No description available.

Bioelectrical reactors (BER) have potential to be utilized in a wide variety of industrial applications. This work explores the kinetics involved with reduction of electron mediators (anthraquinone disulfonate and methyl viologen) in bioelectrical reactors. It also discusses on possible application of BER technology to produce ethanol from CO2 and electricity. It is established that Clostridium ragdahlei is capable of sustaining life and product formation with CO2 as the only carbon source. This means it is theoretically possible to utilize CO2 as he source of carbon and electricity as the source of reducing equivalents for bacterial growth and product formation. A three-step mechanism composed of adsorption, surface reaction, and desorption is developed to model the reaction of dissolved electron mediators at the electrode surface of the BER. The proposed mechanism is then utilized to build a mathematical model to describe the kinetics of the BER system. This model is used to gain greater understanding of experimental kinetic data of electron mediator reduction at different voltage potentials. It is determined that voltage potential has very small effect on the initial rate of reaction in the reactor. However, thermodynamic equilibrium is affected by the change in voltage, resulting in longer sustained initial rate at higher overpotential. Mathematically, this change affects the modeled rate constants by increasing the reverse rate constant of the rate limiting step, and also by affecting the ratio of the thermodynamic equilibrium constants of adsorption. This results in a larger amount of oxidized electron mediator adsorbed to the electrode surface at higher overpotentials, leading to the initial rate persisting further into experimental runs. One key portion of these findings was the determination that the surface reaction step is the rate limiting step of the kinetic mechanism. This has great ramifications on future research and on future considerations for reactor design. This insight allows for better understanding of the key and fundamental workings of BER technology.

Scanning electrochemical microscopy (SECM) was used for the study and characterization of catalytic and electrocatalytic processes occurring at electrodes. The Surface Interrogation mode (SI-SECM) was introduced for the detection and quantification of adsorbed intermediates and products of catalyzed chemical and electrochemical reactions at noble metals (Pt, Au). In SI-SECM two micro electrodes (i.e. an SECM tip and a substrate of the desired material) are aligned concentrically at a micrometric distance where SECM feedback effects operate. A contrast mechanism based on feedback effects allows for the detection of reactive adsorbed intermediates at the substrate: the SECM tip generates a reactive homogeneous species that “micro-titrates” the substrate adsorbates to yield an electrochemical signal that contains information about the amount of intermediate and about its kinetics of reaction with the redox mediator. The technique was used for the study of the reactivity of three model small adsorbates: 1) the reactivity of adsorbed oxygen on Au and Pt with a reducing mediator was explored and suggested the detection of “incipient oxides” at these surfaces; kinetic parameters of the reactivity of Pt oxides with mediators were obtained, fit to theory and used to explain observations about the electrocatalytic behavior of Pt under anodizing conditions; 2) the reactivity of oxidizing mediators with adsorbed hydrogen on Pt was studied and showed the cation of N,N,N,N-tetramethyl-p-phenylenediamine (TMPD) to be a successful interrogation agent, the detection of hydrogen generated by the decomposition of formic acid on Pt at open circuit was investigated; 3) electrogenerated bromine was used to catalytically interrogate carbon monoxide at Pt, this reaction was previously unreported. The mentioned applications of SECM were validated through the use of digital simulations of diffusion in the complex SECM geometry through flexible commercial finite element method software. / text

No description available.

Miniature electrochemical sensors can be produced by thick-film technology. The optimal properties of thick-film electrode system, the production technology optimization of thick-film sensors and the adjustment of optimal technological properties are main problems of sensor design. An area of working electrode and an electrode topology design is the important parts in design of electrode system optimization. The rules for optimization of electrode systems in classical electrochemistry exist. The design of standard thick-film electrode construction is limited (2-D construction, substrate dimensions, resolution, paste parameters …). Therefore rules for classical electrode systems cannot be used fully in this case and larger electrode area can be making by 3D structure only. One of resolutions is unconventional method. The increase of working electrode surface by unconventional method – ball and wire bonding is discussed in this work.

