Kinetics of hydrogen evolution reaction on nanocrystalline electrodeposited Ni62Fe35C3 cathode in alkaline solution by electrochemical impedance spectroscopy

Ternary nickel-iron-carbon (Ni-Fe-C) alloys have been characterized by means of microstructural and electrochemical techniques in view of their possible applications as electrocatalytic materials for hydrogen evolution reaction (HER). The electrochemical efficiency of the electrodes has been evaluated on the basis of electrochemical data obtained from the steady-state polarization Tafel curves, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 M NaOH solution at 298 K in the absence and presence of cyanide ion as the poison. Steady-state polarization Tafel curves showed that the Ni-Fe-C electrodes were apparently active for the HER. Therefore, the EIS studies were performed to obtain more precise data and find the source of activity. A surface roughness of more than three orders of magnitude was observed for Ni₆₂Fe₃₅C₃ electrode. The rate constants of the forward and backward reactions of Volmer and Heyrovský steps were estimated by using Tafel-impedance data. A comparison between the values obtained for R_f by the EIS and the values obtained for k₂ by approximation of Tafel-impedance data revealed that the increase in activity of Ni₆₂Fe₃₅C₃ electrode toward the HER was partially (20%) originated from increase in the surface roughness, and mostly (80%) from increase in the intrinsic activity.     

Effect of silicon alloying addition on the corrosion behaviour of aluminium in some aqueous media

The corrosion behaviour of three Al–Si alloys was studied after galvanostatic passivation in 0.1 M sodium tartrate, sulfate and borate solutions using EIS techniques. The degree of passivation depends on the anion type, the degree of polarization and the alloy composition. It was also found that increase in pH led to a decrease in polarization resistance R _p. The effect of formation voltage, V _f, on the growth and dissolution kinetics of the oxide grown on the alloys was studied. The polarization resistance value increases as V _f increases up to a certain value; above this the R _p value decreases. This critical V _f depends on the alloy composition and the test solution. The kinetics of oxide layer dissolution in the absence and presence of Cl^– ions was also studied. Increase in immersion time leads to a more severe attack by Cl^– ions as shown by the decrease in the value of R _p. At low Cl^– ion concentration the value of R _p is higher than that in chloride ion free sulfate solutions, because the rate of passive film repair is much higher than that of barrier layer dissolution. However, at high Cl^– ion concentration penetration of Cl^– through defects in the barrier layer leads to formation of an oxyhalide layer.     

Participation of the dissolved O2 in the passive layer formation on Zn surface in neutral media

The composition of the passive layers formed on Zn electrode in naturally aerated and de-aerated 0.1 M KClO₄ solution were studied using X-ray photoelectron spectroscopic measurements (XPS). A correlation between the presence of dissolved O₂ and the formation of an interior passive layer was carried out. Librated Cl⁻ from the perchlorate reduction reaction was detected in its solutions during Zn electrode polarization. The librated Cl⁻ concentration reached its maximum value at −1.4 V. Moreover, in the studied potential range the perchlorate reduction rate increases in absence of dissolved oxygen. Chrono-amperometry and electrochemical impedance spectroscopy (EIS) were performed for the stationary and the rotating disc Zn electrodes in naturally aerated and de-aerated 0.1 M KClO₄ solution. EIS technique showed a change in the electrode impedance with the experimental conditions as a result of changing the reactions occurring in the electrode vicinity. The obtained data were fitted to three different equivalent circuits depending on the electrode potential. The protective nature of the passive layers formed in different experimental conditions was found to decrease with rotating the electrode and de-aerating the solution.     

In situ oxidation/lithiation of Ni-Co alloy in the molten Li0.62/K0.38 carbonates eutectics

In situ oxidation/lithiation reaction of the pure Ni and Ni-Co alloy electrodes were studied in molten Li_0.62/K_0.38 carbonate eutectics saturated with a 0.9O₂ + 0.1CO₂ atmosphere at 923 K. Ni-Co alloy electrodes were prepared on the pure Au foil by the galvanostatic pulse plating method. Open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) were employed to investigate the in situ oxidation /lithiation reaction of electrodes. OCP variation of Ni and Ni-Co alloy electrodes was divided into four regions and charge transfer resistance (R_ct) and diffusion resistance (R_diff) measured as a function of OCP/immersion time in EIS experiment strongly depended on the composition of Ni-Co alloy electrodes and the electrochemical-catalytic activity of Ni-Co alloy electrodes was affected by the surface roughness. In XRD analysis and micro-Raman spectroscopy (RS), the lithiation content increased proportionally with the amount of cobalt in Ni-Co alloy electrodes, which was an important factor to determine the electrochemical-catalytic activity of electrodes.     

