Inorganic Chemistry Commons^™

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 …

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 …

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 …

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 …

Hydrothermal Synthesis, Characterisation, And Magnetic Study Of First-Row Transition Metal Molybdates And First-Row Transition Metal Vanadates, Mahsa Foroughian Foroughian

All Dissertations

Growing high-quality single crystals of transitional metal oxides have been of interest over the last two centuries because of the many applications of these transparent materials in various industries, such as optics, magnetism, semiconductors, and batteries. During this period, a variety of crystal growth techniques have been utilized, each offering unique advantages and disadvantages to the solid-state community.

Traditionally, metal oxides such as molybdates and vanadates are produced using high-temperature techniques (700 to 1200 °C). These methods can cause oxygen to be expelled, resulting in the creation of lattice defects and lower-valence metal ions and complicate precise measurements of physical …

Raw Data For High Entropy Stabilized Platinum Diborides For Poison-Resistant Catalysis, Michael Yeung, Ting Wang

Chemistry Department Faculty Scholarship

Raw data for the publication High-Entropy-Stabilized Platinum Diborides for Poison-Resistant Catalysis including Powder X-ray Diffraction and Nuclear Magnetic Resonance data.

Abstract for publication:

Alloying and solid-solution formation is a powerful technique that enhances and adds properties through elemental mixing, but unfortunately, some elements simply cannot mix as their chemical nature prevents a thermodynamically stable structure. For example, the inherent nobility of platinum group metals does not favor bond formation and precludes their incorporation into higher (boron-rich) metal borides. Here, we demonstrate that when using five or more constituents, the higher mixing entropy will overcome these chemical limitations and form a …

Immobilization Of Ni(Ii) On Amine-Functionalized Mesoporous Silica As Catalyst For Benzyl Alcohol Acetylation Reaction, Wardah Nabilah, Eko Sri Kunarti, Fajar Inggit Pambudi

Makara Journal of Science

In this study, amine-functionalized and Ni(II)-immobilized mesoporous silica materials were synthesized. This research aimed to synthesize mesoporous silica based on rice husk ash functionalized with amine and immobilized with Ni(II). The activity of amine-functionalized and Ni(II)-immobilized mesoporous silica materials was studied for the acetylation of benzyl alcohol with acetic anhydride as the acetylating agent. First, mesoporous silica was synthesized using rice husk ash using the sol–gel method, followed by amine functionalization using (3-aminopropyl)triethoxysilane (APTES) and Ni(II) immobilization through ultrasonic treatment. The results obtained showed that amine-functionalized and Ni(II)-immobilized mesoporous silica (SiO₂/APTES/Ni(II)) were successfully synthesized, confirmed by Fourier transform …

Structural, Electronic And Magnetic Properties Of Vanadium Doped Transition Metal Dichalcogenides (Tmds), Qudsia Ashraf

Dissertations, Theses, and Capstone Projects

Magnetic semiconductors are a prerequisite for spintronic devices but their ferromagnetism disappears at room-temperature hindering application in room temperature electronic devices. Enormous research has been conducted on the room-temperature ferromagnetic order in monolayer form of bulk van der Waals materials but the few layer system has not been extensively explored.

Doping is an effective approach to modulate the structural, electronic and magnetic properties of two-dimensional (2D) Transition metal dichalcogenides (TMDs) and expand their application. The effect of vanadium dopant on structural, electronic and magnetic properties of Tungsten Diselenide (WSe₂) was studied by X-ray Photoelectron Spectroscopy (XPS), Atomic Force …

Studying The Chemistry-Property Relationship In Magnetic And Optical Materials: Spin S = 3/2 Systems Of Neodymium, Manganese, And Cobalt Oxyanions, Xudong Huai

All Dissertations

This dissertation describes the design and tunability of new magnetic and optical materials, emphasizing the intricate relationship between their crystal structures and their optical, electronic, and magnetic properties.