This dissertation has focused on i) optimizing charge transfer rates at indium-tinoxide (ITO) electrodes, and ii) characterization of the supramolecular structure and properties of ultra thin surface modifier films on modified electrodes for various device applications. Commercial ITO surfaces were modified using conducting polymer thin film architectures with and without various chemical activation procedures. Ferrocene derivatives were used as redox probes, which showed dramatic changes in electron transfer rate as the SA-PANI/PAA layers were added to the ITO surface. Highest rates of electron transfer were observed for DMFc, whose oxidation potential coincides with the potential region where these SA-PANI/PAA films reach their optimal electroactivity. Apparent heterogeneous electron transfer rate constants, kS, measured voltammetrically, were ca.10 x higher for SA-PANI/PAA films on ITO, versus clean ITO substrates. These films also showed linear potentiometric responses with retention of the ITO transparency with the capability to create smoothest films using an aqueous deposition protocol, which proved important in other applications. ITO electrodes were also modified via chemisorption of carboxy functionalized EDOTCA and electropolymerization of PEDOTCA/PEDOT copolymers, when properly optimized for thickness and structure, enhance voltammetrically determined electron transfer rates (kS) to solution probe molecules, such as dimethylferrocene (DMFc). Values of kS ≥ 0.4 cm•sec⁻¹, were determined, approaching rates seen on clean gold surfaces. ITO activation combined with formation of these co-polymer films has the effect of enhancing the electroactive fraction of electrode surface, versus a non-activated, unmodified ITO electrode, which acts as a “blocked” electrode. The electroactivity and spectroelectrochemistry of these films helped to resolve the electron transfer rate mechanism and enabled the construction of models in combination with AFM, XPS, UPS and RAIRS studies. The surface topography, structure, composition, work function and contact angle, also revealed other desirable properties for molecular electronic devices. The carboxylic functionality of the EDOTCA molecule adds more desirable properties compared to normal PEDOT films, such as favoring the deposition of smooth films, increasing the optical contrast, participating in hydrogen-bonding, chemisorption to oxide surface, self-doping and providing a linker for incorporation of different functional groups, new molecules, or nanoparticles. Periodic sub-micron electrode arrays can be created using micro-contact printing and electropolymerization. The sinusoidal modulation of the refractive index of such confined conducting polymer nanostructures or nanoparticle stripes allows efficient visible light diffraction. The modulation of the diffraction efficiency at PANI and PEDOT gratings in the presence of an analytical stimulus such as pH or potential demonstrate the sensing capability at these surfaces. The template stripped gold surfaces that are being developed in our lab demonstrate several advantages over commercially available evaporated gold films especially for nanoscale surface modification.

The aim of this thesis is the study of electrochemical oxidation of para-substituted phenol derivates using cyclic voltammetry (CV) and ,,direct current" voltammetry (DCV) on boron-doped diamond electrode (BDD) and comparison with some analogous meta-substituted compounds. Among the studied substances were p-cresol, 4-methoxyphenol, 4-hydroxybenzoic acid, 3-(4-hydroxyphenyl)propionic acid, 4-nitrophenol, 4-chlorophenol and 3-(trifluoromethyl)phenol. The oxidation of the analytes was performed in an acidic (pH 2,0) and basic (pH 11,0) Britton-Robinson buffer on mechanically polished, oxidated and hydrogenated surfaces. Another subject of the thesis is to analyze the influence of different substituents, characterized by the Hammett constant, on the oxidation potential of selected phenols. They are oxidized at more positive redox potentials in acidic media, than in basic media, where they are dissociated. The oxidation on the polished and hydrogenated surfaces were similar, whereas were shifted to higher values on the oxidated surface. Further, the signal intensity decreased on the oxidated one, and the oxidation of phenols was not recognizable in basic media. The passivation of the electrode was less significant in pH 2,0 buffer. The best result of Hammett correlation was achieved on a polished and...

The Master’s Thesis deals with supercapacitators based on principle of eletrical double layer. At the outset there is an explanation of supercapacitor working principal. We discussed advantages and disavantages supercapacitators compared with other related elements in electrotechnics. Materials based on carbon and their structure for production supercapacitators are described too. In next part of Thesis we mention different methods and techniques for the measurement and the evaluation of supercapacitators‘s capacities. Optimal materials for production supercapacitators are presented in conclusion.

