--Chemistry

Organic metal halide perovskites (HPs) are attractive materials for a variety of electronic applications due to their low cost, tunable band gaps, excellent charge transport properties, and high photoluminescence efficiency. As such, HPs are being investigated for use in solar cells, photodetectors, X-ray detectors, light emitting diodes, field effect transistors, lasers, resistive random-access memory, etc. Currently the most popular metal used in HPs is lead, but the use of lead comes with the potential for heavy metal exposure. Tin-based perovskites offer a less hazardous alternative, but their optoelectronic properties lag behind those of lead and less work has been done …

Catalytic Innovation For Sustainable Styrene Production: Green Chemistry Strategies Utilizing Octahedral Ruthenium (Ii) Complexes Supported By A Single Bipyridine Ligand, Kennedy G. Musso, Brandon Quillian, Clifford Padgett, Jose Jimenez

College of Graduate Studies: Theses & Dissertations

This study investigates: 1) the synthesis and reactivity of the mono- substituted systems, [κ²-(t-bipy)Ru(NCMe)2(Ph)(PR3)][BArF'] supported by different ancillary ligands PR3 = (P(OCH3)3 and P(CH3)3) and a single bidentate ligand, 4,4′-di-tert-butyl-2,2′-bipyridine (t-bipy), and 2) UV/heat formation of di-PR3 and tri-PR3 systems supported by a single bidentate ligand to better understand the mechanism of styrene production. Utilizing [(η6-p-cymene)RuI(µ-I)]2 (1), the complexes (η6-p-cymene)RuI2(P(OCH3)3) (2) and (η6-p-cymene)RuI2(P(CH3)3) (3) were synthesized and phenylated to produce (η6-p-cymene)RuI(Ph)(PR3) (6; PR3 = P(OCH3)3 and 7; PR3 = P(CH3)3). Complex 4, (η6-p-cymene)RuCl2(P(CH3)3), was also synthesized and phenylated to produce (η6-p-cymene)RuClPh(P(CH3)3) (5) to understand the impact of chloride versus iodine …

Characterization And Optimization Of Sand And Tung Oil-Based Resins For Binder-Jet 3d Printing, Daniel I. Ajiola

College of Graduate Studies: Theses & Dissertations

Binder-jet 3D printing as a transformative technology in additive manufacturing, offers the ability to fabricate complex structures with diverse materials. This thesis investigates the use of a sustainable tung oil-based resin to create composites, exploring the potential for an eco-friendly alternative to synthetic binders.

The aim of this research is to develop and characterize a bio-based resin formulation, using tung oil as the primary binder, for application in binder-jet 3D printing with sand as the reinforcement. The resin formulation was prepared by combining tung oil, n-butyl methacrylate, divinylbenzene, and di-tert-butyl peroxide in precise proportions, ensuring a balanced mixture that supports …

Synthesis And Characterization Of A Biobased Polymer From Tung Oil And Pine Rosin & Characterization Of Polyhydroxybutyrate., Arijanet P. Osumah

College of Graduate Studies: Theses & Dissertations

This thesis presents two independents but thematically aligned research projects focused on the development and evaluation of sustainable polymers. The first involves the synthesis and characterization of a biobased polymer derived from tung oil and pine rosin. Tung oil, which is a triglyceride was chemically modified to produce tung oil diglyceride (TDG), which subsequently reacted with abietic acid-rich pine rosin to yield tung oil abietate (TOA), a biobased monomer. The TOA monomer was polymerized with butyl methacrylate (BMA) and divinylbenzene (DVB) using di-tert-butyl peroxide (DTBP) as a thermal initiator. The resulting polymer was thoroughly characterized using Fourier transform infrared spectroscopy …

Development, Synthesis And Characterization Of Advanced Low- Cobalt And High-Nickel Cathode Materials For Lithium-Ion Batteries, Arjun Patel

Theses and Dissertations

This dissertation focuses on the improvement of structural and electrochemical stability of active materials for lithium-ion batteries. It explores the modification strategies to mitigate the issues related to Ni-rich cathode materials, along with the continuous production of cathode precursors using a slug flow reactor to improve the quality of the product.

