Chemistry Commons^™

Sulfate Enhances The Adsorption And Retention Of Cu(Ii) And Zn(Ii) To Dispersed And Aggregated Iron Oxyhydroxide Nanoparticles, Emma M. Kocik, Abigail Kim, Miranda L. Aiken, Lauren Smith, Christopher S. Kim

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The adsorption and retention of metal ions to nanoscale iron (hydr)oxides in aqueous systems is significantly influenced by prevailing environmental conditions. We examined the influence of sulfate, the second most common anion in seawater that is present in many other natural aquatic systems, on the adsorption and retention of Cu(II) and Zn(II) to synthetic iron oxyhydroxide nanoparticles (NPs) and their aggregates. Batch uptake experiments with monodisperse NPs and NPs aggregated by changes in pH, ionic strength, and temperature were conducted over sulfate concentrations ranging from 0 to 0.30 M. The introduction of 0.03 M sulfate significantly increased the initial adsorption …

Copper-Indazolate Nanojars: Synthesis And Characterization, Nicholas Alexander Rudell

Masters Theses

The field of synthetic supramolecular chemistry has exploded since the first syntheses of crown ethers by Charles Pedersen in the 1960s, leading to further development in the area of macrocycles and incorporation into a vast array of metal-organic structures. Supramolecular chemistry came to the forefront of science with the 1987 Nobel Prize in Chemistry, awarded jointly to Donald J. Cram, Jean-Marie Lehn, and Charles Pedersen “for their development and use of molecules with structure-specific interactions of high selectivity.”

Nanojars are supramolecular metal-organic complexes with a high affinity for hydrophilic anions and can efficiently transfer such anions from water into organic …

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 …

Use Of Electrochemical Techniques And Statistical Analysis To Investigate The Pitting Probability Of Copper, Sina Matin

Electronic Thesis and Dissertation Repository

The development of a safe permanent disposal plan is essential for the long-term disposal of used fuel bundles. Nuclear Waste Management Organization (NWMO) has been investigating the deep geologic disposal of nuclear waste which offers the optimum passive safety system with a negligible probability of release of radionuclides into the environment.

The proposed used fuel containers (UFC) for the permanent disposal of high-level nuclear waste in Canada is comprised of a carbon steel vessel coated with a 3 mm corrosion-resistant copper layer deposited using a combination of electrodeposition and cold spray deposition. Although copper is often considered to be thermodynamically …

Characterization Of Deposited Copper Oxide Films On Copper Substrates, Millicent Castillo

Electronic Thesis and Dissertation Repository

The deposition of copper oxide films on copper substrates was investigated by the electrochemical, thermal, and hydrothermal oxidation of copper. The formed oxides were characterized using various surface analytical techniques to determine the film’s morphology, composition, and thickness. The results show that by growing oxides electrochemically, a duplex layer composing of CuO and Cu₂O film was formed on the copper surface, having characteristics of being porous and possessing needle-like structures. An oxide film composed of CuO and Cu₂O, which shows minimal porosity and possess mixtures of crystalline and non-crystalline structures, is formed on the copper surface …

Surface Modification Of Carbon-Based Electrodes For Electrochemical Conversion Processes: Oxygen Reduction Reaction And Bicarbonate Conversion, Udari Shyamika Kodithuwakku Arachchige

Theses and Dissertations--Chemistry

Oxygen reduction reaction (ORR) and conversion of bicarbonate into value-added chemicals are two significant electrochemical processes for energy storage and conversion. ORR is an important electrochemical reaction in fuel cells and metal-air batteries that provide power conversion and storage capacity, respectively, for portable electronics, and electric vehicles. However, the performance of catalysts (e.g., platinum-based) is critically limited by slow kinetics, inefficient four-electron pathway, and surface deactivation. This limited performance of platinum-based catalysts, the scarcity of platinum, and vulnerable supply chains for critical minerals require the development of alternative electrocatalysts now more than ever. Carbon-based materials possess several key properties that …

