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The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels 2023 University of Louisville

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 …


Structural, Magnetic, Electrical, Pseudocapacitive, And Electrocatalytic Properties Of Bilayered Ruddlesden-Popper Oxides., Chandana Kananke-Gamage 2023 University of Louisville

Structural, Magnetic, Electrical, Pseudocapacitive, And Electrocatalytic Properties Of Bilayered Ruddlesden-Popper Oxides., Chandana Kananke-Gamage

Electronic Theses and Dissertations

Ruddlesden Popper (RP) oxides are perovskite-derived functional materials with the general formula An-1Aʹ2BnO3n+1, where A/Aʹ is often a lanthanide or alkaline earth metal, and B is usually a transition metal. These materials contain perovskite-like connectivity, where BO6 units share apexes to form layers that are stacked above each other. The number of layers in each stack is represented by n in the above formula. The spaces between stacks are often occupied by lanthanide or alkaline-earth metals (Aʹ-site metals), which also reside in intra-stack spaces (A-site) between the octahedra. Oxide materials derived from perovskites have been studied for a wide range …


Carbon Dioxide Reduction On Large Area Liquid Metal Gallium-Indium Electrocatalysts, Thomas Hollis 2023 University of Arkansas, Fayetteville

Carbon Dioxide Reduction On Large Area Liquid Metal Gallium-Indium Electrocatalysts, Thomas Hollis

Chemistry & Biochemistry Undergraduate Honors Theses

Carbon dioxide (CO2) is widely known as a greenhouse gas that contributes to global warming due to the burning of fossil fuels. The carbon dioxide reduction reaction (CO2RR) is widely studied to reutilize CO2 to useful products, including methane, ethane, and carbon monoxide. This project studies the use of liquid metal gallium-indium as an electrocatalyst to perform CO2 reduction to carbon monoxide (CO) or possibly solid carbon in various solutions. Gallium-indium is characterized and studied through its “wetting” properties and adhesion to substrate foil through the measurement of contact angles inside solution. These liquid …


Impacts Of Preferential Flow On Tc-99and Np-237 Vadose Transport In Soils At The Savannah River Site, Josh Parris 2023 Clemson University

Impacts Of Preferential Flow On Tc-99and Np-237 Vadose Transport In Soils At The Savannah River Site, Josh Parris

All Theses

Since the 1950s, the United States has produced approximately 90,000 metric tons of spent nuclear fuel (SNF) (Office of Nuclear Energy, 2022); however, no long-term storage solutions are available. Technecium-99 and neptunium-237, two fission products found in SNF, readily form highly mobile species in oxidizing conditions (Hu, 2008; Bondietti, 1979) and have respective half-lives of 2.13 x 105 and 2.14 x106 years (Hu, 2010). Considering these characteristics, 99Tc and 237Np are two risk-driving isotopes found in SNF storage. The process of macropore-facilitated preferential flow, transport through cracks within a soil matrix, has been recognized to increase …


Synthesis Of A Phenyl Substituted Zinc Dipyrrin Complex For The Purpose Of Analyzing Aromatic Substitutions On The Characteristics Of Compounds Of This Class, Kole Owen 2023 East Tennessee State University

Synthesis Of A Phenyl Substituted Zinc Dipyrrin Complex For The Purpose Of Analyzing Aromatic Substitutions On The Characteristics Of Compounds Of This Class, Kole Owen

Undergraduate Honors Theses

The field of photochemistry is as innovative in development as it is broad in application. However, utilization of energy from the sun’s electromagnetic radiation remains secondary to the combustion of fossil fuels for the global energy consumption. This is neither a sustainable nor renewable system, and it has contributed to a major decline in the health of our global environment as the greenhouse gases emission has led to an incline in global temperatures and ocean acidity. To develop effective ways to utilize solar energy, experimental effort is being directed towards the understanding of photosensitizers, molecules which absorb solar radiation and …


Synthesis Of 2-Bromo-6-Alkylaminopyridines, 2,6-Dialkylaminopyridines, And Tren Based Ligands, Stephanie E. Carter 2023 Georgia Southern University

