Comments on the review ‘Anomalous behaviour of hydrogen extraction from hydride-forming metals and alloys under impermeable boundary conditions’, by J.-W. Lee, S.-I. Pyun, Electrochim. Acta 50 (2005) 1777-1805

The review by Lee and Pyun, which was published recently [Electrochim. Acta 50 (2005) 1777-1805], provides a comprehensive survey of the anomalous behaviours of hydrogen transport in hydride-forming electrodes, with particular emphasis on hydrogen extraction under the impermeable boundary condition during potentiostatic current transients. Some theoretical derivations presented in the above review, as well as the validity domains of theoretical results obtained by Lee and Pyun are discussed in these comments in terms of potential step amplitude, interfacial reaction mechanism, electrode kinetics and influence of Ohmic drop. In particular, the concepts of ‘constraint by constant concentration’, ‘constraint by Butler-Volmer behaviour’ and ‘constraint by hydrogen transfer of absorbed state to adsorbed state’ used by Lee and Pyun to discriminate between the boundary conditions at the electrode surface during hydrogen extraction are examined thoroughly in these comments. The ‘transition of the boundary condition at the electrode surface during hydrogen extraction’ is also discussed, as well as the influence of Ohmic potential drop on the chronoamperometric responses to large-potential steps.     

Investigation of hydrogen transport through Mm(Ni3.6Co0.7Mn0.4Al0.3)1.12 and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient

Hydrogen transport through such metal-hydride electrodes as Mm(Ni_3.6Co_0.7Mn_0.4Al_0.3)_1.12 and Zr_0.65Ti_0.35Ni_1.2V_0.4Mn_0.4 was investigated in 6 M KOH solution by using potentiostatic current transient technique. From the shape of the anodic current transient and the dependence of the initial current density on the discharging potential, the boundary conditions at the electrode surface were established during hydrogen extraction from the as-annealed and as-surface-treated electrodes. Especially, it was experimentally confirmed that the diffusion-limited boundary condition is no longer valid at the electrode surface during hydrogen transport in case hydrogen diffusion is coupled with either the interfacial charge transfer reaction or the hydrogen transfer reaction between adsorbed state on the electrode surface and absorbed state at the electrode sub-surface. From the transition behaviour of the boundary condition, it was further recognised that the boundary condition at the electrode surface during hydrogen transport is not fixed at the specific electrode/electrolyte system by itself, but it is rather simultaneously determined even at any electrode/electrolyte system by the potential step and the nature of the electrode surface, depending upon e.g. the presence or absence of the surface oxide scales.     

Analysis of anodic current transient measured on Pd electrode with fractal surface: Hydrogen diffusion coupled with interfacial charge transfer

Hydrogen transport through Pd electrode with fractally rough surface was investigated in 0.1 M NaOH solution by analysis of the anodic current transient. The Pd electrode surfaces were electrochemically modified to be rough by redox cycling in 1 M H₂SO₄ solution. From the triangulation analysis of the atomic force microscopy images, it was found that the modified electrode surfaces exhibited self-similar scaling properties with different fractal dimensions, depending upon the number of redox cycles. The anodic current transient measured on the surface-modified fractal electrode subjected to the hydrogen discharging potentials of 0.3-0.7 V reversible hydrogen electrode, (RHE) showed the non-generalised Cottrell behaviour, which resulted from the constraint of hydrogen diffusion mixed with interfacial charge transfer during hydrogen transport. Especially, it displayed an inflexion point at the time that corresponds to the temporal outer cut-off of fractality, i.e. the crossover time required for the fractal to flat transition. In addition, the temporal outer cut-off under the constraint of mixed control was observed to be shortened with increasing hydrogen discharging potential, which could be accounted for by the increased growth rate of diffusion layer in the electrode accompanying the facilitated charge transfer kinetics at the electrode/electrolyte interface.     

The kinetics of hydrogen transport through amorphous Pd82−yNiySi18 alloys (y=0-32) by analysis of anodic current transient

Hydrogen transport through amorphous Pd_82−yNi_ySi₁₈ alloys (y=0-32) was investigated in 0.1 M NaOH solution by analysis of the anodic current transient. It was found that the anodic current transient shows the non-Cottrell behaviour, but its shape and value remain nearly constant regardless of the hydrogen discharging potential. From the coincidence of the anodic current transient theoretically calculated with that experimentally measured, it is suggested that the change in surface concentration of hydrogen with time is uniquely given by the rate of hydrogen transfer from absorbed state at the electrode sub-surface to adsorbed state on the electrode surface. This means that neither the ‘constraint of constant concentration’ nor the ‘constraint by Butler-Volmer behaviour’ is effective at the electrode surface during hydrogen extraction. On the basis of the theoretical current-time relation under the ‘constraint by hydrogen transfer of absorbed state to adsorbed state’, the hydrogen diffusivity was determined to have an almost constant value of (1.3±0.4)×10⁻⁸ cm² s⁻¹, irrespective of the Ni content and in the absence of Ni. On the other hand, it is inferred that the rate constant of hydrogen transfer decreases markedly with increasing Ni content due to the Ni(OH)₂ layer formed on the electrode surface.     