Copper-Catalyzed Dehydrogenative Decarboxylation Reactions Of Carboxylic Acids To Alkenes, Michael P. Stanton

Graduate Theses, Dissertations, and Problem Reports

Linear alpha olefins (LAOs) are important building blocks in the production of linear low-density polyethylene, a plastic used in products such as shrink wraps, plastic bags, tubing, plasticizers, among others. Commercial methods for generating LAOs utilize ethylene oligomerization, but this method is reliant on fossil fuels and leads to unselective product formation. Synthesis of LAOs from renewable resources, namely carboxylic acids, by decarbonylative dehydration strategies has been well studied, however, this method has inherent drawbacks rooted in the formation of internal olefin side-products through isomerization pathways. With the goal of avoiding internal isomerization, this thesis explores a dehydrogenative decarboxylation strategy …

Interactions Of Bioactive Trace Metals In Shipboard Southern Ocean Incubation Experiments, Shannon M. Burns, Randelle M. Bundy, William Abbott, Zuzanna Abdala, Alexa R. Sterling, P. Dreux Chappell, Bethany D. Jenkins, Kristen N. Buck

OES Faculty Publications

In the Southern Ocean, it is well‐known that iron (Fe) limits phytoplankton growth. Yet, other trace metals can also affect phytoplankton physiology. This study investigated feedbacks between phytoplankton growth and dissolved Fe, manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and cadmium (Cd) concentrations in Southern Ocean shipboard incubations. Three experiments were conducted in September–October 2016 near the West Antarctic Peninsula: Incubations 1 and 3 offshore in the Antarctic Circumpolar Current, and Incubation 2 inshore in Bransfield Strait. Additions of Fe and/or vitamin B₁₂ to inshore and offshore waters were employed and allowed assessment of metal (M) …

Synthesis Of Copper Nano/Microparticles Via Thermal Decomposition And Their Conversion To Copper Oxide Film, Çağdaş Allahverdi̇

Turkish Journal of Chemistry

Copper nano/microparticles were synthesized in octadecene at 290 °C by thermal decomposition method. Copper acetate monohydrate, stearic acid, and 1-octadecanol were used as copper precursor, capping and mild reducing agents, respectively, at the synthesis. Borosilicate glass substrates submerged into the reaction solution during the synthesis were coated by copper nano/ microparticles. Thermal decomposition and coating techniques were combined in this study. Copper nano/microparticles were thoroughly characterised via X-ray powder diffraction, X-ray photoelectron, Raman, and attenuated total reflectance-Fourier transform infrared spectroscopies, and scanning and transmission electron microscopies. The average minimum Feret?s diameter of these synthesized copper particles was measured as ~87 …

Enantioselective Synthesis Of Enantioisotopomers With Quantitative Chiral Analysis By Chiral Tag Rotational Spectroscopy, Mitchell D. Mills, Reilly E. Sonstrom, Zoua Pa Vang, Justin L. Neill, Haley N. Scolati, Channing T. West, Brooks H. Pate, Joseph R. Clark

Chemistry Faculty Research and Publications

Fundamental to the synthesis of enantioenriched chiral molecules is the ability to assign absolute configuration at each stereogenic center, and to determine the enantiomeric excess for each compound. While determination of enantiomeric excess and absolute configuration is often considered routine in many facets of asymmetric synthesis, the same determinations for enantioisotopomers remains a formidable challenge. Here, we report the first highly enantioselective metal-catalyzed synthesis of enantioisotopomers that are chiral by virtue of deuterium substitution along with the first general spectroscopic technique for assignment of the absolute configuration and quantitative determination of the enantiomeric excess of isotopically chiral molecules. Chiral tag …

Alkylthiocarbamate Metal Complexes With Antiproliferation Activity., Kritika Bajaj