Synthesis Of 2-Bromo-6-Alkylaminopyridines, 2,6-Dialkylaminopyridines, And Tren Based Ligands, Stephanie E. Carter

Honors College Theses

Extended metal atom chains (EMAC) are multimetallic complexes that feature a linear metal chain with metal-metal bonds surrounded by stabilizing ligand molecules. When EMACs are formed with paramagnetic metal ions, unique magnetic properties can be derived from direct metal to metal communication. The challenge is that EMAC complexes are challenging to synthesize due to the inherent weakness of most M-M bonds and the specificity of the ligands required to stabilize EMACs. In prior work by the Guillet group, the silyl aminopyridine (SAP) ligands were observed to stabilize very unique triiron complexes, but they were inherently unstable. In other work, scaffolded …


Synthesis And Characterization Of Rhenium 2,2′-Pyridylnaphthyridine Metal Complexes, Benjamin F. Solomon 2023 University of Richmond

Synthesis And Characterization Of Rhenium 2,2′-Pyridylnaphthyridine Metal Complexes, Benjamin F. Solomon

Honors Theses

Rhenium (Re) is a group 7 heavy 5d transition metal in the same family as manganese (Mn) and technetium (Tc). Re-carbonyl complexes are known to be catalysts for many different kinds of reactions from C-C bond formation to reduction reactions like CO2 reduction (CO2RR)1,2. With this in mind, we have prepared a set of six Re-carbonyl complexes of 2,2′-pyridyl-1,6-naphthyridine (1,6- pynap) and 2,2′-pyridyl-1,8-naphthyridine (1,8-pynap), a redox non-innocent ligand containing a bpy moiety as well as an additional aryl nitrogen binding location at which another metal-ligand bond could form. We have synthesized these complexes as precursors …


Chemically Responsive Hydrogels, Properties, Pharmaceuticals, And Agricultural Applications: A Review, Mohammad Alrbaihat, Qusay Abu-Afifeh, Firas Al-Zeidaneen 2023 Tafila Technical University JORDAN

Chemically Responsive Hydrogels, Properties, Pharmaceuticals, And Agricultural Applications: A Review, Mohammad Alrbaihat, Qusay Abu-Afifeh, Firas Al-Zeidaneen

Al-Bahir Journal for Engineering and Pure Sciences

A review of the literature on chemically responsive hydrogels about the selection of selectivity based on classification, properties, and application is presented in this article. Chemically responsive hydrogels are a type of hydrogel that undergo changes in their properties in response to specific stimuli. These hydrogels have attracted significant attention due to their potential applications in various fields, including pharmaceuticals and agriculture. Chemically crosslinked hydrogels are synthesized by covalent crosslinking of end-functionalized macromeres. Currently, a great deal of research is being conducted on hydrogel networks, also known as smart networks or hungry networks. This is owing to their potential use …


Bis(Difluoroborylamidinates) With Flexible Ethylene Bridges As Bifunctional Aggregation-Induced Emitters, Connor Welch 2023 Kennesaw State University

Bis(Difluoroborylamidinates) With Flexible Ethylene Bridges As Bifunctional Aggregation-Induced Emitters, Connor Welch

Symposium of Student Scholars

4,4-Difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) represent one of the most prominent classes of dyes, since they are ubiquitously used in protein and DNA labelling, photodynamic therapies, as luminescent tags, sensors, laser dyes, paint and ink compositions, as well as for electroluminescent devices. [1] This is because of their robustness in terms of photochemical stability, polarity and pH changes of their environment, in particular under physiological conditions. The versatility to introduce multiple functional substituents and ability of BODIPYs to strongly absorb UV-light while providing sharp fluorescence peaks, combined with high quantum yields make these dyes highly attractive for numerous applications. Closely related azaBODIPYs offer …


Synthetic, Catalytic, And Mechanistic Studies Of Supermesityl Phosphiranes And Phosphines, Ryan M. Tipker 2023 Dartmouth College