An investigation of lithium transport through vanadium pentoxide xerogel film electrode by analyses of current transient and ac-impedance spectra

Lithium transport through vanadium pentoxide xerogel film electrode has been investigated in a 1 M solution of LiClO₄ in propylene carbonate by employing potentiostatic current transient technique and ac-impedance spectroscopy. From the comparison of the initial current experimentally measured with those initial currents theoretically calculated from the Ohm’s law and the Cottrell equation, it was confirmed that the cell-impedance-controlled constraint at the electrode surface is changed to the real potentiostatic boundary condition (diffusion-controlled constraint) when the potential step exceeds a critical value over the whole range of the lithium content. It was also found that the slope of the logarithmic current transient obtained at the lithium contents above 0.4 positively deviates in absolute value from 0.5 even under the real potentiostatic boundary condition, but the phase angle of the diffusion impedance under the semi-infinite diffusion condition negatively deviates in absolute value from 45° with increasing lithium content. With the aid of the X-ray diffractometry, the anomalous behaviours of the current transient and the diffusion impedance were discussed in terms of lithium transport through the interlayers with widely distributed spacings across the quasi-ordered xerogel film electrode. Furthermore, the current transient theoretically determined by employing the concept of interlayer spacing distribution coincided fairly well in form with that current transient experimentally measured.     

Electrochemical modeling of hydrogen storage in hydride-forming electrodes

An electrochemical kinetic model (EKM) is developed, describing the electrochemical hydrogen storage in hydride-forming materials under equilibrium conditions. This model is based on first principles of electrochemical reaction kinetics and statistical thermodynamics and describes the complex, multi-stage, electrochemical (de)hydrogenation process. A complete set of equations have been derived, describing the equilibrium hydrogen partial pressure and equilibrium electrode potential as a function of hydrogen content in both solid-solution and two-phase coexistence regions. The EKM has been applied to simulate the isotherms of thin film Pd electrodes of various thicknesses. Good agreement between experiment and theory is found in all cases. Relevant energy and kinetic parameters are obtained from the simulations.     

Investigation of the hydrogen evolution reaction at a 10 wt% palladium-dispersed carbon electrode using electrochemical impedance spectroscopy

The hydrogen evolution reaction (h.e.r.) at a 10 wt % palladium-dispersed carbon (Pd/C) electrode in 0.1 m NaOH solution has been investigated with reference to that on carbon (Vulcan XC-72) and palladium foil electrodes by analysing the a.c.-impedance spectra combined with cyclic voltammograms. From the coincidence of the maximum charge transfer resistances and the minimum hydrogen evolution resistances for the h.e.r. at the respective electrode potential for the Pd/C, carbon and Pd foil electrodes, it is suggested that the h.e.r. at the Pd/C electrode takes place along with the absorption and diffusion of hydrogen above –1.10 V vs SCE, whereas the former dominates over the latter below –1.10V vs SCE. In the case of the Pd foil electrode the transition of absorption and diffusion to evolution occurs at –0.96V vs SCE. In contrast to the Pd/C and Pd foil electrodes the h.e.r. occurs strongly at the carbon electrode below –1.20V vs SCE. The hydrogen evolution overpotential on the Pd/C electrode is decreased by 0.10 V in comparison to the carbon electrode due to the larger electrochemical active area of the finely dispersed Pd particles.     

Amorphous PdZr alloys for water electrolysis cathode materials

Amorphous Pd_0.35Zr_0.65 alloys prepared by a melt—quench technique were investigated for their possible use as water electrolysis cathodes. The Tafel—Volmer reaction route of the hydrogen electrode reaction was concluded. Kinetic parameter values of the constituent steps were evaluated by a transient technique. The electrocatalytic activity for cathodic hydrogen evolution on the as-obtained electrode was 10² times lower than Pd foil electrodes, but it was improved after the electrodes were treated in acids, typically aqueous HF. The activity in the highest state exceeds that of Pd by one order of magnitude. SEM and XPS observations indicated that the improvement in activity is due to increased surface Pd concentration after removal of a Zr-enriched surface layer which was produced during fabrication of the amorphous alloy specimens. Crystalline alloy electrodes prepared by heat treatment of the amorphous alloy were very brittle but showed electrocatalytic activity close to that of the amorphous electrodes.     

