Electrochemical deposition and characterization of NiFe coatings as electrocatalytic materials for alkaline water electrolysis

In this study, nickel (Cu/Ni), iron (Cu/Fe) and nickel-iron (Cu/NiFe) composite coatings with various chemical compositions were electrochemically deposited on a copper electrode and characterized using cyclic voltammetry (CV), atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques in view of their possible applications as electrocatalytic materials for the hydrogen evolution reaction (HER) in an alkaline medium. The electrocatalytic activity of the coatings for the HER was studied in 1 M KOH solution using cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. The presence of nickel along with iron increases the electrocatalytic activity of the electrode for the HER when compared to nickel and iron coatings individually. The HER activity of the composite coatings depends on the chemical composition of the alloys. The Cu/NiFe-3 electrode (with a molar concentration ratio of Ni²⁺:Fe²⁺ of 4:6 in the plating bath) was found to be the best suitable cathode material for the HER in an alkaline medium under the experimental conditions studied. Furthermore, the electrocatalytic activity of the Cu/NiFe-3 electrode for the HER was tested for extended periods of time in order to evaluate the change in the electrocatalytic activity of the electrode with operation time. The HER was activation controlled and has not been changed after electrolysis. A constant current density of 100 mA cm⁻² was applied to the electrolysis system, and the corrosion behavior of the Cu/NiFe-3 electrode was investigated after different operation times using EIS and linear polarization resistance (LPR) techniques. For comparison, the corrosion behavior of a Cu/NiFe-3 electrode to which current was not applied was also investigated. The corrosion tests showed that the corrosion resistance of the Cu/NiFe-3 cathode changed when a cathodic current was applied to the electrolysis system.     

Grain dependent electrochemical investigations on pure iron in acetate buffer pH 6.0

The influence of grain orientation on the electrochemical behaviour of iron in acetate buffer pH 6.0 was analyzed using a capillary microcell. Cyclic voltammetry and simultaneous capacity measurements were performed on the two crystal faces of an iron (1 0 0)/(1 1 1) bi-crystal, on the grain boundary between these two orientations and on several single grains of a coarse grain iron sample. The combination with electron back scattered diffraction (EBSD) yields the surface orientation of the analyzed grains and makes it possible to perform orientation dependent experiments on the polycrystalline metal. Clear differences in the electrochemical behaviour, e.g. in corrosion tendency and oxide formation rate were found between the orientations (1 0 0) and (1 1 1) of the iron bi-crystal and between several grain orientations of the polycrystalline sample.     

The structure and electronic properties of passive and prepassive films of iron in borate buffer

The films that form on pure iron during potentiodynamic anodic polarization in aqueous borate buffer were investigated by surface enhanced Raman spectroscopy (SERS), and by electrochemical impedance spectroscopy and Mott-Schottky analysis at selected potentials. According to SERS, the passive film is a bilayer film with an outer layer of an as yet undetermined Fe(III)oxide/hydroxide, identified by a strong Raman peak at 560 cm⁻¹. The inner layer was a spinel compound. The capacitances of passive iron were frequency dependent and a constant phase element (CPE) best described the frequency dispersion. Current increases in cathodic polarization scans confirmed the accuracy of flatband potentials calculated from Mott-Schottky tests at two different film formation potentials. Both films were found to be n-type and flatband potentials of −846 and −95 mV vs. SHE and carrier densities of 1.6 × 10²² and 8.3 × 10²⁰/cm³ were found for films grown at −500 and +1000 mV, respectively. The cathodic polarization curve of passivated iron exhibited a complex shape that was explained by the electronic properties of iron's passive and prepassive films. The reductive dissolution of the films abruptly began when the potential was lowered below their flatband potentials. It is suggested that the cathodic polarization behavior contributes to iron's susceptibility to localized corrosion.     

