Electrochemical analysis of a photoelectrochemical chloralkali reactor

In the present study, the electrochemical model for a newly designed photo electrochemical hydrogen production reactor is discussed. The reactor integrates the photochemical hydrogen production with an electrochemical chloralkali process. To neutralize the hydroxyl ions into the chloralkali process, the ideal minimum required potential is 2.18 V. However, there are losses in the solution, membranes and electrodes. These losses should be calculated to find the exact voltage requirement of the photoelectrochemical hydrogen production reactor. An electrochemical model is developed to calculate these losses in the reactor. Effect of brine concentration, electrolyte concentration, distance between the electrodes, current density and temperature are evaluated. The results show that a minimum voltage is required when the distance between the electrodes becomes a minimum at the highest possible temperature, lowest current density and at highest concentrations of brine and electrolyte. Furthermore, they indicate that brine and electrolyte concentrations do not have significant effect on required voltage.     

Modelling of three-dimensional bipolar electrodes with irreversible reactions

The behaviour of an electrochemical reactor with three-dimensional bipolar electrodes for irreversible reactions is analysed. Copper deposition at the cathodic side and oxygen evolution at the anodic one were adopted as test reactions at the bipolar electrode, from an electrolyte solution with a copper concentration lower than 1000 mg dm⁻³, pH 2 and 1 M Na₂SO₄ as supporting electrolyte. A mathematical model considering the leakage current is proposed, which can represent the tendency observed in the experimental data related to cathodic thickness and potential at both ends of the bipolar electrode. High values of leakage current were determined, which restricts the faradaic processes to small thicknesses at both ends of the bipolar electrode. Likewise, the performance of the bipolar electrochemical reactor for the treatment of effluents is experimentally and theoretically examined. In this case, the conversion for copper removal was 90.1% after 480 min of operation with one bipolar electrode and 94.8% after 300 min of operation with two bipolar electrodes at a total current of 3 A.     

Effect of leakage currents on the primary current distribution in bipolar electrochemical reactors

The primary current distribution in a bipolar electrochemical reactor with outside inlet and outlet electrolyte manifolds was investigated by numerical solution of the Laplace equation and by experimental measurement in simulated cells made from conductive paper and segmented electrodes. The geometric parameters determining the distribution were the interelectrode gap, electrode length, transverse section and length of the electrolyte manifold. The effect of the number of electrodes in the bipolar stack was also analysed. Values obtained numerically have been compared with those obtained experimentally and a good agreement is observed between them. These results are useful for estimating the performance of the bipolar stack.     

Nitric oxide reduction at noble metal electrodes: a voltammetric study in acid solution

Features of the electrochemical reduction of nitric oxide on platinum, palladium, rhodium and ruthenium in aqueous perchloric acid solutions (0.33–1.0 M) are compared. The results from voltammetric studies (ie linear potential sweep and rotating disc electrode) using the bulk metal electrodes are described and compared with residual current voltage plots in acid electrolyte alone. In general, three nitric oxide reduction peaks are observed on the metals. The most anodic peak, at ca E = 0.15 V vs sce is attributed to the one-electron reduction of nitric oxide to an adsorbed NOH intermediate on a bare metal surface (ie one free of oxides or adsorbed hydrogen). The other two peaks occur in potential regions where adsorbed hydrogen is present on the metal surface (ca E = 0.0 and −0.20 V, respectively). The co-adsorbed hydrogen complicates the analysis and precludes an unambiguous interpretation of these two peaks. However, they apparently reflect nitric oxide reduction to nitrogen, hydroxylamine and/or ammonia. In a cathodic scan on the rhodium electrode, a current plateau is seen instead of the first (most anodic) peak, a probable consequence of oxide film formation with subsequent chemical complications. On the ruthenium electrode the first two (most anodic) peaks are not observed probably due to a relatively stable oxide layer. Reaction selectivities at metal black gas diffusion cathodes operating in an electrogenerative (ie galvanic) mode with perchloric acid electrolyte are compared with the voltammetric results at the corresponding bulk electrodes. Dinitrogen formation is observed on the platinum and rhodium black electrodes as suggested from voltammetric results. A series-parallel reaction sequence is proposed to explain the results. Limitations of using simple voltammetric techniques for predicting behavior of large scale preparative electrochemical reactors are discussed.     