The study of hydrogen electrosorption in layered nickel foam/palladium/carbon nanofibers composite electrodes

In the present work, the process of hydrogen electrosorption occurring in alkaline KOH solution on the nickel foam/palladium/carbon nanofibers (Ni/Pd/CNF) composite electrodes is examined. The layered Ni/Pd/CNF electrodes were prepared by a two-step method consisting of chemical deposition of a thin layer of palladium on the nickel foam support to form Ni/Pd electrode followed by coating the palladium layer with carbon nanofibers layer by means of the CVD method. The scanning electron microscope was used for studying the morphology of both the palladium and carbon layer. The process of hydrogen sorption/desorption into/from Ni/Pd as well as Ni/Pd/CNF electrode was examined using the cyclic voltammetry method. The amount of hydrogen stored in both types of composite electrodes was shown to increase on lowering the potential of hydrogen sorption. The mechanism of the anodic desorption of hydrogen changes depending on whether or not CNF layer is present on the Pd surface. The anodic peak corresponding to the removal of hydrogen from palladium is lower for Ni/Pd/CNF electrode as compared to that measured for Ni/Pd one due to a partial screening of the Pd surface area by CNF layer. The important feature of Ni/Pd/CNF electrode is anodic peak appearing on voltammetric curves at potential ca. 0.4 V more positive than the peak corresponding to hydrogen desorption from palladium. The obtained results showed that upon storing the hydrogen saturated Ni/Pd/CNF electrode at open circuit potential, diffusion of hydrogen from carbon to palladium phase occurs due to interaction between carbon fibers and Pd sites on the nickel foam support.     

A study on the potentiostatic current transient and linear sweep voltammogram simulated from fractal intercalation electrode: diffusion coupled with interfacial charge transfer

Potentiostatic current transient and linear sweep voltammogram, theoretically calculated from the well-defined fractal profiles were analysed, with particular emphasis on hydrogen transport under the condition where hydrogen diffusion in the electrode is kinetically coupled with the charge-transfer reaction at the electrode/electrolyte interface. Under such a constraint of mixed control, the simulated current transient from the fractal electrode hardly exhibited the generalised Cottrell behaviour, and, especially, it displayed an inflexion point at the time that corresponds to the temporal outer cut-off of fractality (crossover time required for the fractal to flat transition). In the case of the linear sweep voltammogram computed from the fractal electrode, moreover, the power dependence of the peak current on the scan rate deviated negatively from the generalised Randles-Sev?ik behaviour, above the slow threshold scan rate (crossover scan rate needed for the fractal to flat transition). From the analyses of the current transients and the linear sweep voltammograms calculated with various values of the simulation parameters, it was further recognised that during the potential jump as well as the potential scan, the temporal cut-off ranges of fractality under the constraint of mixed control are crucially determined by the interfacial charge-transfer kinetics, even though the spatial cut-off range and the hydrogen diffusivity in the electrode are maintained constant.     

Hydrogenation of chalcones using hydrogen permeating through a Pd and palladized Pd electrodes

The hydrogenation of benzalacetone and benzalacetophenone was carried out using atomic hydrogen permeating through a palladium membrane. A two-compartment cell separated by a Pd sheet or a palladized Pd (Pd/Pd black) sheet electrode was employed. The reduction products were identified by (GC) gas chromatography, UV-vis absorption spectroscopy and NMR spectroscopy. The carbon-carbon double bond was hydrogenated and the benzylacetone and benzylacetophenone were obtained as products using palladium catalyst. The current efficiency for hydrogenation reaction increases when the current density for water electrolysis decreases and depends on the initial chalcone concentration. It is over 90% at the concentration of 10 mmol L⁻¹. The hydrogen absorption and diffusion into and through a palladium membrane electrode has been studied by using an electrochemical impedance spectroscopy method. The impedance results would indicate that the hydrogen permeated through the membrane is consumed by the chalcone during the hydrogenation process keeping as the permeable boundary condition in the outer side of the Pd membrane the hydrogen activity almost zero. The hydrogen entering the metal through an adsorbed state and the rate of hydrogen absorption is diffusion-controlled.     

