Study of mass transfer in a vertically moving particle bed electrode

A study was made of the influence of process parameters on the mass-transfer coefficient in a flow-through cell with a cascade of rotating drums partially filled with conductive particles (called the vertically moving particle bed). Copper deposition from an acidic sodium sulphate solution was used as the model reaction. To evaluate the experimental data a macrohomogeneous mathematical model of potential and current density distribution inside the cell was developed. The electrolyte flow distribution between the empty space above the particle bed and through the bed was evaluated. On the basis of these results the following correlation is proposed:

Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

Preparation of NaBiO3 and the electrochemical characteristic of manganese dioxide doped with NaBiO3

NaBiO₃ crystal of high purity has been synthesized through chemical oxidization. The morphology and thermal stability of NaBiO₃ were examined with scanning electron microscope (SEM) and thermogravimetry-differential scanning calorimetry (TG-DSC). The electrochemical properties of MnO₂ electrodes with and without doping NaBiO₃ were studied through galvanostatic charge/discharge and cyclic voltammetry. The results indicate that the MnO₂ electrode doped with NaBiO₃ possesses remarkably higher discharge voltage and capacity and better reversibility than the pure MnO₂ electrode and Bi₂O₃ doping MnO₂ electrode.     

Cinétique de dégagement des matières volatiles lors de la pyrolyse d'électrodes de carbone industrielles

In aluminium plants, the anode baking process is associated with an important release of volatile combustible matter. It is the purpose of this study to investigate the kinetics of the evolution of these volatiles. A large thermogravimetry set-up has been designed in such a way that it could simulate real plant conditions. Samples of two distinct masses have been subjected to pyrolysis at different heating regimes. The loss of weight together with the concentrations of the released gases were recorded on a continuous basis during the temperature rise. Kinetic results were found for methane, hydrogen and tar. No variation of the order of reaction with the heating rate was observed, whereas the activation energy and the pre-exponential factor increased. Furthermore, for the range of sample dimensions studied, it was found that the mass of the solid had no significant influence on the kinetic parameters.     

A novel high-performance counter electrode for dye-sensitized solar cells

A novel Pt counter electrode for dye-sensitized solar cells (DSC) was prepared by thermal decomposition of H₂PtCl₆ on NiP-plated glass substrate. The charge-transfer kinetic properties of the platinized NiP-plated glass electrode (Pt/NiP electrode) for triiodide reduction were studied by electrochemical impedance spectroscopy. Pt/NiP electrode has the advantage over the platinized FTO conducting glass electrode (Pt/FTO electrode) in increasing the light reflectance and reducing the sheet resistance leading to improve the light harvest efficiency and the fill factor of the dye-sensitized solar cells effectively. The photon-to-current efficiency and the overall conversion efficiency of DSC using Pt/NiP counter electrode is increased by 20% and 33%, respectively, compared to that of using Pt/FTO counter electrode. Examination of the anodic dissolution and the long-term test on the variation of charge-transfer resistance indicates the good stability of the Pt/NiP electrode in the electrolyte containing iodide/triiodide.     

氯霉素在聚茜素红薄膜修饰电极上的伏安行为及其测定

研究了聚茜素红薄膜修饰电极(PARE)对氯霉素(Chloramphenicol,CAP)的电催化作用,并应用于对微量CAP的定量检测。实验结果表明:在0.010mol/LHCl+1.0×10-4mol/LCu2++0.10mol/LNaCl测定体系中,CAP的浓度在1.0×10-9mol/L～1.0×10-8mol/L范围内与它的氧化峰电流呈良好的线性关系,线性方程和线性相关系数分别为:ip(μA)=-0.188×10-8CCAP(mol/L)-7.62,γ=0.9997,检出限可达5.0×10-10mol/L。CAP的标准回收率为95.9%~102.9%,八次平行样品测定结果的相对标准偏差3.2%。     

电活性分子L-B膜修饰CdSe薄膜电极的光电化学研究

用电活性分子——硬脂酸二茂铁酯L-B膜修饰了薄膜CdSe电极,在单色光650nm光照下用循环伏安法研究修饰的薄膜电极的光电化学性能。研究结果指出经多层L-B膜修饰后,薄膜CdSe电极的,I-V性能和光稳定性都有明显改善。用界面能级关系讨论了硬脂酸二茂铁酯L-B膜在光照的CdSe薄膜/Fe(CN)_6~(4-)溶液界面起传递电荷的中介作用,加速了界面的电荷转移。     

Comparative study of chemical and electrochemical Fenton treatment of organic pollutants in wastewater

The technological and economic aspects of using the Fenton process to treat industrial wastewater containing morpholyne and diethylethanolamine, as well as sodium salts of naphthalene sulfonic acid and of ethylenediaminetetraacetic acid based on data obtained in pilot tests are discussed. Chemical Fenton technology was tested using commercial 30–35% solutions of H₂O₂ and iron (II) salts, which was followed by the additional electrochemical destruction of organic pollutants in an undivided reactor with catalytic stable anodes (CSA) and 1 g L⁻¹ NaCl as a supporting electrolyte and a source of active chlorine. An alternative electrochemical method involving the electrogeneration of hydrogen peroxide in polluted water at the gas -diffusion cathode was studied both with the addition of ferrous salt to the electrolyte prior to electrolysis (in-cell electro-Fenton) as well as with the post-electrolysis addition of Fe²⁺ in another reactor (ex-cell electro-Fenton). The accumulation of hydrogen peroxide in concentrations sufficient for the mineralization of organic pollutants was achieved in both cases with near 100% current efficiency. In comparison with wastewater treatment processes which use a purchased hydrogen peroxide reagent, the Fenton-like processes achieved an economic savings of as much as 64.5% in running costs due to the on-site electrochemical generation of H₂O₂. Preparative electrolysis in the membrane reactor showed higher current efficiencies and lower specific energy consumptions for H₂O₂ electrogeneration in comparison with the results of tests carried out in an undivided cell.     

The Bromine Electrode. Part I: Adsorption Phenomena at Polycrystalline Platinum Electrodes

A cyclic voltammetric study of the behaviour of Br^– and Br^– ₃ at Pt electrodes, in the potential range between hydrogen and oxygen evolution, is described. Different experiments were carried out, in the presence of Br^– and Br^– ₃, in which the ratio between the species has been kept constant and equal to 1. The halide concentration was varied between 4 × 10^–6 and 1 × 10^–3 and mol dm^–3, at constant ionic strength, in 1 M HclO₄ as well as in 1 M NaClO₄ adjusted to a pH of 2. Underpotential deposition of Br is observed at potentials as low as –0.125 V vs SCE. The adsorption parameters of Br species were determined from the adsorption/desorption peak pair in the hydrogen adsorption/desorption region, and from the oxide reduction peak data. In the absence of oxygen adsorption, a relatively high coverage of the electrode surface is attained. A Langmuir-type adsorption is observed under the different experimental conditions.     

Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm⁻³ and varying H⁺ concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H⁺ concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO₂ and RTO. The expression of the kinetic current as a function of chlorine and H⁺ concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential.