Characterization of Fe implanted yttria-stabilized zirconia by cyclic voltammetry

The technique of cyclic voltammetry has been applied to study reduction and oxidation phenomena which are observed at low oxygen partial pressures during steady state current-overpotential measurements of the Au, O2(g)/Fe implanted yttria-stabilized zirconia interface. The redox potential (EO) of the observed redox couple is in close agreement with the thermodynamic potential of coexistent Fe2O3 and Fe3O4 phases. Hence in the forward sweep of the cyclic voltammogram, defined for negatively swept potential, part of the Fe3+ is reduced to Fe2+. The peak currents in the voltammogram result from a redox reaction which is rate limited by the diffusion of electrons or electron holes in the Fe implanted YSZ surface to the implanted Fe ions rather than by the diffusion of the Fe ions themselves

Co-reduction of aluminium and lanthanide ions in molten fluorides : application to cerium and samarium extraction from nuclear waste

This work concerns the method of co-reduction process with aluminium ions in LiF–CaF2 medium (79–21 mol.%) on tungsten electrode for cerium and samarium extraction. Electrochemical techniques such as cyclic and square wave voltammetries, and potentiostatic electrolyses were used to study the co-reduction of CeF3 and SmF3 with AlF3. For each of these elements, specific peaks of Al–Ce and Al–Sm alloys formationwere observed by voltammetry aswell as peaks of pure cerium and aluminium, and pure samarium and aluminium respectively. The difference of potential measured between the solvent reduction and the alloy formation suggests expecting an extraction efficiency of 99.99% of each lanthanide by the process. Different intermetallic compounds were obtained for different potentiostatic electrolysis and were characterised by Scanning Electron Microscopy with EDS probe. The validity of the process was verified by carrying out cerium and samarium extractions in the form of Al–Ln alloy; the extraction efficiency was 99.5% for Ce(III) and 99.4% for Sm(III)

Oxidation of the borohydride Ion at silver nanoparticles on a glassy carbon electrode (GCE) using pulsed potential techniques

Direct oxidation borohydride fuel cells are very attractive energy conversion devices. Silver has been reported as one of the few materials which can catalyze an 8-electron oxidation. Potential step amperometric pulse techniques to synthesize nanostructured silver material on flat glassy carbon electrodes is reported and significant differences with bulk silver deposit have been observed. The oxidation of borohydride ion on the silver particles occurs at -0.025 V vs. SCE and the potential decreases towards negative values at longer cycle times. The oxidation current also decreases with the number of cycles, suggesting that the silver active sites become partially blocked by oxidation products of borohydride. The electroactive area per unit electrode area of silver was relatively low for particles deposited using potential step amperometric techniques on glassy carbon (0.002 cm2 per cm-2) compared with the area found at a polycrystalline silver electrode (0.103 cm2 per cm-2

Active Carboxylic Acid-Terminated Alkanethiol Self-Assembled Monolayers on Gold Bead Electrodes for Immobilization of Cytochromes c

It is extremely difficult to immobilize cytochrome c (cyt c) on carboxylic acid-terminated alkanethiol self-assembled monolayers (HOOC-SAM) on gold bead electrodes prepared in a hydrogen flame. We found that simple pretreatment of a HOOC-SAM/gold bead electrode by potential cycling in buffer solution in the range ±300 mV prior to immobilization of the protein facilitated stable cyt c binding to HOOC-SAMs. The stability of cyt c on the HOOC-SAMs is independent of the topology of the gold surface

On the use of electrochemical techniques to monitor free oxide content in molten fluoride media

The electrochemical behaviour of oxide ions has been studied in fluoride melts(LiF/NaF eutectic) by cyclic voltammetry, square wave voltammetry and chronopotentiometry. The purpose is to determine whether these techniques can be used for titration of free oxide ions (O2-) in molten fluorides released by lithium oxide additions. Cyclic voltammetry is shown to be unsuitable for this purpose due to oxygen bubbling disturbing the oxidation peak, while square wave voltammetry is far more appropriate because the observed signal is a well defined oxidation peak with a height proportional to the oxide content. Thus, the present work is focused on a strategy of oxide ions titration by square wave voltammetry. In addition, this work allows assessing that the electrochemical reduction of oxide ions proceeds by diffusion of these species, and the O2- diffusion coefficient is estimated by chronopotentiometry