A study of current distribution in a DEM cell during bromate formation

The anodic oxidation of potassium bromide to potassium bromate is performed in an undivided cell with hydrogen evolution the major reaction at the counter electrode. The cell used is a dished electrode membrane (DEM) cell. Current density distribution, measured using a segmented electrode, shows a variation in the two principle dimensions; along the length of the electrode and over the width of the electrode. Current densities are highest at the electrolyte flow inlet and also exhibit a localized maximum along the electrode length. The variation in current density is due to the influence of electrolytic gas evolution on the effective electrolyte conductivity and mass transport and also due to the change in shape of the dished electrode, which influences mass transport, electrical potential field and flow at the cell inlet and exit.     

In Situ Soft X‐ray Microscopy Study of Fe Interconnect Corrosion in Ionic Liquid‐Based Nano‐PEMFC Half‐Cells

This in situ soft X‐ray scanning microscopy electrochemical study of model proton exchange cathodic and anodic nano‐fuel cells is exploring the evolving structure and chemical composition of key cell components represented by Au and Fe electrodes in contact with Nafion‐ionic liquid composite electrolyte containing Pt black catalyst particles. Morphological and chemical changes of the electrodes as well as the chemical state and fate of the Fe species released into the electrolyte are monitored in short circuit and with applied cathodic or anodic polarization. The in situ X‐ray absorption images of the cathodic cell fed with 2.5 × 10^–5 mbar O₂ have revealed corrosion‐induced morphology changes in the Fe electrode, being more pronounced in the vicinity of Pt‐black particles, and deposition of the Fe species released into the electrolyte, onto the intact Au counter electrode upon cathodic polarization. The Fe electrodes of the anodic cell containing NaBH₄ in the electrolyte appear relatively more corrosion resistant. The Fe L₃ absorption spectra taken in different locations within the Fe electrode have shown lateral variations in the relative ratio between Fe²⁺ and Fe^3&4+ oxidation states, whereas the Fe species released into the RTIL electrolyte are only in the high Fe^3&4+ oxidation states.     

Synchronized current oscillations of formic acid electro-oxidation in a microchip-based dual-electrode flow cell

We investigate the oscillatory electro-oxidation of formic acid on platinum in a microchip-based dual-electrode cell with microfluidic flow control. The main dynamical features of current oscillations on single Pt electrode that had been observed in macro-cells are reproduced in the microfabricated electrochemical cell. In dual-electrode configuration nearly in-phase synchronized current oscillations occur when the reference/counter electrodes are placed far away from the micro-electrodes. The synchronization disappears with close reference/counter electrode placements. We show that the cause for synchronization is weak albeit important, bidirectional electrical coupling between the electrodes; therefore the unidirectional mass transfer interactions are negligible. The experimental design enables the investigation of the dynamical behavior in micro-electrode arrays with well-defined control of flow of the electrolyte in a manner where the size and spacing of the electrodes can be easily varied.     

原油储罐底板外侧阴极保护技术

以固体电解质涂层为导电层,石墨导电涂料为阳极涂层,石墨为参比电极,进行原油储罐底板外侧的气相阴极保护。通过实验确定了固体电解质、导电涂料的配方,测定了Q235钢在涂层中的自腐蚀电位、最小保护电位和最小保护电流密度等电化学参数。     

Kinetic behaviour of packed and fluidised bed electrodes

For the reaction of electrochemical quinone reduction at packed and fluidised bed electrodes an experimental parameter analysis of macrokinetic bed cd was carried out showing the influence of electrode potential, flow velocity, bed depth parallel to current flow direction, and electrolyte conductivity. A macrokinetic model of three-dimensional electrodes is established by introducing overpotential distribution within the electrode into the microkinetic rate equation. Theoretical calculations of macrokinetic bed cds yield reliable values as is shown by comparison with the experimental results. Both for packed and for fluidised bed electrodes analytical expressions are derived for penetration depth of diffusion limiting cd into bed electrodes.     

The electrochemical properties of cadmium forms of zeolite of type A

The electrochemical behaviour of pressed cadmium forms of zeolite of type A was investigated by various electrochemical methods. It is shown that the behaviour is typical of electrolytic systems but also with anodic and cathodic passivation of platinum electrodes. The electrode processes and the mechanism of charge transport through the electrolyte and the layer adjacent to the electrode are consisdered.     