Electrochemical dissolution of hard metal alloys

Different components of hard metals such as TiC, TiN, pure Ti and the binder metals Fe, Co and Ni were investigated in neutral sodium nitrate solutions by cyclovoltammograms at current densities up to 35 A/cm². All combinations of TiN and TiC dissolve anodically. The surface of pure Ti is blocked by the anodic surface oxide which is not removed by cathodic current densities up to 30 A/cm². Cathodically all samples were conductive and showed a strong hydrogen evolution. The binder metals Fe, Co and Ni should be free of oxide films at cathodic potentials. Anodically, Co dissolves in an active state while Fe and Ni show a potential shift to the passive region. Our surface model developed for machining of Fe seems to be applicable to all other materials except pure Ti.     

In situ Raman spectroscopy and electrochemical techniques for studying corrosion and corrosion inhibition of iron in sodium chloride solutions

The corrosion of single crystal pure iron in 3.5% NaCl solutions and its inhibition by 3-amino-5-mercapto-1,2,4-triazole (AMTA) have been studied using in situ and ex situ Raman spectroscopy, cyclic voltammetry (CV), open-circuit potential (OCP), potentiodynamic polarization (PDP), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) measurements. CV experiments indicated that the iron electrode in the chloride solution alone showed an anodic peak at ∼−650 mV after the 5th cycle shifted to ∼−610 mV after the 20th cycle; another cathodic peak appeared at ∼−990 mV. In the presence of 1.0 mM AMTA, these two peaks shifted to ∼550 and −1050 mV, respectively. OCP, PDP, CA and EIS revealed that the presence of AMTA and the increase of its concentration move the corrosion potential to more positive values and decrease both the corrosion current and corrosion rate. This effect also increases with increasing the immersion time of iron electrode to 24 h in the test electrolyte. In situ and ex situ Raman investigations confirmed that the addition of AMTA molecules to the chloride solution strongly inhibits the iron corrosion through their adsorption onto the surface blocking its active sites and preventing its corrosion.     

Effect of 2-amino-3-mercaptopropanoic acid (cysteine) on the corrosion behaviour of low carbon steel in sulphuric acid

The effect of cysteine (cys) on the corrosion of low carbon steel (LCS) in sulphuric acid solution was investigated using electrochemical and scanning electron microscopy (SEM) techniques. Electrochemical impedance spectroscopy (EIS) results reveal that the presence of cys at low concentrations (0.1-0.5 mmol L⁻¹) promoted the LCS corrosion process, whereas an inhibiting effect was observed at higher concentrations (1.0-5.0 mmol L⁻¹), which was enhanced on deaeration of the test solution. Polarization results revealed that cys actually inhibited the cathodic process at all concentration but exerted a stimulating effect on the anodic metal dissolution reaction. Despite the cathodic inhibiting effect, the polarization resistances at low cys concentrations were less than that in the blank acid. This suggests that the anodic reaction was the predominant influence determining the corrosion rates in the presence of cys. This has been discussed vis-à-vis the catalytic effect of the Fe-cys complex, which turns the Fe surface more electrochemically active.     

Understanding aluminum behaviour in aqueous alkaline solution using coupled techniques: Part I. Rotating ring-disk study

Rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) measurements have been undertaken to study the behaviour of pure aluminum electrodes in alkaline media. The measurements did consist of linear sweep voltammetry from anodic to cathodic potentials on 4N, 5N or 5N5-aluminum samples in 4 M aqueous potassium hydroxide solution. In the potential range studied (−0.7 V versus NHE to −2.5 V versus NHE) the aluminum undergoes oxidation/dissolution into aluminates anions at high electrode potential while it yields strong hydrogen evolution at low potentials. Thanks to the RRDE technique, we show that hydrogen starts to evolve from the aluminum electrode even above the open circuit potential. Also, the oxidation state of superficial aluminum varies according to the electrode potential: whereas non-conducting aluminum oxides are present above the open-circuit potential hindering hydrogen evolution reaction (HER), they tend to disappear below the ocp, due to the strong hydrogen evolution, following the probable porous oxide layer blow up induced by the hydrogen bubbles formation. In consequence at very low potential, HER occurs on bare aluminum, HER kinetics being much faster than on oxide-covered aluminum.     