Electrochemical impedance spectroscopy of oxygen and hydrogen evolution on amorphous alloys in 1 M KOH

The mechanisms of oxygen and hydrogen evolution on amorphous alloys G 14 (Fe₆₀Co₂₀Si₁₀B₁₀) and G 16 (Co₅₀Ni₂₅Si₁₅B₁₀) in 1 M KOH at T = 298 K and 333 K were studied by electrochemical impedance spectroscopy (EIS). Comparative measurements were carried out on polycrystalline Pt electrodes. Impedance spectra in the frequency range 10^?3 Hz ≤ f ≤ 10⁴ Hz were analyzed to determine the kinetic behaviour of amorphous alloys by application of transfer function analysis, using non-linear fit routines. The EIS-data are interpreted in terms of consecutive reaction mechanisms for both oxygen and hydrogen evolution.     

Structure and electrochemical characteristics of TiV1.1Mn0.9Nix (x = 0.1-0.7) alloys

The structure and electrochemical properties of TiV_1.1Mn_0.9Ni_x (x = 0.1-0.7) solid solution electrode alloys have been investigated. It is found that these alloys mainly consist of a solid solution phase with body centered cubic (bcc) structure and a C14 Laves secondary phase. The solid solution alloys show easy activation behavior, high temperature dischargeability, high discharge capacity and favorable high-rate dischargeability as a negative electrode material in Ni-MH battery. The maximum discharge capacity is 502 mAh g⁻¹ at 303 K when x = 0.4. Electrochemical impedance spectroscopy (EIS) test shows that the charge-transfer resistance at the surface of the alloy electrodes decreases obviously with increasing Ni content.     

Effect of Al content on the electrochemical properties of Mg2−xAlxNi thin film hydride electrodes

Thin films of Mg_2−xAl_xNi alloys have been prepared by magnetron sputtering, and the effects of partial substitution of Al for Mg on the electrochemical properties of the films were studied. EIS results indicate the rate-limiting process for the thin film hydride electrode is the charge transfer reaction during the process of total discharge. A theoretical model has been derived for the impedance of a thin film hydride electrode based upon the assumption that hydrogen diffusion is neglected in the electrode. The charge-transfer reaction rate at the electrode surface and hydrogen diffusivity in the Mg_2−xAl_xNi thin film hydride electrodes were observed to initially decrease then increase with increasing Al content. Results from capacitance measurements indicate n-type semiconductor properties for the corrosion layer during the charge–discharge process. Hydrogen atom and OH⁻ transfer became more difficult with increasing Al content until x = 0.3, after which a significant drop in the barrier resistance was observed.     

Low temperature electrochemical properties of LaNi4.6−xMn0.4Mx (M = Fe or Co) and effect of oxide layer on EIS responses in metal hydride electrodes

Iron is a key element in the development of Co-free AB₅-type hydrogen storage alloys. The aim of this work is to systematically investigate the effects of Fe and Co on the electrochemical properties of LaNi_4.6−xMn_0.4M_x (M = Fe or Co, x = 0, 0.25, 0.5 and 0.75) hydrogen storage alloys under relatively low temperatures (273, 253 and 233 K). The results showed that substitution of Fe for Ni reduced the low temperature electrochemical performance much more seriously than that of Co. Exchange current density (I₀), charge-transfer resistance (R_ct) and hydrogen diffusion coefficient (D) were determined based on the study of linear polarization, electrochemical impedance spectrum (EIS) and galvanostatic discharge, respectively. Both the hydrogen diffusion in the bulk of alloy particles and the electrochemical reaction at the alloy electrolyte interface were found to be greatly limited as the decrease of temperature. During the EIS analysis, interestingly, we found that the semicircle in the high frequency region increased dramatically with the decrease of temperature. The electrochemical process corresponding to this semicircle was proposed to be related to the oxide layer on the surface of alloy particles. Novel explanations of EIS response in metal hydride electrodes were proposed accordingly.     

