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Approche électrochimique de l'activation réductrice du dioxygène à l'aide d'un complexe de fer(II) non hémique / Electrochemical Approach of the Reductive Activation of O2 by a Non heme Fe(II) complexBohn, Antoine 07 December 2018 (has links)
Les cytochromes P450 sont des enzymes mononucléaires de fer qui catalysent l’oxydation de liaisons C-H en utilisant le dioxygène de l’air. L’activation de O2 nécessite sa réduction partielle par l'apport de deux protons et deux électrons. Ces derniers sont fournis par le réducteur naturel NADPH par l'intermédiaire d'une flavoprotéine qui permet de convertir l’adduit fer(II)-O2 en un intermédiaire de type fer(III)-peroxo dont les protonations successives permettent la rupture hétérolytique de la liaison O—O et l’obtention d’un intermédiaire de type fer-oxo responsable de l’oxydation du substrat.1 Ce projet s’inscrit dans le cadre de la chimie bio-inspirée, il a pour objectif de développer des catalyseurs de fer non-hémiques afin de réaliser l’oxydation de petites molécules organiques en utilisant le dioxygène de l’air. L’activation du dioxygène est assurée par le biais d’une électrode qui sert de source d’électrons mais également de sonde mécanistique. Pour comprendre le mécanisme de l’activation du dioxygène il est nécessaire (i) de générer les intermédiaires réactionnels oxydants (fer-oxo, fer-(hydro)peroxo) par le biais d’oxydants chimiques comme le PhIO et H2O2 puis (ii) de les caractériser par spectroscopie et électrochimie à basse température. Enfin (iii) l’étude expérimentale par voltampérométrie cyclique de la réaction du complexe de Fe(II) en présence de dioxygène couplée à des simulations de voltampérogrammes de cette même réaction (à l’aide de données thermodynamiques et cinétiques obtenues en (ii)) permettent ainsi de valider le mécanisme de l’activation réductrice du dioxygène de ce système. Ce travail a démontré que les complexes de FeII avec des ligands amines/pyridine peuvent activer le dioxygène à la surface d’une électrode en suivant un mécanisme proche de celui du cytochrome P450. A présent, la difficulté principale est de s’affranchir de la réduction prématurée des intermédiaires lorsqu’ils sont générés à l’électrode. En se basant sur ces résultats, l’essentiel du travail est à présent ciblé sur la compréhension des différents paramètres (première sphère de coordination, conditions expérimentales, …) qui peuvent modifier la stabilité des intermédiaires et donc l’efficacité de la catalyse. / Cytochrome P450 is a mononuclear iron enzyme, which catalyzes the oxidation of robust C-H bonds using O2. Activation of O2 is achieved at the Fe(II) center and requires an electron transfer to convert the iron(II)-dioxygen adduct into an iron(III)peroxo intermediate. After protonation, this latter may directly oxidize substrates or evolves to yield a powerful high valent iron-oxo moiety. In such natural systems, the necessary electrons are provided by a co-substrate NAD(P)H and are conveyed through a reductase.1The aim of this project is to develop non-heme iron(II) complexes as catalysts for the oxidation of small organic molecules by O2. Our objective is to use an electrode to deliver the electrons while providing mechanistic information at the same time thanks to a combined experimental/simulation approach using cyclic voltammetry. This work has shown that simple Fe(II) complexes bearing amine/pyridine ligands can activate O2 at an electrode surface following a mechanism that is reminiscent of the one of P450. However, the main scientific lock is to avoid the fast reduction of the reaction intermediates when they are generated at the electrode. We are currently studying how alterations of the first coordination sphere of the metal center and experimental conditions modulate the formation and the stability of these intermediates and thus, the efficiency of the catalysts.
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Novel Microelectrodes and New Material for Real-Time Electrochemical Detection of NeurotransmittersLi, Yuxin January 2021 (has links)
No description available.
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CYCLIC VOLTAMMETRIC DETERMINATION OF 17-α-ETHINYL ESTRADIOL ON DISPOSABLE SCREEN-PRINTED CARBON ELECTRODESQian, Zepeng 12 August 2019 (has links)
No description available.