Two new frustrated magnets, ANd(SO₄)₂ (A = Rb, Cs), were designed and synthesized to examine the influence of the the counter cation A site in Nd lanthanide materials featuring a distorted triangular magnetic lattice with S = 3/2. This work demonstrates how the tunability of magnetic and photoluminescent properties can be achieved through the A sites, with findings validated through density functional theory calculations.

AMnTeO₆ (A = Ca, …

The Chemistry Of Heavy Elements: Probing Relativistic Chemical Bonding, Barbara Maria Teixeira Costa Peluzo

Chemistry Theses and Dissertations

The bottommost part of the periodic table has a unique chemistry, where the high velocities of the inner-shell electrons prevent their description by the usual Schrödinger equation. The resulting so-called relativistic effects have numerous chemical implications, on both macro and microscale, ranging from physical properties to reactivity. However, experimental probes on these intriguing atoms are limited by their natural availability and, more importantly, the danger associated with their radioactivity. Quantum chemical calculations, on the other hand, face the challenge of far more complex algebra, which demands substantial computational resources. Relativistic Hamiltonians, which act over all electrons in the system, are …

Synthesis, Electrical Conductivity, Electrocatalytic Activity For Water Splitting, And Pseudocapacitive Properties Of Perovskite Oxide Derivatives., Kinithi Meththa Kumari Wickramaratne

Electronic Theses and Dissertations

Developing green and sustainable energy solutions is crucial to addressing the energy and environmental challenges. Hydrogen is an attractive candidate given its high energy density and low carbon emission compared to gasoline and coal. Electrochemical water splitting through a water electrolyzer is recognized as a green method for generating hydrogen and oxygen gases. Developing cost-effective electrocatalysts to reduce overpotential in hydrogen and oxygen generation is essential for the overall process. The growing interest in perovskite oxides as versatile and sustainable catalysts is driven by their compositional flexibility, tunable electronic structure, earth abundance, and inherent catalytic performance. In our research, we …

Structure-Property Relationship Studies Of Electrically Conductive Metal-Organic Framework Materials, Shiyu Zhang

All Dissertations

Electrically conductive metal-organic frameworks (EC-MOFs) are among the most promising materials due to their tunable structures, properties, and diverse functions. However, the lack of comprehensive understanding of their structure-property relationship hinders the development of EC-MOFs. My dissertation focuses on the design, construction, and structure-property relationship studies of EC-MOFs.

Chapter 1 describes how MOFs' structural features and compositions affect the electronic properties and demonstrates conductive mechanisms and the corresponding design strategies to develop EC-MOFs.

Chapter 2 describes the synthesis, characterization, electronic and optical properties of four novel alkali-metal-based (Na, K, Rb, and Cs) 3D-MOFs with continuous tetrathiafulvalene tetracarboxylate (TTFTC) π-stacks, systematicly …

Solution Combustion Synthesis And Characterization Of Fumarolic Mineral Dolerophanite, Copper (Ii) Oxide Sulfate, Eric J. Cyganowski

Chemistry & Biochemistry Theses - Archive

Dolerophanite Cu₂OSO₄ is a rare mineral found almost exclusively in the fumaroles of volcano systems and is sensitive to temperature and humidity conditions. It has a monoclinic C2/m crystal structure characterized by two-dimensional layers composed of sulfate anions dispersed amongst copper (II) oxide backbones. There has been recent interest in dolerophanite due to the magnetic properties of its Kagome-like lattice as well as its potential use as a photocatalyst or Li-ion battery electrode. Literature on the material however has been limited by the available synthesis strategies. As such, this thesis work presents a novel strategy …

Elucidation Of The Optical Properties Of Si And Si-Ge Alloy Nanostructures With Visible To Near-Ir Photoluminescence, Griffin Spence

Theses and Dissertations

Silicon and silicon-germanium alloy nanostructures have garnered increasing attention in the past 25 years due to their favorable optical properties, visible to near-IR luminescence, and inherently low toxicity. While many synthetic routes have been discussed in the literature, the high-temperature, solid-state disproportionation of hydrogen silsesquioxane (HSQ) has become the most popular way to produce highly crystalline, size-tunable Si and Si-based nanostructures (NCs). It has been shown in this work that maximum annealing temperature from 450°-1100°C and the addition of GeI₂or SnCl₄ precursors can be used to achieve different morphologies, alloying efficiency, and sizes. Directly annealing HSQ from …