A comparative electrochemical study of iron deposition onto n- and p-type porous silicon prepared from lightly doped substrates

Electrodeposition of iron from acidic sulfate solutions onto porous silicon (PS) prepared from n- and p-type (1 0 0) substrates is studied by electrochemical measurements. Results from current-potential curves show that deposition of iron on p-type PS can only be achieved under illumination and cathodic polarization, whereas the deposition is found to proceed on n-type even in the dark. The measurements of the cathodic current efficiency indicate that the fraction of current used for iron deposition decreases with the applied potential due to hydrogen evolution reaction which is a competing reaction to metal deposition. Scanning electron microscopy shows that very fine iron crystallites with an average size of 40-70 nm are formed under double potential step conditions. The energy band diagrams of silicon-solution interfaces determined by electrochemical impedance measurements reveal that the iron deposition mechanism on both substrates is electron transfer from the conduction band.     

Kinetic and mechanistic study of CO2 corrosion inhibition by cetyl trimethyl ammonium bromide

The kinetics of the inhibition of carbon dioxide (CO₂) corrosion on high purity iron (Fe) electrodes by cetyl trimethyl ammonium bromide (CTAB) were investigated in order to elucidate the mechanism of inhibition. The test condition was: 25 °C, 3 wt.% NaCl brine, pH 4, 1 bar CO₂ partial pressure. The inhibition process was studied by electrochemical methods and by X-ray photoelectron spectroscopy (XPS). The inhibition was found to be a combination of two processes: first a rapid process (order of minutes) connected to diffusion limited adsorption of the inhibitor, leading to the inhibition of the anodic part reaction, and a second slower process (order of hours) leading to a reduction in the corrosion rate through the inhibition of the cathodic part reaction(s).     

Effect of anodic prepolarization on hydrogen entry into iron at cathodic potentials in 0.1 M NaOH without and with EDTA or sodium molybdate

Efficiency of cathodes for water electrolysis decreases after shut-downs due to corrosion at open-circuit potential. In the present work the effect of prepolarization at various potentials on hydrogen entry into iron during cathodic potential sweeps was studied by the measurement of the hydrogen permeation rate (HPR) through a 35-μm thick iron membrane in 0.1 M NaOH without and with EDTA or Na₂MoO₄ at 25 °C. Two types of the enhanced hydrogen entry at low cathodic polarizations were distinguished: one after prepolarization at low cathodic or low anodic potentials, and another after prepolarization at high anodic potentials. It is suggested that both types can be explained by acidification at the metal surface, the former due to anodic oxidation of iron, and the latter due to cathodic reduction of oxide layer (mainly of Fe₃O₄). XPS analysis revealed the presence of hydrated Fe-O species of unidentified valence. EDTA and Na₂MoO₄ increased the efficiency of hydrogen entry (j_H/j_c ratio), and molybdates also strongly increased cathodic currents of HER. Some of the effects of these additives can be explained in terms of their effect on surface layers.     

Electrochemical studies on the alternating current corrosion of mild steel under cathodic protection condition in marine environments

Alternating current (AC) corrosion of mild steel in marine environments under cathodic protection (CP) condition was studied. Electrochemical studies at the two protection potentials namely −780 and −1100 mV versus SCE were examined by different techniques. DC polarization study was carried out for mild steel in natural seawater and 18.5 g/L NaCl solution to evolve corrosion current density. The corrosion rate determination, pH of the end experimental solution and surface morphology of the mild steel specimens under the influence of different AC current densities were studied. The amount of leaching of iron into the solution was estimated using inductively coupled plasma spectrometry. All these techniques revealed that AC influences the corrosion of mild steel in the presence of marine environments even though CP was given. Surface micrographs revealed that spreading of red rust products noticed on the mild steel surface. At −780 mV CP, red rusts are visually seen when the AC source was above 10 A/m² in both the media but red rusts are appeared after 20 A/m² in the case of −1100 mV CP. Weight loss measurements coupled with surface examination and solution analysis is a effective tool to characterize and quantify the AC corrosion of mild steel in marine environments.     