The First part of the dissertation examines the effect of substitution of cobalt with aluminum and iron on the electrochemical stability of Ni-rich lithium nickel cobalt manganese oxide (NCM) materials. This study investigates how Al and Fe doping work and how they impact the performance and stability of these …

Facile Synthesis Of Gold, Copper, And Silicon Nanostructures By Laser Ablation In Liquid, Nicholas Simpson

Theses and Dissertations

Metal nanoparticle (NP) synthesis is a continually evolving area of research, owing to the widespread application of NPs in fields such as catalysis, drug delivery, and biosensing. Compared to bulk metal material, NPs contain a larger proportion of surface atoms and exhibit unique optical properties, thus making them ideal for applications where maximizing surface interactions is key. Moreover, their compositions can be altered in several different ways, as evidenced by metal alloy, core/shell, supported, and defective NPs. While conventional synthesis methods are capable of producing NPs in large quantities, they often require conditions of high temperature and pressure, strong reducing …

Functional Design Of Dissymmetric Ligands For Coordination Systems, Kaitlyn R. Brown

Theses and Dissertations (Comprehensive)

Herein, the functional design of dissymmetric ligands for coordination systems is explored with a focus on their synthesis and structural characterization. The design strategy of these ligands incorporates the ability to coordinate both metal cations and anions along with a ligand site for other functionalization. Their synthesis, structural and other characterization, Hirshfeld surface analysis, and some metal-coordinated complexes are discussed. Chapter 1 introduces supramolecular and coordination chemistry, along with relevant literature that supports this research and outlines the thesis objective. Chapter 2 investigates the hydrogen bonding of a dissymmetric pyrimidine thioether ligand in its neutral form, water solvate, protonated nitrate …

Single-Step Synthesis Of Activated Carbon From Arabica Spent Coffee Ground Using K2co3 As Activator Agent, Ghina Ivana Mieldan, Yuliusman Yuliusman

Journal of Materials Exploration and Findings

Activated carbon is a nanomaterial that is often used as an effective adsorbent. Activated carbon raw materials can use biomass, such as coffee grounds, which can be found along with the growth of public interest in coffee drinks. Chemical activators are used for activation to increase biomass carbon's adsorption capacity. Using K₂CO₃ activator to increase the specific surface area of activated carbon is more harmless than KOH. The use of spent coffee grounds as carbon source and food additive K₂CO₃ as an activator can make food-grade activated carbon that can be used for food. …

Effect Of Alkyd And Polyester Resin Compositions On Corrosion Resistance, Blistering, And Adhesion In Utilization Of Oily Sludge As Anti-Rust Coating Material, Gerets Land Kakalang, Yohanes David Kristianto, Johny Wahyuadi Mudaryoto

Journal of Materials Exploration and Findings

Oil sludge is a waste derived from upstream and downstream activities of the oil and gas industry which is estimated at 10,000 tonnes generated from all PERTAMINA downstream activities spread across various fields, processing units and depots throughout Indonesia. Oil sludge has the same characteristics as asphalt, where asphalt in previous studies can be used as an anti-rust coating, so that the handling of oily sludge can be topped up by reusing and having its own added value. The purpose of this research is to utilise waste oily sludge as an alternative anti-rust coating material and compare alkyd resin and …

Dendrite-Free Strategies For Aqueous Zinc-Ion Batteries: Structure, Electrolyte, And Separator, Gang Wu, Wu-Hai Yang, Yang Yang, Hui-Jun Yang