Mechanisms Of Dendritic Shorting In Lithium Metal Batteries With Li7la3zr2o12 Solid Electrolytes, Lukas Karapin-Springorum

Pomona Senior Theses

Energy storage will play a crucial role in efforts to mitigate the effects of climate change caused by greenhouse gas emissions from human activity. Lithium metal batteries using solid electrolytes like Li₇La₃Zr₂O₁₂ have higher energy density than lithium-ion batteries, which may enable a more rapid and complete electrification of transportation. However, lithium metal batteries suffer from undesirable short-circuiting when metallic lithium deposits connect the two electrodes. It has been debated whether these lithium dendrites generally grow directionally from the anode or are generated by the reduction of lithium ions inside the solid electrolyte, …

Compton Scattering Of Mammographic Soft X-Ray Beams By Alkali And Transition Metal Salt Filters Produce X-Ray Interference Zones That May Have Treatment Potential For Localized Cancer Lesions, Subhendra N. Sarkar, Eric Lobel, Sabina Rakhmatova, Derbie Desir, Somdat Kissoon, Daler Djuraev, Katie Tam

Publications and Research

In breast x-ray imaging scattered radiation adds 50% of harmful radiation dose from anisotropic Compton scattering mechanism. We have been working with double layered inorganic salt materials that can induce Compton scattering to the incident mammographic x ray beams (in 20-30 kVp range) with adequate isotropy (angular control). Typically metal nitrates and alkali halide salt layers are shown here to cause low energy radiation interference zones with high and low photon intensities and local flux heterogeneity in terms of flux covariance. Spatial variation of low energy photon flux creates concentrated and sparse radiation zones that may be used to induce …

Effect Of Π-Conjugated Ligands And A* Site Organic Cations On The Energetic Properties And Photovoltaic Performance Of Metal Halide Perovskites, Harindi R. Atapattu

Theses and Dissertations--Chemistry

Metal halide perovskites have gained interest in optoelectronic applications such as photovoltaics, lasers, LEDs, transistors, and photodetectors due to their excellent semiconducting properties considering their low cost. Metal halide perovskite (HP) photovoltaics have rapidly increased in power conversion efficiency (PCE), which now exceeds 25%. HPs have gained attention in these applications due to their high tolerance towards defects, long charge carrier diffusion lengths, high charge carrier mobility, high optical absorption, and bandgaps that are tunable over a large range. Even though HP photovoltaic PCEs are improved these are still not commercially available due to them showing lower stability and energy …

Stability Of Organic Metal Halide Perovskites, S S M Tareq Hossain

Theses and Dissertations--Chemistry

Perovskites have emerged as a promising candidate for low-cost production of solar cells. However, the most critical barrier for commercialization of perovskite solar cells (PSCs) is the inadequate stability of the organic metal halide perovskites (OMHPs). The degradation of OMHPs is induced by light, heat, air, and electrical bias. The known degradation pathways involve the oxidation of I- and Sn2+, dissolution of perovskites by moisture, irreversible reactions with water, ion migration, and ion segregation. To improve the stability of OMHPs various methods are adopted, such as additive engineering, perovskite surface treatment, and composition engineering. Surface ligands are used on top …

Fundamental Studies Of Optical Properties And Electrocatalytic Properties Of Low Dimensional Nanomaterials Carbon Nano Dots And 2d Transition Metal Dichalcogenides, Nadeesha Kothalawala

Theses and Dissertations--Chemistry

Low dimensional nanomaterials are widely used in a variety of applications such as opto-electronics, energy production and storage, and bio-medical applications due to their unique optical, catalytic, electronic, and mechanical properties. Most of the nanomaterials offer a plethora of modifications in their structure, composition, morphology, and dimensionality that can lead to the manipulation of their physiochemical properties. This dissertation presents insight into two types of compelling nanomaterials: carbon nanodots (CND) and transition metal dichalcogenides (TMD), investigating their optical and electrocatalytic properties respectively.