Electronic Theses and Dissertations

Bis(thiosemicarbazones) (BTSCs) and their metal complexes have been extensively studied for various applications including catalysis for hydrogen evolution reactions, treatment of neurodegenerative diseases, hypoxia imaging, and a wide range of pharmacological purposes including antitumor, antiviral, antibacterial, and antifungal agents. The paramount property that makes BTSC metal complexes interesting for their use in these applications is the reduction potential of the coordinated metal, which can be selectively tuned by varying the substituents present on the ligand framework. Although the BTSCs have shown a great deal of success as potential cancer therapeutic agents, they lack selectivity towards cancer cells. For this matter, …

Characterization Of Bimetallic Silver-Copper Nanoinks With Hydroxyethyl-Cellulose Additives, Daniel Brunick

Undergraduate Honors Theses

Coinage metal nanoparticles remain an intriguing subject for research due to their industrial versatility. Primary applications of coinage metal nanoparticles include printed electronics, solar panels, and sensors. Inks formulated with the nanoparticles are conductive and thus useful for fabricating sensors. Silver-copper nanoalloy inks are viable for the fabrication of flexible sensing devices for the detection of volatile organic compounds. One of the challenges is the ability to synthesize composition-controllable alloy nanoparticles at room temperature through wet chemical methods and achieve controllable sintering at room temperature. This work addresses the challenges by investigating the room-temperature synthesis of silver-copper alloy nanoparticles and …

The Effects Copper Has On Casting Glass, K. Malika Haver

Honors Projects

The aim of this honors project was to discern the difference between how various types of copper reacted with glass. The two disciplines that were connected were chemistry and glassblowing. The basic components learned in chemistry were applied to glass with an end goal of a project installation that visualized the discoveries with copper. The glassblowing technique used was lost wax casting, and the two types of copper used were copper foil and fine copper metal powder. The copper was found to turn the glass into various blues with the intensity and darkness of the blues being dependent on the …

Synthetic Methods For Improved Scope And Efficiency Of Copper-Catalyzed Regioselective Alkene Boracarboxylation, Steven William Knowlden

Graduate Theses, Dissertations, and Problem Reports

The synthesis of carboxylic acids is important to the chemistry community, owing to the broad applicability of these compounds as fine chemicals and pharmaceuticals. Method development over the last decade has focused on the preparation of carboxylic acids through transition metal catalysis utilizing CO₂ as a C1 synthon. Copper-catalyzed heteroelement(bora and sila)-carboxylation protocols provide functional group rich carboxylic acid products, yet remain underdeveloped and thus underutilized. Consequently, catalytic reductive difunctionalization methodologies in which CO₂ and B(pin) (pin = pinacolate: 2,3-dimethyl-2,3-butanediolate) are installed across the double bond of a vinyl arene were recently developed. These boracarboxylation protocols provided novel, …

Analysis Of Copper(Ii) Using The Ascorbate/Oxygen System – A Valuable Undergraduate Resource, Sean Tobin, John Cassidy, Kevin Kurian, Tony Betts

Articles

In deionised water, ascorbic acid (AH−), through oxidation by oxygen in the presence of copper(II), was found to degrade with zero-order kinetics. The magnitude of the reaction rate varied directly with the copper(II) concentration. At a higher pH (7.4), the same reaction was found to be pseudo-first order. Once again, the magnitude of the rate increased linearly with copper(II) concentration at a micromolar level. Dissolved oxygen levels, in excess AH− and trace copper(II), displayed similar kinetics under both conditions. Monitoring of either AH− levels or dissolved oxygen concentration was found to be a useful novel undergraduate practical laboratory for trace …

Preconcentration Of Trace Amount Cu(Ii) By Solid-Phase Extraction Method Usingactivated Carbon-Based Ion-Imprinted Sorbent, Kübra Turan, Ruki̇ye Saygili Canlidi̇nç, Orhan Murat Kalfa