Corrosion and passivation of iron and its nitrided layer in borate buffer

The aim of this work was to gain better understanding of the reasons of enhanced resistance to pitting corrosion of nitrogen-containing iron. Gas nitrided (570 °C, 4 h) and untreated Armco iron were examined in a borate solution of pH 8.4 without and with chlorides or ammonia. Enhanced pitting resistance and enhanced anodic currents were exhibited by nitrided Fe and also by untreated Fe in the solution with added ammonia. XPS showed that anodic films on nitrided Fe contained much larger amounts of iron oxides, in particular of magnetite, than those on untreated Fe. It is suggested that the anodic behaviour of nitrided Fe is determined mainly by the effect of evolving ammonia on corrosion products. Increased anodic dissolution can be explained by the formation of soluble complexes with ammonia, whereas increased amounts of magnetite can be due to the ammonia-promoted conversion of FeOOH + Fe(II) to Fe₃O₄. It is proposed that the enhanced pitting resistance of nitrided Fe results mainly from the formation of large amounts of iron oxides and from binding of chloride anions into a Fe-NH₃-Cl complex.     

Investigation of the surface properties and the hydrogen evolution reaction, HER, at thermal rhodium oxide electrodes

A systematic investigation was conducted of the surface properties and the HER at electrodes of nominal composition Ti/Rh_xTi_(1−x)O_y prepared by thermal decomposition (T_cal: 500 °C; t_cal: 2 h; O₂ flux: 5 dm³ min⁻¹) from salt precursor solutions dissolved in 6.0 mol dm⁻³ HNO₃. Films were characterized ex situ by SEM, EDX, XPS and XRD and in situ by open circuit potential measurements and CV. The electrochemical behaviour was investigated by CV as function of the anodic, E_λ,a, and cathodic, E_λ,c, switching potentials showing the Rh surface oxidation states strongly depend on these experimental variables. Surface Rh-sites are reduced to metallic rhodium in the cathodic potential region while higher oxidation states (I-III) are formed at more positive potentials (E ≥ 0.5 V/RHE). Hydrogen adsorption and desorption peaks as well as a short double layer charging region are observed at intermediate potential values. The HER was investigated by Tafel coefficients and reaction order with respect to H⁺ as function of nominal Rh-content.     

Influence of pulse plating parameters on the synthesis and preferred orientation of nanocrystalline zinc from zinc sulfate electrolytes

The influence of pulse electrodeposition parameters (current on-time T_on, current off-time T_off, and pulse current density J_p) was investigated on the surface morphology and grain size of zinc electrodeposited from a sulfate bath containing polyacrylamide and thiourea additives. The grain size and surface morphology of zinc deposits were studied by field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM), and the preferred orientation of the deposits was studied by X-ray diffraction. At constant current off-time and pulse current density, the grain size decreased asymptotically with increasing current on-time. In contrast, increase in the current off-time at constant current on-time and pulse current density resulted in grain growth. A progressive decrease of the grain size was observed with increasing pulse current density at constant current on-time and off-time. Nanocrystalline zinc with an average grain size of 38 nm was obtained at a pulse current density of 1200 mA/cm². The crystallographic orientations developed were correlated with the change in the cathodic overpotential, the angle between the preferred oriented plane and the lowest energy of formation plane (0 0 0 2), and the pulse electrodeposition parameters.     