Journal of Electrochemistry

Continued growth in energy demand and increased environmental pollution constitute major challenges that need to be addressed urgently. The development and utilization of renewable, sustainable, and clean energy sources, such as wind and solar, are crucial. However, the instability of these intermittent energy sources makes the need for energy storage systems increasingly urgent. Aqueous zinc-ion batteries (AZIBs) have received widespread attention due to their unique advantages, such as high energy density, cost-effectiveness, environmental friendliness, and safety. However, AZIBs face significant challenges, mainly the formation of zinc dendrites that seriously affect the stability and lifetime of the batteries, leading to battery …

Electrochemical-Method-Induced Strong Metal-Support Interaction In Pt-Cnt@Sno2 For Co-Tolerant Hydrogen Oxidation Reaction, Shen-Zhou Li, Zi-Jie Lin, Qi-An Chen, Zhao Cai, Qing Li

Journal of Electrochemistry

Inducing the classic strong metal-support interaction (SMSI) is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles (NPs) with supports. Conventional thermal reduction method for inducing SMSI processes is often accompanied by undesirable structural evolution of metal NPs. In this study, a mild electrochemical method has been developed as a new approach to induce SMSI, using the cable structured core@shell CNT@SnO₂ loaded Pt NPs as a proof of concept. The induced SnO_x encapsulation layer on the surface of Pt NPs can protect Pt NPs from the poisoned of CO impurity in …

Contributions To Journal Of Electrochemistry, The Flagship Journal Of Chinese Chemical Society Electrochemical Committee, Will Be Listed As A New Recommendation Policy For China Youth Awards Of Electrochemist, Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.

All-Solid-State Sodium-Ion Batteries: A Leading Contender In The Next-Generation Battery Race, Rui-Jie Zhu, Ze-Chen Li, Wei Zhang, Akira Nasu, Hiroaki Kobayashi, Masaki Matsui

Journal of Electrochemistry

All-solid-state lithium-ion batteries (LIBs) using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety. However, in the pursuit of all-solid-state LIBs, the issue of lithium resource availability is selectively overlooked. Considering that the amount of lithium required for all-solid-state LIBs is not sustainable with current lithium resources, another system that also offers the dual advantages of high energy density and safety— all-solid-state sodium-ion batteries (SIBs) —holds significant sustainable advantages and is likely to be the strong contender in the competition for developing next-generation high-energy-density batteries. This article briefly introduces the research …

Development Of Methods For Predicting Second Harmonic Generation (Shg) Responses Of New Infrared Nonlinear Optical (Ir-Nlo) Materials, Katherine Colbaugh

Electronic Theses and Dissertations

Dissertation supervised by Dr. Jennifer A. Aitken.

In this work, calculations-based methods were evaluated for use in prediction of second harmonic generation (SHG), specifically χ⁽²⁾ values, of infrared nonlinear optical (IR-NLO) materials. Net dipole moment and dipole moment per volume were calculated by the bond valence sum method. Average F-index, proposed in this research, and group F-index, both representing induced dipole moment were also calculated. Each calculation was evaluated by comparing the results to single crystal and powder χ⁽²⁾ measurements of IR-NLO materials. The selected dataset consisted of ninety-six compounds including polar and nonpolar structures, newly discovered and …

Developing A Method To Identify Tyre Particles By Detecting Benzothiazole Via Gc-Ms, Emma Paull

The Plymouth Student Scientist

Tyre particles are a dominant source of microplastic pollution in our environment. However, their chemical and physical properties are poorly understood and no standardised methods for identifying and quantifying them exist. This study looked to develop a method to identify tyre particles using two tyre samples of differing particle sizes, fine (62 - 125 µm) and coarse (250 – 500 µm). Both samples underwent ultrasound-assisted extraction before being analysed via gas chromatography-mass spectrometry (GC-MS) in both full scan and SIM mode, using benzothiazole as a marker. Both samples were also analysed via particle size analysis, scanning electron microscopy (SEM) and …

Analysis Of Dense Metals Accumulation In Shikaripara Stone Mines, Gopinath Gorai, Nirajan Kumar Mandal