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Electrosynthesis of Lithium Borohydride from Trimethyl Borate and Hydrogen GasOmweri, James Mokaya January 2019 (has links)
No description available.
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Mullite Membrane Reference Electrode Evaluation and Application for Ni-Cr Corrosion Behavior in High Temperature Chloride SaltsMeilus, Emily Vanda 28 June 2023 (has links)
Molten salt reactors (MSRs) using chloride-based salt-matrixes as coolants or fuels are a promising option for advanced nuclear reactors, but the extreme temperatures and corrosivity of molten salts pose a challenge for implementation. Molten MgCl2-NaCl-KCl is a viable candidate for MSRs that is considered in this work.
Thermochemical properties are derived from electrochemical tests that aid in characterizing the properties of salts. To study these properties, some work has proposed using a three-electrode system with a reference electrode housed in a ceramic membrane. This research aims to develop a stable high-temperature reference electrode using a ceramic membrane that is then applied to develop an on-line monitoring system of Ni-Cr alloy corrosion in chloride salt.
A mullite tube used as the membrane of a Ni(II)/Ni reference electrode in molten MgCl2-NaCl-KCl is studied. The performance of two different membrane thicknesses (1.325mm and 0.255mm) was studied in temperature ranges from 635oC to 835oC and data collected on the calculated formal potential of the Ni(II)/Ni system. Tests indicated that the results were stable and repeatable, and the formal potential for both systems differed from the previous experimental data by 0.12V at most, indicating that the system can be applied as an effective reference electrode. Using the reference electrode, on-line monitoring the corrosion of Ni-15wt.%Cr, Ni-20wt.%Cr, and Ni-30wt.%Cr was studied for 120 hours in MgCl2-NaCl-KCl. The on-line measurements showed the concentration changes of dissolved Cr and Ni by corrosion in the bulk molten salt.
This work confirms that Ni(II)/Ni reference electrodes with a mullite tube membrane are stable and effective in molten chloride salt systems, particularly MgCl2-NaCl-KCl. The mullite membrane prepared by the manufacturer may be used directly for electrochemical applications without polishing, simplifying the reference electrode manufacturing process, and making it easier to replicate. The use of a Ni(II)/Ni reference electrode provides an avenue to study a different range of salt systems than previous reference electrodes allowed, particularly alloys in chloride salts at high temperatures. This work also confirms that the mullite tube may be used to perform on-line analysis of alloy corrosion in high temperature molten chloride salts. The study of Ni-Cr alloys in chloride salts better prepares the nuclear industry to select coolant salts and alloy containers with the best set of thermochemical and corrosion resistant characteristics for MSRs. / Master of Science / The United States receives approximately 18% of its energy from nuclear technology. Many of the reactors supplying this energy are at the end of their lifecycle and the decommissioning of some of these plants has already begun. In order to replace this older generation of nuclear reactors, a safer and cheaper option has been suggested: Molten Salt Reactors. Molten salt reactors (MSRs) using high temperature salts as a fuel or coolant are a promising option, but the extreme conditions of molten salts pose a challenge for construction and use of MSRs. Molten MgCl2-NaCl-KCl is a salt being considered for MSR application, and is considered in this work.
Properties of the salts considered for MSRs are being studied diligently before implementation of these reactors. Electrochemical tests are used to study and monitor these properties. These electrochemical tests use a three-electrode system with a reference electrode housed in a membrane. In this work, a mullite tube is used as a ceramic membrane for a reference electrode in molten MgCl2-NaCl-KCl. The performance of two different membrane thicknesses (1.325mm and 0.255mm) was studied in temperature ranges from 635oC to 835oC. Results indicate that the system is an effective reference electrode. Using this innovative reference electrode, a method of monitoring on-line corrosion of Ni-15wt.%Cr, Ni-20wt.%Cr, and Ni-30wt.%Cr alloys was studied for 120-hour time periods during exposure to MgCl2-NaCl-KCl.
