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:

Preparation of a Novel Composite Material Based on a Nafion® Membrane and Polypyrrole for Potential Application in a PEM Fuel Cell

The process of embedding polypyrrole (PPy) on the surface of a Nafion^® membrane was studied. Three methods of PPy synthesis directly on the membrane surface were compared. The diffusion method based on the separation of monomer and oxidant (peroxidisulphate) solutions by the membrane to be modified is proposed as the most promising one. The monomer diffuses through the membrane to the oxidant side, where it is polymerized. In this case sulphate is incorporated into the film as a counter-ion. PPy film prepared in this way adheres well to the Nafion^® surface and shows promising electrochemical activity. The permeability of the composite for monomer in comparison to self-standing Nafion^® film is reduced significantly. This may be important for the potential application of this composite, especially in a direct methanol fuel cell, as an alternative membrane-electrode assembly (MEA), particularly with regard to the currently used MEA’s permeability for fuel.     

Bulk and Surface Properties of a VPO Catalyst Used in an Electrochemical Membrane Reactor: Conductivity-, XRD-, TPO- and XPS-study

In the first part of this work, the electrical conductivity of vanadium phosphorous oxide (VPO) catalyst was investigated by means of the 2-probe EIS method. The VPO showed an extremely low conductivity at low oxygen partial pressure, which is the prevailing condition in the anodic compartment in an electrochemical membrane reactor (EMR). In the second part of this study, fresh as well as VPO catalyst already used in an EMR were characterised with XRD, XPS and temperature programmed oxidation (TPO). The XRD measurements revealed an unchanged bulk phase structure after operation in the EMR. Significant differences in the average oxidation states of vanadium in the catalyst layer in the EMR were determined via XPS, where the catalyst surface facing the electrolyte membrane was more oxidised than the surface facing the anodic gas compartment. The lowered uptake and release of oxygen was observed in TPO experiments for the catalyst used in the EMR.     

Review of Mechanically Related Failures of Ceramic Capacitors and Capacitor Materials

This paper reviews the brittle fracture behavior of dielectric ceramics such as barium titanate, and describes some of the relationships between defects such as cracks and electrical degradation and failure of multilayer capacitors. Stresses arising from the ferroelectric phase transformation in these dielectric materials are shown to play a part as a driving force for crack growth. In addition, possible contributions to failure from stresses arising from thermal excursions in the capacitor are discussed. Low-voltage failures arising from a short between the electrodes in multilayer capacitors are shown to be related to the growth of cracks in the dielectric. A technique for predicting the onset of these types of failures based upon fracture mechanics techniques is described. Possible effects of the electric field itself in promoting or retarding the growth of cracks are discussed.     

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%。     

Influence of anode material on the electrochemical oxidation of 2-naphthol: Part 2. Bulk electrolysis experiments

The electrochemical oxidation of 2-naphthol has been studied by galvanostatic electrolysis, using a range of electrode materials such as lead dioxide, boron-doped diamond (BDD) and Ti-Ru-Sn ternary oxide anodes. The influence of some operating parameters, such as current density, flow-rate and chloride concentration on naphthol oxidation has been investigated in order to find the optimum experimental conditions. Measurements of chemical oxygen demand, HPLC and total organic carbon have been used to follow the oxidation. The experimental data indicate that on PbO₂ and BDD, naphthol oxidation takes place by reaction with electrogenerated hydroxyl radicals and is favoured by low current density and high flow-rate. On the contrary, on a Ti-Ru-Sn ternary oxide the mineralisation of naphthol occurs only in the presence of chloride ions that act as redox mediators and COD removal is affected by chloride concentration and is not significantly influenced by the current density and mass-transfer coefficient. From a comparison of the results of the three electrodes it has been found that boron-doped diamond gives a faster oxidation rate and better current efficiency.     

Electrochemical polymerization of toluene in the mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid

Poly(methylphenylene) (PMeP) films were prepared by direct oxidation of toluene in the mixed electrolytes of boron trifluoride diethyl etherate (BFEE) and trifluoroacetic acid (TFA). The oxidation potential of toluene in pure BFEE was measured to be 1.52 V versus saturated calomel electrode (SCE). This value was much lower than that determined in a neutral medium such as acetonitrile (2.13 V versus SCE). The introduction of TFA into BFEE decreased the oxidation potential of toluene and also improved the properties of as‐formed polymer films. Infrared and Raman spectra confirmed the formation of PMeP films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 189–195, 2004     

Alkaline peroxide generation using a novel perforated bipole trickle-bed electrochemical reactor

A novel perforated bipole trickle-bed electrochemical reactor is investigated for the electro-synthesis of alkaline peroxide. The process uses a relatively simple cell configuration in which a single electrolyte flows with oxygen gas in a flow-by graphite felt cathode, sandwiched between a micro-porous diaphragm and a perforated bipolar electrode plate. The graphite felt cathodes are 120 mm high by 25 mm wide and have a thickness of 3.2 mm. The reactor is operated at current densities in the range 1–5 kA m⁻², ca. 800 kPa (abs) pressure and temperature (In/Out) 20–45 °C with one and two-cells. The reactor shows good performance (current efficiency ∼78% at 2 kA m⁻² and a specific energy of 5 kWh per kg of peroxide generated) with peroxide concentrations from 0.02 to 0.15 M in 1 M NaOH.     

Atmospheric Dependence on Dielectric Loss of 1/6Ba5Nb4O15· 5/6BaNb2O6 Ceramics

Samples of 1/6Ba₅Nb₄O₁₅·5/6BaNb₂O₆ along with the pure end members, Ba₅Nb₄O₁₅ and BaNb₂O₆, were sintered under low oxygen partial pressure. The degradation mechanisms of dielectric loss in this reducing atmosphere have been studied. We found that the degradation occurred primarily due to the formation of oxygen vacancies caused by the reduction of Nb⁵⁺. This was determined by measuring the electrical conductivity, and through X-ray photoelectron spectroscopy. More importantly, the dielectric loss of 1/6Ba₅Nb₄O₁₅·5/6BaNb₂O₆ samples with higher temperature stability was further decreased on sintering in a reducing atmosphere. This observation has been explained by considering the increased porosity and formation of a reduced second phase, Ba_0.65NbO₃.     

多壁碳纳米管与聚(2-乙酰基-5-溴噻吩)复合纳米材料修饰玻碳电极同时检测对苯二酚、邻苯二酚和对甲苯酚

该文利用多壁碳纳米管(MWCNTs)和聚(2-乙酰基-5-溴噻吩)复合纳米材料修饰电极,用于同时检测对苯二酚(HQ)、邻苯二酚(CC)和对甲苯酚(PC)。通过循环伏安法(CV),示差脉冲伏安法(DPV)和透射电镜(TEM)表征了该复合纳米材料的电化学性能和表面形貌。结果表明该电极对HQ、CC和PC具有较高的灵敏度和选择性。DPV峰电流与HQ、CC和PC的浓度在1.0×10-5～8.0×10-4mol/L,5.0×10-6～5.5×10-4mol/L和5.0×10-6～7.5×10-4mol/L范围内分别呈良好的线性关系,且检测限分别为3.0×10-6 mol/L,1.7×10-6 mol/L和2.0×10-6mol/L。