Carbon nanodots (CND) are a promising class of photoluminescent nanomaterials that hold a significant potential in many optoelectronic …

Concentration Effects Of Ytterbium(Iii) Ions On The Physical, Structural, Thermal, And Optical Properties Of Barium Phosphate Glasses, Richard Amesimenu

College of Graduate Studies: Theses & Dissertations

Ytterbium(III)-doped glasses are widely known for their application in near-infrared (NIR) lasers and nowadays attract attention for solar spectral conversion in photovoltaic cells. In this study, the effects of ytterbium(III) concentration on the physical, structural, optical, and thermal characteristics of Yb-doped phosphate glasses were investigated. The glasses were synthesized using the melt-quenching technique with nominal compositions of 50P₂O₅:(50 – xBaO):xYb₂O₃ (x = 0, 0.5, 1.0, 2.0, 3.0 and 4 mol%). The properties were then examined by density and related parameters, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform-infrared …

Molecular-Level Design Of Heterometallic Precursors For Rechargeable Battery Cathode Materials, Yuxuan Zhang

Electronic Theses & Dissertations (2024 - present)

The synthetic methods for rechargeable battery cathodes are rapidly evolving along with the continuous advancement of the materials themselves. Utilizing precursors for the synthesis of Li- and Na-ion cathode materials are known to ensure a phase-pure product with isotropic element distribution, thereby further enhancing the electrochemical properties of the cathode material. As more cathode materials with complex compositions continue to emerge, the strategies for designing the corresponding precursors are also getting diversified. One of the most promising directions is the employment of single-source precursors (SSPs), defined as molecules that contain all necessary elements in the proper ratio and decomposable under …

Conversion Of Cellulose To 5-Hydroxymethylfurfural As Sustainable Energy: A Bibliometric Analysis By Vosviewer, Royyan Faradis, Ardiansyah Bagus Suryanto, Irmina Kris Murwani

Journal of Environmental Science and Sustainable Development

The developments of the global economy and society impact resources and the environment. This condition requires an alternative to find new, safe, and sustainable energy types. The conversion of cellulose to 5-hydroxymethylfurfural (5-HMF) has become a significant area of research interest. It has triggered the development of research directions related to biomass and energy because it can be an intermediary source for making polymers, solvents, pharmaceuticals, and biofuels. The primary objective of this study is to give a bibliometric analysis of 1753 reports on the development of research on cellulose conversion to 5-HMF from 1965 to 2021. The data were …

Optimization Of Transition-Metal Inclusive Carbon Aerogels For Electrochemical Energy Applications, Allen Dalton Davis

Electronic Theses & Dissertations

The ever-growing need for energy alongside rising concerns for climate change demands the development of renewable energy technologies. Hydrogen fuel cells are a promising technology that can serve to either supplement energy generation or act as a lone power source. Yet for these devices to be truly green, the hydrogen that serves as fuel must be procured from a renewable resource. Electrolytic water splitting is a process that allows for the dissociation of water into H₂ and O₂. For this process to be practical, the electrolyzer needs to demonstrate high efficiency and stability, as well as a …

Exploring Soybean Oil-Based Polyol And Effect Of Non-Halogenated Flame Retardants In Rigid Polyurethane Foam, Sahithi Kondaveeti

Electronic Theses & Dissertations

To address the increasing demand for sustainable biomaterials due to the depletion of fossil fuel resources and growing environmental concerns, a new type of biodegradable and environmentally friendly rigid polyurethane foam (RPUF) has been synthesized. These foams are derived from chemically modified soybean oil-based polyol obtained from soybean oil by epoxidation followed by a ring-opening reaction. Polyurethane foam is generally used in construction, furniture, and automobile industries but is highly flammable and releases toxic gases and smoke during combustion. In this study, a highly efficient synergistic effect halogen-free flame-retardant (FR) melamine salt, 2-carboxyethyl(phenyl)phosphinic acid melamine salt (CMA) was synthesized from …