Turkish Journal of Chemistry

In this study, preconcentration conditions of trace amounts of copper ions were investigated with solid-phase extraction (SPE) method by synthesizing activated carbon-based ion-imprinted sorbent (Cu(II)-IAC) with a novel and selective approach. Flame atomic absorption spectrometry (FAAS) was used for the determination of metal ions concentrations. For the characterization of the sorbents, scanning electron microscopy, energy dispersive X-ray (SEM/EDX) analysis, and Fourier transform infrared spectroscopy (FTIR) were used. Optimum conditions for the SPE procedure, various parameters such as pH value, eluent type and concentration, sample volume, sample flow rate, adsorption capacity, and selectivity were studied. The adsorption isotherm was analyzed by …

Co2 Absorption Into Primary And Secondary Amine Aqueous Solutions With And Without Copper Ions In A Bubble Column, Hamed Yousefzadeh, Cansu Güler, Can Erkey, Erdal Uzunlar

Turkish Journal of Chemistry

Chemical absorption of CO2 into aqueous amine solutions using a nonstirred bubble column was experimentally investigated. The performance of CO2 absorption of four different primary and secondary amines including monoethanolamine (MEA), piperazine (PZ), 2-piperidineethanol (2PE), and homopiperazine (HPZ) were compared. The effects of initial concentration of amine, the inlet mole fraction of CO2, and solution temperature on the rate of CO2 absorption and CO2 loading (mol CO2/mol amine) were studied in the range of 0.02-1 M, 0.10-0.15, and 25-40 °C, respectively. The effect of the presence of copper ions in the amine solution on CO2 loading was also studied. By …

Effects Of Gamma-Radiation On The Evolution Of Copper Corrosion Dynamics In Deep Geological Repository Solution Environments, Lindsay J. Grandy

Electronic Thesis and Dissertation Repository

The Canadian plan for permanent disposal of used nuclear fuel involves a used fuel container (UFC), a carbon steel vessel with a copper coating to provide the corrosion protection. The corrosion conditions for the copper layer of the UFC are expected to involve small, stagnant water volumes, pH values between 6 and 9, and a continuous flux of γ-radiation emitted from the radionuclides trapped in the fuel matrix. While γ-radiation does not affect the copper metal directly, humid air and water will radiolytically decompose into redox-active and acidic species which will be produced at constant concentrations and can alter the …

Cu-Catalyzed Phenol O-Methylation With Methylboronic Acid, Mairead E. Bartlett, Yingchuan Zhu, Uma Bhagwat Gaffney, Joyce Lee, Miranda Wu, Betemariam Sharew, Angela K. Chavez, David J. Gorin

Chemistry: Faculty Publications

A Cu-catalyzed oxidative cross-coupling of phenols with methylboronic acid to form aryl methyl ethers has been developed, expanding the scope of Chan-Evans-Lam alkylation. Electron-deficient phenol derivatives with a broad array of functional groups are methylated in high yields. Increased reaction temperature and catalyst loading enables the methylation of substrates incorporating pyridine and dihydroquinolone motifs. Electron-rich phenol derivatives are poor substrates for the methylation; the characterization of C−H homodimerization products formed from these substrates illuminates a competing mechanistic pathway.

Copper Corrosion Dynamics Under Deep Geologic Repository Conditions, Masoumeh Naghizadeh

Electronic Thesis and Dissertation Repository

Canada’s plan for the permanent disposal of spent nuclear fuel involves a multiple-barrier system contained within a deep geologic repository (DGR). The key engineered barrier is the used fuel container (UFC), which is a copper-coated carbon steel vessel. The environments to which the copper coating will be exposed in the DGR are very different from those commonly encountered in copper corrosion studies. The copper (Cu) will be in contact with thin stagnant layers of water, and the corrosion system will be exposed to a continuous flux of γ-radiation. In the presence of γ-radiation, water and humid air decompose to redox-active …

Analysis And Differentiation Of Uniform And Localized Corrosion Of Cu, Roshan J. Daljeet