Synthetic, Catalytic, And Mechanistic Studies Of Supermesityl Phosphiranes And Phosphines, Ryan M. Tipker

Dartmouth College Ph.D Dissertations

Methylation of P-stereogenic phosphiranes Mes*PCH2CH(R) (Mes* = 2,4,6-(t-Bu)3C6H2, R = Me, Ph) with MeOTf gave P-stereogenic phosphiranium cations; [Mes*P(Me)CH2CH(Ph)][OTf] underwent syn-anti isomerization via P-epimerization. Mechanistic studies suggested ring opening gave a hyperconjugation-stabilized carbocation in which pyramidal inversion at P was promoted by s-interaction with the pendant cation. Attempted phosphirane protonation with HOTf resulted in ring opening and C-H activation of an o-t-Bu group to give phospholanium cations. Treatment of [Mes*P(Me)CH2CH(Ph)][OTf] with LiPPh2 gave bis(phosphino)ethanes. Copper- catalyzed P-alkylation of the secondary phosphine PHPh(Mes*) with benzyl bromides gave P-stereogenic tertiary phosphines with a supermesityl substituent.


Epitaxial Single-Domain Cu-Btc Metal-Organic Framework Thin Films And Foils By Electrochemical Conversion Of Cuprous Oxide, Xiaoting Zhang, Bin Luo, Avishek Banik, John Z. Tubbesing, Jay A. Switzer 2023 Missouri University of Science and Technology

Epitaxial Single-Domain Cu-Btc Metal-Organic Framework Thin Films And Foils By Electrochemical Conversion Of Cuprous Oxide, Xiaoting Zhang, Bin Luo, Avishek Banik, John Z. Tubbesing, Jay A. Switzer

Chemistry Faculty Research & Creative Works

Metal-Organic Frameworks (MOFs) Are an Important Class of Crystalline Porous Materials with Extensive Chemical and Structural Merits. However, the Fabrication of MOF Thin Films Oriented Along All Crystallographic Axes to Achieve Well-Aligned Nanopores and Nanochannels with Uniform Apertures Remains a Challenge. Here, We Achieved Highly Crystalline Single-Domain MOF Thin Films with the [111] Out-Of-Plane Orientation by Electrochemical Conversion of Cuprous Oxide. Copper(II)-Benzene-1,3,5-Tricarboxylate, Cu3(BTC)2 (Referred to as Cu-BTC), is a Well-Known Metal-Organic Open Framework Material with a Cubic Crystal System. Epitaxial Cu-BTC(111) Thin Films Were Manufactured by Electrochemical Oxidation of Cu2O(111) Films Electrodeposited on Single-Crystal Au(111). …


Determining Bond Strengths And Dissociation Dynamics Of Diatomic Metal-Containing Ions By Photofragment Imaging, Schuyler P. Lockwood 2023 University of Massachusetts Amherst

Determining Bond Strengths And Dissociation Dynamics Of Diatomic Metal-Containing Ions By Photofragment Imaging, Schuyler P. Lockwood

Doctoral Dissertations

Studies of simple metal ion – ligand complexes have primarily focused on understanding their roles in activating C-H and C-C bonds. However, data are often lacking on the fundamental properties of these species, which can have unusual bond orders and cluttered electronic structures with many states of multi-reference character, complicating their treatment in theoretical studies. Experimental work determining high-precision bond energies, ground state identities and excited state dynamics of a wider variety of metal-containing ions is needed to establish a robust set of well-characterized benchmark molecules. This work describes studies of the energetics and dynamics of several MX+ species, …


Synthesis And Characterization Of Some Disubstituted Cyclopentadienyl Rhenium Complexes As Potential Candidates In Semiconductive Materials, Chloe Vernon 2023 Liberty University

Synthesis And Characterization Of Some Disubstituted Cyclopentadienyl Rhenium Complexes As Potential Candidates In Semiconductive Materials, Chloe Vernon