Makara Journal of Science

This study aimed to measure the amount of dangerous substances in the cultivated area of the Shikaripara stone mines in Jharkhand, India, which are well known for their stone quarrying. Sixteen soil samples were collected at varying dis-tances from the Shikaripara stone mines in the Dumka District of Jharkhand. The metals found in these samples in-clude Pb, As, Zn, Mn, Cd, Cu, Fg, and Fe. The combined amount of the elements was calculated by inductively coupled plasma mass spectrometry. Enrichment factor, accumulation index, contamination factor, pollution load index (PLI), Nemerow index, and ecological risk index (RI) were employed to assess …

Physical Properties Of Aqueous Imide-Based Electrolyte Solutions, Mollie Harr

Honors Capstones

In order to observe the effects that cations have on the physical properties of -TFSI [-bis(trifluoromethane sulfonyl)imide] based salts, four salts (LiTFSI, NaTFSI, Mg(TFSI)2, and Al(TFSI)3) were selected for testing. The data gathered shows that when the anion is large and bulky like -TFSI, the size of the cation does not have a large effect on the physical properties, but the oxidation state of the cation may have a significant effect. The ion-ion interactions, such as collisions, aggregation, and repulsion are more significant when the cation has a higher oxidation state due to the increased ratio of anion per molecule …

Medium-Entropy Engineering Of Magnetism In Layered Antiferromagnet CuXNi2(1-X)CrXP2S6, Dinesh Upreti, Rabindra Basnet, M. M. Sharma, Santosh Karki Chhetri, Gokul Acharya, Md Rafique Un Nabi, Joshua Sakon, Mourad Benamara, Mansour Mortazavi, Jin Hu

Physics Faculty Publications and Presentations

Antiferromagnetic van der Waals-type M₂P₂X₆ compounds provide a versatile material platform for studying 2D magnetism and relevant phenomena. Establishing ferromagnetism in 2D materials is technologically valuable. Though magnetism is generally tunable via a chemical way, it is challenging to induce ferromagnetism with isovalent chalcogen and bimetallic substitutions in M₂P₂X₆. Here, we report co-substitution of Cu¹⁺ and Cr³⁺ for Ni²⁺ in Ni₂P₂S₆, creating Cu_xNi_2(1-x)Cr_xP₂S₆ medium-entropy alloys spanning a full substitution range ( …

Fitting Quality Of Nmr Relaxation Data To Differentiate Asphalt Binders, Rebecca M. Herndon, Kevin Lai, Magdy Abdelrahman, Klaus Woelk

Civil, Architectural and Environmental Engineering Faculty Research & Creative Works

Asphalt binder performance grades (PGs) are important metrics in designing pavements for effective transportation infrastructure. the PG system relies on the binder's stiffness and is determined through energy- and time-intensive physical testing. Physical properties, like stiffness, can also be determined by spin–lattice NMR relaxometry, a non-destructive chemical method. NMR relaxometry can quantify the molecular mobility of materials by determining relaxation times from exponential decays of excited nuclear magnetization. While relaxation times have been used to determine physical properties of materials, a quantitative relation to the PG grades of asphalt binder is yet to be established. in this study, T1 NMR …

Thermal Conductivity Characterization Of High Oleic Vegetable Oils Based Hybrid Nanofluids Formulated Using Gnp, Tio2, Mos2, Al2o3 Nanoparticles For Mql Machining, Anthony Chukwujekwu Okafor, Tobechukwu Kingsley Abor, Saidanvar Esanjonovich Valiev, Ignatius Echezona Ekengwu, Abiodun Saka, Monday Uchenna Okoronkwo