This work confirms that reference electrodes with a mullite membrane may be used for electrochemical applications when studying molten chloride salts. The use of a Ni(II)/Ni reference electrode with a mullite membrane provides an avenue to study a different range of salt systems than previous reference electrodes and ceramics allowed, particularly chloride salts. Additionally, this mullite membrane Ni(II)/Ni reference electrode system may be used for monitoring on-line corrosion of Ni-Cr alloys in chloride salt systems.
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Using Biochar Electrodes for Brackish Water DesalinationStephanie, Hellen 11 August 2017 (has links)
Capacitive deionization based on electrosorption has become a viable process for brackish water desalination. In this study, activated biochar was employed as low-cost and alternative carbon-based electrodes substituting activated carbon with comparable adsorption capacity. Effects of different activation temperatures of the biochar were studied by physical characterization (i.e. SEM, TEM, elemental analysis, and Raman spectroscopy) and electrochemical characterization (i.e. cyclic voltammetry and galvanostatic charge/discharge measurement) based on the electrical double layer theory. The highest specific capacitance obtained (118.50 F g-1) was from activated biochar electrode treated at 800°C. The removal capacity was investigated by AAS and conductivity measurements. Several limitations associated with them were identified to improve the measurements. The removal capacity of biochar electrode is ~ 2 mg g-1 with significant results for both one-sided and two-sided t-test. In summary, activated biochar can be used as a cheap-alternative electrode material for desalination based on capacitive deionization.
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In Situ Induction Heating of Electrodes and ApplicationsRahman, Mohammad Azizur 10 August 2018 (has links)
This thesis describes the fabrication of an induction heating apparatus and its use to directly heat small platinum and gold electrodes in electrolyte solution. The heating characteristics of the electrodes were studied via the entropic shift of redox potential with temperature and change in Faradaic current. Temperature pulse voltammetry (TPV) and cyclic voltammetry were used for temperature calibration under various heating conditions. The maximum temperature reached at a 0.25 mm diam platinum electrode surface in solution was 84 degrees C. At heated electrodes an increase in current was found to be due to convection and diffusion. TPV was performed with inductively heated gold (0.5 mm diam) and platinum electrodes, which gave complete current-potential-temperature information. Induction heated Pt electrodes were employed to investigate the kinetics and mass transfer process of oxygen reduction reaction (ORR) in acidic and alkaline media.
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Novel aromatic dendritic-co-poly(3-hexylthiophene) composites for photovoltaic cell applicationRamoroka, Morongwa Emmanuel January 2021 (has links)
Philosophiae Doctor - PhD / Fossil fuels are part of fuels that are formed from natural processes and they are called non-renewable sources of energy. These include natural gas, coal and oil. They have been used for decades to produce energy globally. However, there are some factors that related with the use of fossil fuels which results in an increase in the requirement of large amounts of energy. In addition, the use of fossil fuels as energy source has a negative impact on the environment and they cannot be reused. It is expected that at some point they will run out. Thus, a need for a renewable, clean and plentiful source of energy is urgent. Solar energy is one of the energy sources that may overcome fossil fuel drawbacks.
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Electrochemical Study of Ceramic (BaTiO3 based)/ Polymer Composite electrodes for Supercapacitor applicationsMegharaj, Prabhu January 2012 (has links)
No description available.
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The <em>In Vitro</em> Cellular Uptake and Physiochemical Properties of Tocotrienols.Zuo, Tianming 11 August 2003 (has links) (PDF)
This research, focusing mainly on tocotrienols, includes two parts. The first part concerns the uptake and growth inhibition of tocotrienols in PC-3 cells. The second part is a study of the physiochemical properties of Vitamin E.
In the cellular study our results suggested that position 5 of chroman head and side-chain are very important in determining the uptake of tocotrienols and growth inhibition of PC-3 cells. The uptake and growth inhibition are not necessarily related to the antioxidant properties of tocotrienols.
Of the physiochemical studies, the results suggested that the antioxidant properties of vitamin E are due to the phenolic O-H group. In ethanol solution, each tocotrienol has a higher oxidation potential than its corresponding tocopherol. The oxidation potentials of vitamin E are in the order ofα-form < γform < δ-form. The theoretical calculations show that the side chains of tocotrienols are less ordered than those of tocopherols.
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