Electronic Thesis and Dissertation Repository

The current plan for disposal of used nuclear fuel in Canada involves sealing the waste in steel containers coated with 3 mm of copper and burying them in a deep geologic repository (DGR). The purpose of the copper coating is to provide corrosion resistance. To achieve long term containment, it is necessary that the copper layer corrodes slowly and predictably via active dissolution rather than passivating due to film formation. Film formation could allow pitting corrosion to occur in early phase repository conditions when groundwater ions such as Cl– , SO4 2– and HCO3 – play a dominant role in …

Galvanic Corrosion Of Carbon Steel Coupled To Copper In Used Nuclear Fuel Containers, Lindsay J. Braithwaite

Electronic Thesis and Dissertation Repository

Deep geological containment of used nuclear fuel will rely on multiple engineered and natural barriers, two of which are the copper-coated used fuel containers and the compacted bentonite clay buffer boxes in which the containers will rest. This work focused on possible galvanic interactions between the copper coating and the steel substrate of the container, which may occur at a hypothetical through-coating defect. In the presence of various amounts of chloride, bentonite, and oxygen, corrosion of the copper/carbon steel couple was studied using electrochemical tests complemented by surface characterization and 3D X-ray imaging. We investigated the effects of copper-to-steel area …

Green Dehydrogenation Of Dimethylamine Borane Catalyzed By Cheaply Copper(0) Nanocatalysts Without Any Stabilizer At Nearly Room Temperature, Ali̇ Özdemi̇r, Si̇bel Duman

Turkish Journal of Chemistry

In this work, the findings of the work on the green dehydrogenation behavior of molten dimethylamine borane (DMAB) catalyzed by the precatalyst copper(II) acetylacetonate (Cu(acac)2) in solvent-free medium (green) at near room temperature (nRT, 30.0+0.1°C) were reported. Herein, a complete study has been presented, which includes the following steps: (i) synthesis and catalytic activity of Cu(0) NCats in solvent-free medium, (ii) determination of activation energy for Cu(0) NCats catalyzed green dehydrogenation of DMAB, (iii) demonstration of catalytic lifetime of Cu(0) NCats, (iv) test of isolability and reusability of Cu(0) NCats, (v) poisoning experiments using carbon disulfide on a per-active-copper-atom basis, …

A Fluorescent Sensor-Based Tripodal-Bodipy For Cu (Ii) Ions: Bio-Imaging On Cells, Ahmed Nuri̇ Kurşunlu, Mustafa Özmen, Ersi̇n Güler

Turkish Journal of Chemistry

A general synthetic method was improved to synthesize a chemosensor based on a tripodal Bodipy (t-BODIPY) structure. The product and its intermediate products were successfully prepared and fully characterized. The metal ion sensing performance of the tripodal compound was evaluated by UV/Vis and fluorescence spectroscopies. According to the obtained data, t-BODIPY is a selective and sensitive fluorescence probe for detection of Cu2+ ions in the presence and in the absence of competing ions. This chemosensor presents relatively a low detection limit of 5.4 x10-7 M for Cu2+. Bio-imaging studies on living yeast cells suggest that t-BODIPY has some advantages over …

Vortex-Assisted Magnetic Solid Phase Extraction Of Pb And Cu In Some Herb Samples On Magnetic Multiwalled Carbon Nanotubes, Di̇lek Kamaş, Aslihan Karatepe, Mustafa Soylak

Turkish Journal of Chemistry

This study is the development of a new solid phase extraction method based on using magnetic multiwalled carbon nanotubes impregnated with 1-(2-pyridylazo)2-naphthol (PAN) for separation, preconcentration, and flame atomic absorption spectrometric determination of Pb(II) and Cu(II). Optimization of the method was done by investigating pH effect, amount of magnetic multiwalled carbon nanotubes impregnated with PAN, eluent type and volume, matrix effects, and volume of the sample. The optimum adsorbent amount was found to be 75 mg and the optimum pH value was found as 5.5. The detection limits were 16.6 μg L-1 for Pb(II) and 18.9 μg L-1 for Cu(II). …