The electrochemical generation of ferrate at porous magnetite electrode

In this work, ferrate(VI) was generated by the electrochemical oxidation of porous magnetite electrodes, made by melting pure magnetite grains. Pretreatment of the anode by cathodic polarization was necessary for ferrate(VI) generation and the achievement of high current efficiency. A electrolyte composition was found to be 16 M NaOH. In this electrolyte, the effect of anode current density J on Fe(VI) synthesis rate, current efficiency, and internal cell temperature were studied. An optimum result was obtained at J=3.3 mA cm⁻², 30 °C in 16 M NaOH for 5 h.     

Influence of 8-aminoquinoline on the corrosion behaviour of copper in 0.1 M NaCl

The corrosion behaviour of copper in aerated 0.1 M NaCl solution in presence of 8-aminoquinoline (8-AQ), using open circuit potential (OCP) measurements, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements and atomic force microscopy (AFM), was studied. The measurements revealed that the effect of 8-AQ is dependent on its concentration. For concentrations up to 10⁻³ M, the organic compound displaces the corrosion potential following no trend and also reduces the anodic current. In contrast, for concentrations higher than 10⁻³, 8-AQ reduces markedly both, the anodic and cathodic currents and consequently, the corrosion current density of copper. After 9 days of exposure in chloride solution, containing the organic compound, potentiodynamic polarization analyses showed a significant reduction in the anodic response and a less significant reduction in the cathodic response, which is associated with a film formed at the copper surface of about 10 μm in thickness and visually observed by a colour change of the copper surface.In order to elucidate the most likely interaction between the 8-AQ molecule and the different molecular structures probably present on copper surfaces in chloride solutions, some results obtained from theoretical calculations are presented. The following molecular structures were considered: CuCl molecule, CuCl₂⁻ complex, and little copper clusters defect representation built as five atoms on C_4v symmetry. Thus, based on the geometric, energetic, frontier orbital, and Total Electronic Density analysis done for the optimized states found for the systems investigated, we suggest that the most probable interaction of 8-AQ proceeds above CuCl units and free copper sites.     

Influence of electrochemical potential on the tribocorrosion behaviour of high carbon CoCrMo biomedical alloy in simulated body fluids by electrochemical impedance spectroscopy

The corrosion and tribocorrosion behaviour of a high carbon CoCrMo alloy sliding against alumina in simulated body fluids under potentiostatic conditions was investigated. The electrochemical behaviour of the sample in two electrolytes at different potentials (−1 V_Ag/AgCl, −0.5 V_Ag/AgCl, +0.05 V_Ag/AgCl, +0.5 V_Ag/AgCl and +0.75 V_Ag/AgCl) was studied by means of electrochemical impedance spectroscopy (EIS). The effects of solution chemistry and applied potential on the wear volume and anodic current were determined. Result shows that wear of CoCrMo alloy is negligible under cathodic and in the cathodic-anodic transition and considerably increases in the passive domain. Third body behaviour depends on surface chemistry which also varied depending on solution chemistry and electrochemically applied potential thus, modifies the tribocorrosion rate of CoCrMo alloy.     

Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

Steel corrosion in alkaline batteries

During extended shelf storage and accelerated aging, low carbon steel may corrode producing soluble iron species that cause internal cell shorting and/or gassing (leakage), thus undermining battery reliability. Soluble iron may be generated from the active/passive and/or transpassive dissolution of the battery can steel. To minimize corrosion effects in commercial battery applications, NiCo plated steel is typically used. This report focuses on corrosion behavior of pure metals (iron, nickel, and cobalt) in 40% KOH at temperatures between 20 °C and 80 °C. A marked difference is found for the elements regarding the actual passivating behavior with time and temperature. As expected, nickel spontaneously passivates at all temperatures under study (20-80 °C). Cobalt on the other hand, is active at all temperatures but shows an active/passive-transition. Iron spontaneously passivates only at temperatures below 60 °C and activates at temperatures >60 °C. At sufficiently anodic potentials, passivity of Fe is lost by transpassive Fe dissolution to form ferrates [FeO₄]²⁻. The latter is considered the most likely cause for corrosion-induced failure in alkaline batteries.     

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.