Electrochemical behaviour of palladium electrode: Oxidation, electrodissolution and ionic adsorption

In electrochemistry, Pourbaix diagrams also known as potential-pH diagrams map out the regions of stability of metals as well as the regions of possible existence of stable compounds. The stable states other than the metallic one are macroscopic compounds, typically oxides and hydroxides, or their hydrated forms. Yet, several noble metals possess the ability to form thin surface oxides, to adsorb anions, and to adsorb or to absorb hydrogen in the potential range of water stability. Palladium is a unique noble metal owing to its ability to adsorbed and to absorb H, as well as to form compact and stable surface oxides. Anodic polarization of Pd results in the formation of a surface oxide. Thus, a great majority of anodic electrode processes takes place not at a metallic surface but at a surface covered with an oxide layer. Although thin surface oxides reveal metallic conductivity, the presence of O-containing species affects the electron transfer kinetics and the adsorption behaviour of reactants, intermediates, and products. Thus, the electrocatalytic properties of Pd electrodes, and the mechanism and kinetics of the reaction under consideration are strongly affected by the oxide layer, its thickness, chemical composition (Pd oxidation state and nature of O-containing species) and 3D structure, degree of oxide hydration, and electronic properties. This contribution presents an overview of the current understanding of electro-oxidation of Pd in aqueous acidic and basic electrolytes. In particular, it describes the formation of Pd oxides under various experimental conditions and discusses their chemical and physical nature. It examines the reduction of O-containing species present on Pd electrodes as well as the adsorption of anions and cations. Since Pd can undergo electrodissolution that results in material loss, the process is analyzed in relation to experimental parameters. Recent developments in the electrochemical behaviour of single-crystal Pd electrodes are discussed. Electrochemical parameters such as the potential of zero charge, potential of zero total charge and potential of zero free charge are of importance to the structure of the electric double layer; thus, their values are discussed in relation to the absence/presence of Pd surface oxides. Finally, various experimental procedures commonly used to determine the real surface area of Pd electrodes are outlined and compared.     

Preparation and Characterization of Codeposited Palladium‐Nickel/Titanium Electrodes and Palladium‐Nickel/Polymeric Pyrrole Film/Titanium Electrodes

Palladium‐nickel/titanium (Pd‐Ni/Ti) and palladium‐nickel/polymeric pyrrole film/titanium (Pd‐Ni/PPy/Ti) electrodes were prepared by electrochemical deposition. The electrochemical characteristics of the Pd‐Ni/Ti and Pd‐Ni/PPy/Ti electrodes were studied by means of cyclic voltammetry (CV) based on orthogonal experiments. CV studies on the electrodes were conducted in 0.5 mol/L sulfuric acid solution. Experimental results indicate that the hydrogen adsorption peak value of the Pd‐Ni/PPy/Ti electrode seen at ca. –500 mV is larger than that of Pd‐Ni/Ti electrode. Scanning electron microscope (SEM) images indicate that polymeric pyrrole film, which formed on electrode can modify the electrode surface configuration significantly and provide the surface of the Pd‐Ni/PPy/Ti electrode with more layers and a larger surface area.     

Voltage-step transient on circular electrodes

Using the well-known Cottrell asymptote, voltage-step transient (VST) experiments in a two-electrode cell may provide data on the bulk concentration and diffusion coefficient of a working depolarizer, essential for interpretation of liming-diffusion-current (LDC) experiments. However, the Cottrell asymptote is never applicable in the early stages of the voltage-step transient process. There are three additional transport resistances to the basic diffusion transport that cannot be neglected at extremely high initial currents: Faradaic resistance at the working electrode surface, overall Ohmic losses in the electrochemical cell, and a possible galvanometric constraint in the outer circuit, involving the galvanometer, current follower, potentiostat, etc. The effect of these additional transport resistances on the transient current at higher polarization voltage is non-linear. In the present analysis, a 1D approximation is used, assuming tacitly uniform accessibility of the working electrode and negligible transport resistances at the counter electrode. The Faradaic resistance of a redox couple O + ne ⁻ = R according to Butler–Volmer electrode kinetics is considered. The results of 1D theory are corrected for edge effects using the Oldham asymptote. The effect of convection at longer times is included using the recent model of a transient process for circular working electrodes in the LDC regime.     