Mechanical and Aerospace Engineering Faculty Research & Creative Works

This paper presents the results of thermal conductivity characterization of six high oleic soybean oil (HOSO) and four high oleic canola oil (HOCO)-based hybrid nanofluids formulated with four types of nanoparticles (Graphene nanoplatelet (xGnP), TiO2, MoS2, and Al2O3) at nanoparticles wt.% concentration from 1 % to 7 % in 1 % increment using the two-step method for use in MQL machining of difficult-to-cut metals. Thermal conductivity of the formulated hybrid nanofluids were measured using Thermtest Transient Hot Wire Liquid Thermal Conductivity Meter at temperatures from 25 °C to 75 °C in increment of 10 °C. Obtained results showed that thermal …

Experimental Evaluation Of A Recrosslinkable Co2-Resistant Micro-Sized Preformed Particle Gel For Co2 Sweep Efficiency Improvement In Reservoirs With Super-K Channels, Adel Alotibi, Tao Song, Ali Al Brahim, Baojun Bai, Thomas P. Schuman

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

A recross linkable CO₂-resistant branched preformed particle gel (CO₂-BRPPG) was developed for controlling CO₂ injection conformance, particularly in reservoirs with super-permeable channels. Previous work focused on a millimeter-sized CO₂-BRPPG in open fractures, but its performance in high-permeability channels with pore throat networks remained unexplored. This study used a sand pack model to evaluate a micro-sized CO₂-BRPPG under varying conditions of salinity, gel concentration, and pH. at ambient conditions, the equilibrium swelling ratio (ESR) of the gel reached 76 times its original size. This ratio decreased with increasing salinity but remained stable …

Understanding Defect Dynamics In Black Phosphorene Under Noble Gas Ion Irradiation., Saransh Gupta

Electronic Theses and Dissertations

Controlled introduction of defects in phosphorene using high-energy ion beams offers a promising route to design novel high-performance materials for energy technologies. However, this potential remains underexplored due to a lack of fundamental understanding of the atomic-scale mechanisms governing the production, accumulation, and temporal evolution of defects during ion irradiation. Here, we employ a combination of classical and ab initio molecular dynamics simulations to elucidate the effects of ion energy, angle of incidence, noble gas ion size/mass, and fluence on (a) defect generation (i.e., point defects, topological imperfections, voids), (b) atomic-scale mechanisms of defect formation and re-arrangement, and (c) defect …

Thermal Conductivity Characterization Of High Oleic Vegetable Oils Based Hybrid Nanofluids Formulated Using Gnp, Tio2, Mos2, Al2o3 Nanoparticles For Mql Machining, Anthony Chukwujekwu Okafor, Tobechukwu Kingsley Abor, Saidanvar Esanjonovich Valiev, Ignatius Echezona Ekengwu, Abiodun Saka, Monday Uchenna Okoronkwo

Chemical and Biochemical Engineering Faculty Research & Creative Works

This paper presents the results of thermal conductivity characterization of six high oleic soybean oil (HOSO) and four high oleic canola oil (HOCO)-Based hybrid nanofluids formulated with four types of nanoparticles (Graphene nanoplatelet (xGnP), TiO₂, MoS₂, and Al₂O₃) at nanoparticles wt.% concentration from 1 % to 7 % in 1 % increment using the two-step method for use in MQL machining of difficult-to-cut metals. Thermal conductivity of the formulated hybrid nanofluids were measured using Thermtest Transient Hot Wire Liquid Thermal Conductivity Meter at temperatures from 25 °C to 75 °C in increment …

Nickel Electrocatalysts On Carbon Supports For The Hydrogen Evolution Reaction., Mohan Paudel

Electronic Theses and Dissertations

Hydrogen is an important energy storage alternative to fossil fuels due to its high energy density. Currently, most hydrogen is produced through petroleum feedstocks, which produce large amounts of carbon dioxide. However, a more eco-friendly method is the electrocatalytic splitting of water into hydrogen and oxygen. Efficient catalysts for the hydrogen evolution reaction (HER) are typically platinum group metals, which are rare and expensive. There is growing interest in developing HER electrocatalysts with earth-abundant metals for water electrolysis. Nickel, which lies in the same group in the periodic table as Pt and has similar chemical properties, is explored extensively for …