Multi-layer configuration for the cathode electrode of polymer electrolyte fuel cell

This paper conducts a one-dimensional theoretical study on the electrochemical phenomenon in the dual-layer cathode electrode of polymer electrolyte fuel cells (PEFCs) with varying sub-layer thicknesses, and further extends the analysis to a triple-layer configuration. We obtain the explicit solution for a general dual-layer configuration with different layer thicknesses. Distributions of the key quantities such as the local reaction current and electrolyte overpotential are exhibited at different ratios of the ionic conductivities, electrochemical kinetics, and layer thicknesses. Based on the dual-layer approach, we further derive the explicit solutions for a triple-layer electrode. Sub-layer performances are plotted and compared. The results indicate that the layer adjacent to the electrolyte membrane may contribute a major part of the electrode faradic current production. The theoretical analysis presented in this paper can be applied to assist electrode development through complicated multi-layer configuration for cost-effective high performance electrodes.     

Calculation of ohmic resistance effects in rectangular electrodes of finite thickness

The current distribution in electrochemical cells consisting of parallel rectangular plates is determined. The calculations involve the evaluation of the appropriate analytical solution of Laplace's equation within the electrodes and electrolyte, with boundary conditions corresponding to potential continuity (primary current distribution) or linear electrode kinetics (secondary current distribution) at the electrode-electrolyte interface, and do not make the usual assumption that current flow in the resistive electrode is one-dimensional. The current distributions are given in the form of Fourier series that allow the effects of electrode resistance and electrical contact geometry to be determined.     

Electrochemical behavior of La0.8Sr0.2FeO3 electrode with different porosities under cathodic and anodic polarization

Electrochemical behavior of La_0.8Sr_0.2FeO₃ (LSF) electrode with different porosities under cathodic and anodic current polarization has been investigated by electrochemical impedance spectroscopy and the galvanostatic method. The activation and degradation behavior of the LSF electrode may be related to the partial reduction and oxidation of the Fe ions under cathodic and anodic polarization, especially in the LSF electrodes with high porosities. The performance of the LSF electrode has been found to depend on the oxygen vacancies at the LSF surface, which would promote the transport of oxygen intermediate species at the LSF surface close to the triple-phase boundary (TPB) region. Results show that the polarization resistance (Rp) of the LSF electrode decreases at the beginning with the increase of cathodic polarization time, while Rp always increases with the increase of anodic polarization time. The effect of cathodic and anodic polarization becomes predominant with the increasing of the porosities of the LSF electrode, which is ascribed to the decrease of the interface area between electrode and electrolyte.     

Comparison between the influence of applied electrode and electrolyte temperatures on porous anodizing of aluminium

A new approach for studying the effect of temperature on anodic oxide growth on aluminium is presented in this paper. Using an in-house developed electrode holder, anodizing is performed under conditions of applied and controlled electrode temperature. The influence of temperature on the process is evaluated by experiments in a broad temperature range for both the electrode and the electrolyte temperature. The electrochemical behaviour of the aluminium electrodes is demonstrated to be more susceptible to variations of the electrode temperature than to variations of the electrolyte temperature. Concerning the morphology of the anodic film it is shown that by cooling the electrode a normal oxide layer could be grown at high electrolyte temperatures, whereas anodizing in a cool electrolyte at high electrode temperature results in a collapsed porous structure at the oxide surface. Furthermore, the electrode temperature affects the formation ratio of the oxide to a larger extent than the electrolyte temperature, indicating its important influence even on the level of the ionic conductivity during anodic oxide growth. All observations indicate that merely considering the electrolyte temperature upon studying the influence of temperature on the process is not sufficient; the electrode temperature is much more determining.     

Influence of geometric variables on the current distribution uniformity at the edge of parallel plate electrodes

In electrochemical processes, the reaction is controlled by electrodes relative placement; to many respects parallel plates seems close to the ideal configuration. However, edge effect represents a detrimental phenomenon that can compromise overall process efficiency. Cell's enclosing insulating walls can attenuate extreme current densities occurring at the electrode edge if appropriately designed to modify the current flow paths. Configurations comprising a limited counter electrode width, an enclosing normal insulating wall, an enclosing oblique insulating wall and a thin parallel mask have been studied. Potential distribution and electrical current lines of these configurations are obtained from algebra operations of complex variables owing to conformal mapping method. It was found that current distribution non-uniformity is conveniently expressed as the absolute deviation from the prescribed value. The dependence of this parameter on geometric variables can be mapped. The picture given by these maps solved the engineering problem of deducing the cell geometry complying with a given current distribution uniformity. Furthermore, optimal parameters providing the best possible performance of each configuration have been identified. Among the geometric variables, the gap between electrodes is the governing parameter of uniformity; it scales the magnitude of edge effect.     