Senior Honors Theses

Since 2000, when the Nobel Prize in Chemistry as awarded for conductive polymer research few studies have been performed concerning the conductive capabilities of discrete organometallic compounds. For this project, organometallic compounds were formed specifically with a transition metal included in the structure. Through oxidation and reduction reactions, the variation in the electrical conductivity could allow for an analysis of whether this unique structure would allow for tunability. The goal of this research was to begin with aromatic substituted fulvenes and perform various multistep synthesis processes, utilizing thallium salt intermediates, to produce several disubstituted cyclopentadienyl rhenium complexes. In this project, …


Synthesis And Characterization Of Terbium(Iii) Complexes: Can We Manipulate The Emission Signature?, Ryan Gagnon 2023 Belmont University

Synthesis And Characterization Of Terbium(Iii) Complexes: Can We Manipulate The Emission Signature?, Ryan Gagnon

Belmont University Research Symposium (BURS)

Successful Lewis acid/base reactions of terbium(III) nitrate with 2,2’-bipyrdine (22’bpy), 1,10-phenanthroline (phen), and 2,6-pyridine dimethanol (pydm) have yielded the products: Tb(22’bpy)2(NO3)3, Tb(phen)2(NO3)3, and [Tb(pydm)3](NO3)3, respectively. In accord with the well-known antenna-effect, the absorption spectrum of each complex is similar to the spectrum of the free ligand, while the emission spectrum of the complex is identical for the free terbium(III) ion. In contrast, the substitution of a ligand containing a third-row nonmetal strategically placed near the terbium may force interaction between the 3p nonmetal …


Synthesis, Characterization, And Cytotoxicity Studies Of A Copper(Ii) Complex With Vanillin 3-Ethyl-Thiosemcarbazone A Ligand, Novia Mann, Ifeoluwa Oyeyemi, Duaa R. Alajroush, Elizabeth A. Tonsel-White, Stephen J. Beebe, Alvin Holder 2023 Old Dominion University

Synthesis, Characterization, And Cytotoxicity Studies Of A Copper(Ii) Complex With Vanillin 3-Ethyl-Thiosemcarbazone A Ligand, Novia Mann, Ifeoluwa Oyeyemi, Duaa R. Alajroush, Elizabeth A. Tonsel-White, Stephen J. Beebe, Alvin Holder

Undergraduate Research Symposium

Triple-negative breast cancer (TNBC) is one of the most aggressive and challenging breast cancer subtypes to treat, as these cancer cells lack three common receptors: estrogen, progesterone, and human epidermal growth factor receptor 2. The multiple oxidation states transition metals can occupy have made this narrowly explored group popular for anti-cancer research in recent decades. Furthermore, the success of cisplatin, which has platinum as a metal center, while being a cancer-fighting agent with serious side effects, has caused other metal centers to be investigated as possible alternatives as chemotherapeutic drugs. Copper, as a biologically essential metal, makes an attractive candidate …


Investigating The Structure Of Metal-Organic Frameworks And The Behaviors Of Adsorbed Guest Molecules In Mofs Via Solid-State Nmr Spectroscopy, Yihao Shen 2023 The University of Western Ontario

Investigating The Structure Of Metal-Organic Frameworks And The Behaviors Of Adsorbed Guest Molecules In Mofs Via Solid-State Nmr Spectroscopy, Yihao Shen

Electronic Thesis and Dissertation Repository

Metal-organic frameworks (MOFs) are a class of hybrid organic-inorganic microporous materials with lots of significant applications including gas capture and storage, gas separation, batteries, catalysis, ion exchange and drug delivery. MOFs based on s-block metals are important due to their many practical applications. These MOFs are also very interesting because the s-block MOFs often exhibit unpredictable behavior of coordination. In this thesis, the structures of six s-block metal (Li, Na, Cs, Mg, Ca, Sr) based MOFs involving V-shaped link, 4, 4′- sulfonyldibenzoate (SDB) are characterized by various techniques including, powder X-ray diffraction, TGA and solid-state NMR spectroscopy. 13C CPMAS …


Optimized Peptide Nanomaterials As Delivery Vehicles For Hydrophobic Metal-Based Anticancer Agents, Yaron Marciano 2023 The Graduate Center, City University of New York