Enhanced Mechanical Strength Of Soybean Oil-Based Non-Isocyanate Polyurethane Adhesive For Wood Application By Introducing Nanofillers, Vatsal Chaudhari

Electronic Theses & Dissertations

Polyurethane (PU) is a versatile material that finds extensive use in various industries including bedding, construction, automotive, and packaging. Historically, this particular polymer relied significantly on petrochemical resources, a practice that was considered to have negative environmental impacts. The conventional method for preparing PU involves the use of isocyanate, which is a disadvantage due to its negative impact on the environment and human health. The resolution of this problem entails identifying an appropriate substitute for petroleum-derived products that minimize their impact on both the environment and human health. The researchers earlier utilized soybean oil, for the formulation of PUs in …

Castor Oil Polyol-Based Adhesives With Additional Crosslinker For Improvement In Mechanical And Thermal Properties., Yash Desai

Electronic Theses & Dissertations

Polyurethanes (PU) have been promising polymeric materials with many applications, including adhesives. Projecting an estimated revenue from 42.8 billion $ in 2021 to 61.5 billion $ by 2026. However, a large number of PU adhesives are sourced from petroleum products. Therefore, to lower the dependence on non-renewable resources and provide sustainable and affordable alternatives. In this work will synthesize bio-based adhesives of polyurethane from modified castor oil-based polyol. Generally, polyurethane reaction depends on the properties of polyol and isocyanates. The most important aspect of these reactions is the OH number of the polyol, which is responsible for the crosslinking and …

Chemical And Biological Catalysis Using A Functionalized Fluorinated Phthalocyanine, Mary Chiọma Okorie

Seton Hall University Dissertations and Theses (ETDs)

Phthalocyanines, a class of photosensitizers that generate ¹O₂ using visible light, have been widely used in a variety of applications such as catalysis, solid-state materials, and photodynamic therapy. A 3^rd generation, namely functionalized fluorinated phthalocyanines, F₄₈H₇(COOH)PcMetal, containing a carboxylic acid “tail” allows the Pc to be anchored onto supports such as metal oxides, producing a new family of supported photocatalysts, F₄₈H₇(COOH)PcZn-Oxides.

These new materials photooxidize toxic thioethers mainly to less toxic sulfoxides using visible light and air, a genuine green chemistry pathway. The catalysts are robust and survive reactive …

Scalable Solution Processing Of Niox Nanoparticles., Peter James Armstrong

Electronic Theses and Dissertations

Perovskite solar cells (PSCs) are a promising alternative to silicon-based photovoltaics. However, PSCs face several challenges due to shortcomings in their stability, module efficiency, and scaled production. Although PSCs is still a young field of research, significant attention has been given to demonstrating power conversion efficiencies that are on par with traditional silicon. With that target reached, converting the laboratory demonstration into practical materials to increase access and abundance of solar energy are among the next large targets for the field. This comes with material challenges for perovskite and their companion charge transport layers (CTLs). Among the charge transport materials …

Antibacterial Testing On Silver/Zinc Oxide Nanoparticles/Organoclay Reinforced Chitosan Biocomposites, Lisna Junaeni Muiz, Ariadne Lakshmidevi Juwono, Zulkarnaen Paputungan, Yuni Krisyuningsih Krisnandi

Makara Journal of Science

Herein, bionanocomposites of chitosan (CS)/silver nanoparticle/organoclay/zinc oxide nanoparticle (CS/Ag/OC/ZnO) were prepared for antibacterial food packaging. This study examines the time variation in the AgNP synthesis method by comparing local (74˗85% deacetylated) and commercial chitosan (75%˗85% deacetylated) as a reducing and capping agent and seeks to reconstruct the optimum ratio formulations of AgNPs and ZnONPs in bionanocomposites for food packaging. The results reveal that the synthesis of AgNPs was successfully carried out using a local chitosan solution as a reducing and capping agent. The CS/Ag/OC/ZnO films exhibit structural, mechanical, and optical properties suitable for food packaging and antibacterial activity on Staphylococcus …