An electrochemical method for measurement of mass transport in polymer membranes using acetaminophen as a model system

An electrochemical approach has been used to model and measure acetaminophen transport through a microporous polycarbonate membrane. The dynamic response of a membrane covered planar electrode system was investigated to derive a simplified middle point formula, the time at which amperometric current reaches half steady state value, that provided reliable solute diffusion coefficients. Experimental values may be noise-contaminated; when this noise is significant, the diffusion coefficient by this method needs to be refined. Here a direct simulation method with a bipartite mathematical expression for current transient was used, which fitted calculated current transients to experimental data. A best fit was reached by minimising the standard deviation between the simulated and experimental current profiles. Mathematically, the simulated curve was linear operated, i.e. shifted and stretched vertically, as well as shifted and stretched horizontally to coincide with the experimental curve. The single point formula, bipartite expression and simulation approach allowed extraction of accurate diffusion values from a previously reported approximated method. The computation approach is not only valid for membrane covered electrodes, but is suitable for other experimental set ups where a one-dimensional Fickian diffusion model is valid, for example, for axial diffusion through cylindrical geometries.     

Voltammetry in the presence of ultrasound: mass transport effects

The voltammetry of various well-defined systems in acetonitrile solution has been studied using both micro and macroelectrodes in the presence of power ultrasound. A simple model is established which quantifies the mass transport observed under these conditions; this assumes that the effect of ultrasound is to promote mixing within the bulk of the solution up to within a certain distance of the electrode surface. Thus the ultrasound serves to thin the diffusion layer which would exist at the corresponding electrode under silent conditions. The relative enhancement of transport limited currents by ultrasound is dependent on the size of the electrode; for micrometre-sized electrodes the steady state limiting current observed tends to that predicted under silent conditions whereas for large electrodes a thin, steady-state diffusion layer is seen with a thickness which is power dependent. In addition to steady-state experiments, a.c. impedance measurements and potentials steps are used to verify the model proposed.Author to whom corresponding should be sent.     

Tungsten carbide-based electrochemical sensors for hydrogen determination in gas mixtures

An amperometric study of gas-diffusion electrodes (GDE) catalysed by two types of tungsten carbide, WC₍₁₎ and WC₍₂₎, which differ considerably in their specific surface area (0.5 and 6 m² g^–1), was carried out. The H₂–air gas mixture (H₂ 1–4%) measurements show that for this range of hydrogen concentration the hydrogen limiting diffusion current (i _d(H2)) may be attained so that a curve of limiting current density against hydrogen concentration can be obtained. The response and stability of the electrode performance were compared to those of platinum catalysed GDEs. The most promising for use in amperometric hydrogen sensing is the WC₍₁₎ catalyst of small specific surface area. Electrodes catalysed with this catalyst show inferior response time in comparison to electrodes catalysed with the other two catalysts (WC₍₂₎ and Pt) but their overall stability is much better.     

流化床电极的极化性能和过电位分布

文中解析了流化床电极的一维模型.得到了电荷传递系数为1/3,1/2,2/3,电极反应为活化控制时过电位分布的确切解.还得到了电荷传递系数取任意值且无因次电阻参数较大时,电极反应分别处于活化控制、扩散控制、混合控制或伴有副反应等各种情况下的极化方程.上述结果亦适用于全浸没立体电极.还讨论了参数对电流效率的影响.     

Application of pulse methods to the determination of the electrochemical characteristics of lithium intercalates

The transfer processes proceeding in insertion electrodes with surface control on the application of a potential or current step are considered theoretically. The theoretical relationships have been verified by the determination of the kinetic and diffusion parameters of electrochemical lithium intercalation into thin carbon films. The overall electrode polarization is divided, both theoretically and experimentally, into the kinetic component, related to hindered ion transfer in the passive surface layer, and the diffusion one, related to decelerated lithium diffusion in the carbon matrix. The polarization dependence of kinetic current is shown to obey the same regularities that the current-potential function of the lithium electrode. The concentration dependences of the surface layer parameters and the diffusion coefficient of lithium in carbon have been determined.     

Reduction of metal ions in dilute solutions using a GBC-reactor Part II: Theoretical model for the hydrogen oxidation in a gas diffusion electrode at relatively low current densities

The GBC-reactor is based on the combination of a gas diffusion anode and a porous cathode. A theoretical model for gas diffusion electrode, valid at relatively low current densities, is derived. This is based on the pseudohomogeneous film model including an approximation of the Volmer–Tafel mechanism for the hydrogen oxidation kinetics. Results show a severe mass transfer limitation of the hydrogen oxidation reaction inside the active layer of the gas diffusion electrode, even at low current densities. Empirical formulae are given to estimate whether leakage of dissolved hydrogen gas into the bulk electrolyte occurs at specific process conditions. A simplified version of the model, the reactive plane approximation, is presented.