Dopant induced effect on electrocatalytic reduction of nitrobenzene using conducting polypyrrole thin film electrodes

Conducting polypyrrole electrodes were prepared by electrochemical polymerization of pyrrole on vacuum‐metallized glass substrates. These electrodes were modified by doping with a range of metal halides as dopant ions having different electronegativity. Electrochemical reduction of nitrobenzene using these electrodes was studied by means of cyclic voltammetry technique in acetonitrile medium containing aqueous HClO₄ (0.1M) as supporting electrolyte. It was found that the electronegativity of the dopant ion played a very important role in the electrocatalytic activity. Polypyrrole doped with nickel chloride gave the highest anodic current at the reduction potential of nitrobenzene. The results were explained on the basis of charge transfer efficiency at the electrode–electrolyte interface, which was associated with the acceptor state created by the dopant in the semi‐conducting polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Comparative study on surface behaviors of copper current collector in electrolyte for lithium-ion batteries

The chemical and electrochemical stability of Cu current collectors in electrolyte for lithium-ion batteries is investigated. During long-term storage, the surface section of Cu foil is oxidized to copper compounds along with the reduction reaction of electrolyte. A continuous surface film can be formed on the Cu current collector after the foil is immersed in electrolyte for lithium ion batteries at room temperature for 30 days. This surface film is composed of inorganic compounds located in the inner layer and organic/inorganic mixed components stayed outside. It comes from the spontaneous reaction at the interface between Cu foil and electrolyte for the existence of trace water in electrolyte. Different from SEI film spontaneous formation during storage, surface film generated on Cu foil during electrochemical process shows different characteristic and mechanism. By using metal lithium as counter electrode, SEI film on Cu foil in Cu foil/metal Li battery is formed from surface chemical species floating from lithium counter electrode and electrochemical oxidation/reduction process. In contrast, thinner SEI film can be generated merely from electrochemical electrolyte decomposition and precipitation. All the evidences reveal that the structure of SEI film from different conditions is similar, which shows inorganic fluorides located in the inner layer and organic/inorganic mixed lied in the outer layer.     

The behaviour of porous electrodes in a flow-by regime—I. theoretical study

A mathematical model is presented to describe the behaviour of three-dimensional electrodes operating under limiting current conditions. Principal results are the effect of electrolyte resistivity, hydrodynamic and cell geometrical parameters on the distribution of the electrolyte potential and overpotential inside the structure. The most pertinent parameters of the electrode and application to the design of a reactor having perpendicular directions of current and electrolyte flow are given.     

Improved current efficiency equation for the electrodeposition of copper

The current efficiency of copper deposition is controlled by the extent of the competing hydrogen formation reaction which acts on mass transfer of copper ions together with further mass transfer mechanisms. An available current efficiency equation taking account only of the bubble-induced microconvection fails in the case of forced electrolyte flow. The equation is now extended to all other mechanisms. Results are compared with experimental data.     

The influence of electrolyte purity on electrochemical measurements using platinum electrodes

The influence of electrolyte purity on electrochemical processes at low-area platinum electrodes has been studied by a fast potential-step method and by cyclic voltammetry. Pre-purification of the electrolyte had no significant influence on the metal surface area available for H adsorption determined immediately after an electrochemical cleaning step. Maintaining the electrode potential within the ‘double-layer’ region of platinum (at 0.5 V vs rhe) for relatively long periods of time (1–30 min) results in the progressive suppression of H adsorption, owing to the adsorption of impurities blocking active Pt sites. All samples of electrolyte, irrespective of the degree of pre-purification, exhibited this effect. In the determination of current-time transients during the first few hundred milliseconds of the methanol electro-oxidation reaction, impurities in the untreated electrolyte contribute to the measured anodic currents at Pt electrodes working in the potential range of 0.4–0.6 V. The anomalous effects observed within this potential range can be largely eliminated by pre-electrolysis of the H₂SO₄ electrolyte for several days using Pt wire gauze electrodes at 2.1 V.