Optimized Peptide Nanomaterials As Delivery Vehicles For Hydrophobic Metal-Based Anticancer Agents, Yaron Marciano

Dissertations, Theses, and Capstone Projects

Enzyme-responsive materials have been well explored, particularly as therapeutic and diagnostic agents. In this thesis we demonstrate that anionic self-assembling peptides can be utilized as delivery vehicles for metal-based hydrophobic payloads. The tunability of the system is highlighted as well as the increase in cytotoxicity and selectivity in vitro. The rapid degradation of peptides in cell media may lead to the formation of new peptide-drug bioconjugates with increased activity and selectivity. The physiological stability of these peptide delivery vehicles has been optimized by capping the N-terminus with an acetyl group. This simple backbone modification was shown to not prevent self-assembly, …


Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran 2023 The University of Western Ontario

Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran

Electronic Thesis and Dissertation Repository

Nickel is a widely abundant and inexpensive metal. Catalysts are substances that remain unconsumed and increase the rate of reactions by reducing the activation energy barrier, often by providing an alternative route. The main goal of this study is to prepare Ni(II) complexes that can promote a catalytic aerobic oxidation reaction by breaking allylic C-H bonds. Based on previous studies, allylnickel N-heterocyclic carbene complexes react with molecular oxygen to give useful carbonyl compounds with a Ni(II)-OH by-product, which undergoes dimerization. In order to achieve catalysis, dimerization of the Ni(II)-OH should be prevented and C-H activation has to be achieved to …


Influence Of Synthesis Conditions On The Physicochemical And Electrocatalytic Properties Of Non-Stoichiometric Ba2sr2la2ti4o12 Perovskites, Ofeliya Kostadinova, Iliyan Popov, Simeon M. Stankov, Hristo Kolev, Tamara Petkov 2023 Institute of Electrochemistry and Energy Systems Acad. Evgeni Budevski, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl 10, 1113 Sofia, Bulgaria

Influence Of Synthesis Conditions On The Physicochemical And Electrocatalytic Properties Of Non-Stoichiometric Ba2sr2la2ti4o12 Perovskites, Ofeliya Kostadinova, Iliyan Popov, Simeon M. Stankov, Hristo Kolev, Tamara Petkov

Karbala International Journal of Modern Science

Present work studies the influence of the pretreatment milling media (deionized water (BLTOS-H) and isopropanol (BLTOS-i)) on the surface characteristics, structure, chemical composition and catalytic activity of non-stoichiometric Ba2Sr2La2Ti4O12 perovskites. The IR spectroscopy and XRD analyses shows a difference in the structure and phase composition of the two materials. X-ray photoelectron spectroscopy detects a Ba2+- and La3+-enriched and Sr2+-depleted surface. The BLTOS-i sample appears to exhibit higher specific surface area (SSA) and pore volume in comparison to BLTOS-H. The electrochemical tests showed that BLTOS-H sample have similar behavior to platinum at current densi-ties up to 10 mA cm-2, while BLTOS-i …


Synthesis Of A Novel Terbium(Iii) Complex For Application In Metal Nanoparticle Surface Modification, Lauralee E. Hurst, Davon Ferrara, Justin Stace 2023 Belmont University

Synthesis Of A Novel Terbium(Iii) Complex For Application In Metal Nanoparticle Surface Modification, Lauralee E. Hurst, Davon Ferrara, Justin Stace

Science University Research Symposium (SURS)

Lanthanide ions, such as terbium(III), exhibit bright luminescence when bound to organic ligands which strongly absorb light. This property has been used in creating chemical sensors or luminescent tags for microscopy. Complexes centered with terbium(III) exhibit a yellow-green luminescence upon excitation by shortwave ultraviolet light. In this work, a bifunctional ligand, 4-mercaptobenzoic acid (4mba), was chosen to selectively coordinate terbium(III) to the oxygens of the acid functional group, leaving the thiol group available for another compound. Thiol groups are effectively used in surface coordination to noble metal nanoparticles (NP). In efforts to create a novel 4mba-terbium(III)-NP system, a one pot …


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