Synthesis, Characterization, And Biological Evaluation Of New Copper Complexes Ofnaphthyl Pyrazole Ligands, Melek Hinis, Kuldip Singh, Demet Erdönmez, Ayfer Menteş

Turkish Journal of Chemistry

Two naphthalene pyrazole ligands were synthesized using KOH/DMSO and Cu catalyst and characterized with FT-IR, ESIMS, 1H, and 13C NMR spectroscopies. The crystal structures of 1-(2-methylnaphthalen-1-yl)-1H-pyrazole (MeNap-Pz) ligand have been determined with X-ray crystal structure analysis. Reaction of the ligands with Cu(NO3)2x3.5H2O gave two new complexes and characterized with magnetic susceptibility, molar conductance, FT-IR, LCMS-MS, ICP-OES, NMR, thermogravimetric analysis, and ESR spectra. The spectral data of the ligands are coordinated to the metal ion through the nitrogen atoms of the pyrazole ring. Consequently, it has been determined that [Cu(MeNap-Pz)2 (NO3)]NO3.2H2O complex showed square planar geometry and [Cu(NapMe-Pz)2(NO3)2].H2O complex showed octahedral …

The Electrochemical And Corrosion Study Of Copper For Nuclear Waste Containers Under Deep Geological Disposal Conditions, Mengnan Guo

Electronic Thesis and Dissertation Repository

The proposed method for the safe disposal of Swedish, Finnish, and Canadian high-level nuclear waste (HLNW) is to isolate it in iron or steel containers with an outer copper (Cu) shell or coating and bury it in a deep geological repository (DGR). Copper has been selected as the corrosion barrier due to its stability in the aqueous anoxic environments anticipated in DGR conditions. The container will initially be exposed to humid aerated conditions which will evolve to cool and anoxic as radiation fields in the fuel decay and heat production ceases. When the DGR is cool and anoxic, sulphide (SH …

The Statue Of Liberty Laboratory Activity: The Chemistry Of Copper, Jihyun Kim, Marcus D. Allen

Open Educational Resources

In this lab activity we observe chemical changes of copper in acidic conditions, salt water, and a mixture of lemon juice and vinegar and salt, and we discuss whether the Statue of Liberty would hold as much cultural icon today had the Lady Statue remain the original shiny brown color.

Fabrication, Characterization And Applications Of Chemically Modified Planar Metallic Electrodes From Copper Clad Sheets, Rana T. K. Alsaidi

Theses

In this work, we developed a fabricating method for planar electrodes by milling and cutting copper-clad sheets. The main objectives of this thesis are to produce customized planar electrodes with different geometries with relatively higher reusability compared to the screen-printed electrodes available by commercial vendors. The fabricated electrodes from copper-clad sheets were electroplated with different metals using commercial electroplating baths to produce different metallic planar electrodes. Also, the fabrication of planar electrodes with cavities to be filled with modified carbon paste was done. The electroplated planar electrodes were characterized by the cyclic voltammetry technique. In addition to that, they were …

The Influence Of Radiolytically Produced Nitric Acid On The Corrosion Resistance Of Copper-Coated Used Nuclear Fuel Containers, Joseph P. Turnbull

Electronic Thesis and Dissertation Repository

In Canada, the proposed disposal method for high level nuclear waste involves sealing the waste in steel containers with a 3 mm outer copper coating and burying it in a deep geologic repository. However, the thickness of the container is significantly reduced making a reassessment of the influence of γ-radiation, emitted by the waste form, on container corrosion a potential licensing requirement. Under humid aerated conditions, the formation of nitric acid is expected, potentially resulting in the formation of droplets or wetted layers on the container surface. Currently available literature on the corrosion of copper in nitric acid does not …