Exploration of the global antioxidant capacity of the stratum corneum by cyclic voltammetry

Cyclic voltammetry is proposed as a new method for evaluating the antioxidant capacity of skin based on the reducing properties of low molecular weight antioxidants (LMWA). Experiments were performed simply by recording the anodic current at 0.9 V/SCE of a platinum microelectrode placed directly on the epidermis surface without any gel or water. This method ensured a direct, rapid (less than 1 min), reliable (accuracy 12%) and non-invasive measurement of the global antioxidant capacity of the stratum corneum with a high spatiotemporal resolution. At the same time, the pH of the skin surface was determined by recording the cathodic current at 0 V/SCE. Based on an exploratory study involving nine volunteer subjects, the evolution of the amperometric response of the microelectrode with time revealed a periodic modification of the redox properties

Elaboration of integrated microelectrodes for the detection of antioxidant species

(Pt–Pt–Ag/AgCl) and (Au–Pt–Ag/AgCl) electrochemical microcells (ElecCell) were developed for the detection of redox species by cyclic voltammetry. A special emphasis was placed on the SU-8 waferlevel passivation process in order to optimize the electrochemical properties of the different “thin film” metallic layers, i.e. gold or platinum for the working electrode, platinum for the counter electrode and silver/silver chloride for the reference electrode. (Au–Pt–Ag/AgCl) microcells were applied for the detection of antioxidant species such as ascorbic and uric acids in phosphate buffer solution, evidencing high sensitivity but low selectivity. Works were extended to skin analysis, demonstrating that a good electrical contact with the skin hydrolipidic film allowed the effective evaluation of the skin global antioxidant capacity

Electrochemical behaviour of thorium(IV) in molten LiF–CaF2 medium on inert and reactive electrodes

The electrochemicalbehaviour of the Th(IV)/Th system was examined in moltenLiF–CaF2medium on inert (molybdenum), reactive (nickel) and liquid (bismuth) electrodes in the 810–920 °C temperature range by several electrochemical techniques. Experimental results showed that (i) thorium fluoride was reduced in a single step exchanging 4 electrons and limited by thorium ions diffusion in the solution, (ii) the oxide ions induce the precipitation of Th(IV) in the form of thorium oxide (ThO2), in a process involving as intermediate compound a soluble oxifluoride (ThOF2), (iii) the reduction of thorium ions on reactive (Ni and liquid Bi) electrodes yields compounds Ni–Th and Bi–Th with a potential shift of around 0.7 V (for Ni and Bi) more anodic than the reduction of Th(IV) on inert substrate

Electrostatic Binding of Metal Complexes to Electrode Surfaces Coated with Highly Charged Polymeric Films

Previous reports in which metal complexes have been attached to electrode surfaces coated with polymeric molecules have depended upon the formation of covalent or coordination bonds in the attachment procedure (1-4). Such schemes can be quite successful but depending, as they do, on rather specific surface chemistry, they are not applicable to as wide a variety of metal complexes as might be desirable. We have observed that coating graphite electrodes with polymers bearing charged ionic groups produces surfaces which strongly bind multiply-charged metal complexes bearing charges opposite to that on the attached ionic polymer. By exploiting this observation it is entirely possible that virtually any desired metal ion can be attached in large quantities to electrode surfaces by coordinating the metal ion with ligands that produce a multiply-charged complex ion

Electro-Oxidation of p-Silicon in Fluoride-Containing Electrolyte: A Physical Model for the Regime of Negative Differential Resistance

When Si is anodically oxidized in a fluoride containing electrolyte, an oxide layer is grown. Simultaneously, the layer is etched by the fluoride containing electrolyte. The resulting stationary state exhibits a negative slope of the current-voltage characteristics in a certain range of applied voltage. We propose a physical model that reproduces this negative slope. In particular, our model assumes that the oxide layer consists of both partially and fully oxidized Si and that the etch rate depends on the effective degree of oxidation. Finally, we show that our simulations are in good agreement with measurements of the current-voltage characteristics, the oxide layer thickness, the dissolution valence, and the impedance spectra of the electrochemical system.Comment: 19 pages, 13 figures, accepted for publication in EPJ S