Dans ce travail, nous proposons une approche essentiellement expérimentale. Dans une première partie, nous exposons les résultats obtenus par imagerie rapide et mesures électriques corrélées dans le temps, concernant l’étude de la transition entre des électrodes de cuivre dans l’air et l’argon, et entre des électrodes de tungstène dans l’argon pour des pressions comprises entre 100 mbar et 1 bar. Dans aucun cas une transition à l’arc n’est observée sans constriction quasi-totale de la colonne positive. Dans le cas d’électrodes en tungstène dans l’argon, la vitesse d’extension de la zone filamentaire depuis l’anode vers la cathode a été vue dépendante de la pression et de l’intensité. La durée d’une transition spontanée a été linéairement corrélée à la distance inter-électrode, suggérant un mécanisme propagatif à vitesse constante dans la colonne. Plus la pression est élevée, plus la durée totale des transitions est longue ; par ailleurs, à pression constante, cette durée de transition spontanée décroît à intensité croissante, pour tendre vers une durée limite, correspondant à la durée constante de changement de structure de la zone cathodique. Dans une seconde partie, nous nous intéressons à l’échauffement de surfaces d’anodes et de cathodes en cuivre dans l’air et dans l’argon soumises à des arcs électrique pour plusieurs gammes de courant (de 30 à 120 A). Deux méthodes de mesures sont utilisées. Enfin, nous utilisons les mesures de températures de surface pour proposer deux modèles simples de bilan de puissance à la surface des électrodes (flux de chaleur). L’un considère uniquement le chauffage dû au spot d’arc et l’autre le chauffage supplémentaire de la colonne d’arc. / In this work, an approach which is essentially experimental is proposed. In the first part, results are presented which were obtained by synchronized fast camera imaging and electrical measurements. These concern the study of the transition between copper electrodes in air and in argon, and between tungsten electrodes in argon for gas pressure in the range 100 mbar – 1 bar. In no case was the transition to arc been observed without the quasi-total constriction of the positive column. Considering tungsten electrodes in argon, the propagation speed of the filamentary part of the positive column from the anode to the cathode was found to be dependent on the gas pressure and the discharge current intensity. During spontaneous transition, the transition duration has been linearly correlated to the electrode gap, suggesting a propagative mechanism with a constant speed. The higher the pressure, the longer is the total transition duration. For a constant pressure and discharge current, the duration of spontaneous transition decreases with decreasing gap distance toward a limiting value, which corresponds to the constant duration of the structural change of the cathode root from diffuse to spot. In the second part, heating of copper anodes and copper cathodes submitted to electric arcs in air and in argon and for various current intensity values (from 30A to 120 A) is considered. Two measurement methods are used. Finally, the surface temperature measurements are used to purpose two models of the electrode surface power balance (heat flux). One model only considers the heating due to the arc spot and the second one considers a supplementary heating from the arc column.

<p>Predmet istraživanja ove disertacije predstavlja unapređenje, modelovanje i optimizacija procesa elektroerozivne obrade (EDM) savremenih inženjerskih materijala. Prvo su predstavljene dve inovativne metode: EDM u dielektrikumu sa pome&scaron;anim prahom i EDM sa pomoćnom elektrodom, a zatim i njihova kombinacija. Za generisanje matematičkih modela primenjene su metodologija odzivne povr&scaron;ine i alati ve&scaron;tačke inteligencije. U nastavku su postavljeni optimizacioni procesi određivanja ulaznih parametara sa jednom i vi&scaron;e funkcija cilja koji su re&scaron;eni primenom klasičnih metoda optimizacije. U zavr&scaron;nom osvrtu sprovedena je verifikacija dobijenih modela i optimalnih ulaznih parametara elektroerozivne obrade.</p> / <p>The subject of the research of this dissertation is the improvement, modeling and optimization of the electrical discharge machining (EDM) of advanced engineering materials. First, two innovation methods are presented: EDM in powder mixed dielectric fluid and EDM with assisted electrode and that their combination. The method of response surface and artificial intelligence tools were applied to generate mathematical models. The optimization problems of determining the input parameters with single and multiple target functions are solved by the application of classical optimization methods. Finally, verification of the obtained models and optimal input parameters of electrical discharge machining was carried out.</p>