Effective MgO surface doping of Cu/Zn/Al oxides as water–gas shift catalysts

Trace amounts of MgO were doped on Cu/ZnO/Al₂O₃ catalysts with the Cu/Zn/Al molar ratio of 45/45/10 and tested for the water–gas shift (WGS) reaction. A mixture of Zn(Cu)–Al hydrotalcite (HT) and Cu/Zn aurichalcite was prepared by co-precipitation (cp) of the metal nitrates and calcined at 300 °C to form the catalyst precursor. When the precursor was dispersed in an aqueous solution of Mg(II) nitrate, HT was reconstituted by the “memory effect.” During this procedure, the catalyst particle surface was modified by MgO-doping, leading to a high sustainability. Contrarily, cp-Mg/Cu/Zn/Al prepared by Mg²⁺, Cu²⁺, Zn²⁺ and Al³⁺ co-precipitation as a control exhibited high activity but low sustainability. Mg²⁺ ions were enriched in the surface layer of m-Mg–Cu/Zn/Al, whereas Mg²⁺ ions were homogeneously distributed throughout the particles of cp-Mg/Cu/Zn/Al. CuO particles were significantly sintered on the m-catalyst during the dispersion, whereas CuO particles were highly dispersed on the cp-catalyst. However, the m-catalyst was more sustainable against sintering than the cp-catalyst. Judging from TOF, the surface doping of MgO more efficiently enhanced an intrinsic activity of the m-catalyst than the cp-catalyst. Trace amounts of MgO on the catalyst surface were enough to enhance both activity and sustainability of the m-catalyst by accelerating the reduction–oxidation between Cu⁰ and Cu⁺ and by suppressing Cu⁰ (or Cu⁺) oxidation to Cu²⁺.     

Electrodeposition of Zn and In onto vitreous carbon

The deposition of indium and zinc on vitreous carbon was studied by voltammetric, galvanostatic and single potentiostatic pulse techniques. The morphology and composition of deposits were analysed by SEM/EDX. The codeposition process occurs without the formation of alloys or intermetallic compounds. On the one hand under stagnant conditions or at low electrode rotation speeds, localized alkalization produced by the hydrogen evolution reaction (HER) favours deposition through an indium hydroxide layer, and deposits with the same atomic percentage of In and Zn are attained. On the other hand, under electrode rotation, preferred deposition of Zn takes place. In this case, the reduction of H⁺ by the In⁺ species, intermediate in the In³⁺ reduction process, diminishes the electrochemical HER on the substrate thus favouring Zn deposition. The higher nucleation rate on metallic deposits previously formed on the vitreous carbon surface is also likely.     

Corrosion behavior of different alloys exposed to continuous flowing seawater by electrochemical impedance spectroscopy (EIS)

The corrosion of four types of alloys, under a dynamic condition, has been studied in continuous fresh seawater system using electrochemical impedance spectroscopy (EIS) technique. The materials used in this study were stainless steel 304, Cu-Ni 70-30, Hastelloy G-30, and titanium. The total exposure time of the test was 180 days, in continuous fresh seawater of the Gulf in Kuwait. The EIS tests were carried out by using EG&G software and hardware instrument. Electrochemical parameters such as the polarization resistance (R_P), solution resistance (R_Sol), and the double layer capacitance (C_dL) of these alloys were determined. Then the obtained EIS parameters were used to study the effect of the seasonal change of the Gulf seawater on the corrosion behavior of the tested materials. All the obtained EIS parameters showed that the seasonal changes of the Gulf seawater have a significant effect on controlling the rate of the formation of the marine bio-film on the surface of tested materials. Consequently, the corrosion behavior of the materials tends to vary as a function of the rate formation of the marine bio-film on the surface of tested materials.     

Dielectric properties of CaCu3Ti4O12 ceramics with Zn substitution for Cu

Abstract

CaCu_3–xZn_xTi₄O₁₂ (x is from 0 to 1·0) polycrystalline samples were fabricated via a two-step solid state reaction process. The lattice parameter of the monophasic CaCu₃Ti₄O₁₂ phase increased as Zn content increased. Scanning electron microscopy (SEM) images of the CCTO ceramic show bimodal grain size distribution and the grain size decrease largely with the appearance of Zn₂TiO₄ second phase. The dielectric permittivity of pure CCTO ceramic is ～1·5×10⁴ at f?=?100 Hz. The dielectric constant of the sample largely increased with Zn substitution in the frequency range f<10⁴ Hz. The highest dielectric constant was 6·2×10⁴ at f?=?100 Hz with Zn substitution of x?=?0·8. The improved dielectric properties are believed to be related to the presence of a thin grain boundary barrier layer. The resistivity of the grain boundary decreased largely with Zn substitution as evidenced from the impedance plots.     

Estimation of the effectiveness factor of an outer-sphere redox couple (Fe3+/Fe2+) using rotating disk Ti/IrO2 electrodes of different loading

The effectiveness factor; E _f , defined as the fraction of the surface that participates effectively in a given reaction, is an important parameter when operating three-dimensional (3D) electrodes. The rotating disk electrode (RDE) technique with the Fe³⁺/Fe²⁺ redox couple as a probe reaction has been used for the evaluation of the effectiveness factor of 3D Ti/IrO₂ electrodes with different IrO₂ loading. For this purpose, steady-state polarization measurements using Ti/IrO₂ rotating disk electrodes in 0.5 M Fe³⁺/Fe²⁺ in 1 M HCl were carried out under well-defined hydrodynamic conditions. The low-field approximation relation has been used for the estimation of the exchange current densities j ₀, of the Fe³⁺/Fe²⁺ redox couple. It was found for this redox couple that the effectiveness factor is very low (<2%) and essentially the 2D electrode surface area works effectively in the steady-state polarization measurements.     

Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Sulfolane (also referred to as tetramethylene sulfone, TMS) containing LiPF₆ and vinylene carbonate (VC) was tested as a non-flammable electrolyte for a graphite |LiFePO₄ lithium-ion battery. Charging/discharging capacity of the LiFePO₄ electrode was ca. 150 mAh g⁻¹ (VC content 5 wt%). The capacity of the graphite electrode after 10 cycles establishes at the level of ca. 350 mAh g⁻¹ (C/10 rate). In the case of the full graphite |1 M LiPF₆ + TMS + VC 10 wt% |LiFePO₄ cell, both charging and discharging capacity (referred to cathode mass) stabilized at a value of ca. 120 mAh g⁻¹. Exchange current density for Li⁺ reduction on metallic lithium, estimated from electrochemical impedance spectroscopy (EIS) experiments, was j_o(Li/Li⁺) = 8.15 × 10⁻⁴ A cm⁻². Moreover, EIS suggests formation of the solid electrolyte interface (SEI) on lithium, lithiated graphite and LiFePO₄ electrodes, protecting them from further corrosion in contact with the liquid electrolyte. Scanning electron microscopy (SEM) images of pristine electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of SEI formation. No graphite exfoliation was observed. The main decomposition peak of the LiPF₆ + TMS + VC electrolyte (TG/DTA experiment) was present at ca. 275 °C. The LiFePO₄(solid) + 1 M LiPF₆ + TMS + 10 wt% VC system shows a flash point of ca. 150 °C. This was much higher in comparison to that characteristic of a classical LiFePO₄ (solid) + 1 M LiPF₆ + 50 wt% EC + 50 wt% DMC system (T_f ≈ 37 °C).     

Improvement of methane activation using n-hexane as co-reactant over Zn/HZSM-11 zeolite

Significance of effective conversion of methane (C₁) to more valuable compounds such as aromatics is studied using n-hexane (C₆) as co-reactant. AH yield was as high as 30 mol% C using the following reaction conditions: temperature, 500 °C; contact time w/f=30 g h mol⁻¹ and a C₁ molar fraction, X_C1:=(C₁/C₁ + C₆)=0.60, was achieved. The effect of the contact time, molar fraction, and time on stream was analyzed in order to obtain more information about different species evolution. The C₁ conversion reached at 50 mol% C using Zn/HZSM-11 with 2.13 mol Zn per cell unit.     

Influence of voltammetric parameters on Zn–Ni alloy deposition under potentiodynamic conditions

The phase composition of Zn–Ni alloys electrodeposited from acetate-chloride plating solutions containing Zn⁺² and Ni⁺² ions at ratio of 1–12.8 at 50 °C was investigated by the potentiodynamic stripping method. Two anodic current density (i _a) peaks emerged in potentiodynamic stripping curves (PDC) at E < 0.0 V and E > 0.0 V (vs. Ag/AgCl/KCl_sat), that were attributed to oxidation of certain phases of the Zn–Ni alloy. The ratio of these phases in deposited Zn–Ni alloys under potentiodynamic conditions was affected by the potential sweep rate (ν) and maximum cathodic current density (i _c) The ratio of Zn and Ni in certain phases of Zn–Ni alloy was determined by the partial potentiodynamic stripping technique. Experimental data show that Zn–Ni alloy, containing 6.5 at.% Zn and 93.5 at.% Ni and dissolved in i _a peak H (E > 0.0 V), provides the black coloration of the Zn–Ni alloy.     

Phase structure and electrochemical properties of Ml1?xMgxNi2.78Co0.50Mn0.11Al0.11 hydrogen storage alloys

The effect of magnesium content on the phase structure and electrochemical properties of Ml_1−x Mg _x Ni_2.78Co_0.50Mn_0.11Al_0.11 (x = 0.05, 0.10, 0.20, 0.30) hydrogen storage alloys was investigated. The results of X-ray diffraction reveal that all the alloys consist of the major phase (La, Mg)Ni₃ and the secondary phase LaNi₅. With increase in x, the relative content of the (La, Mg)Ni₃ phase increases gradually, and the maximum capacity and low temperature dischargeability of the alloy electrodes first increase and then decrease. When x is 0.20, the discharge capacity of the alloy electrode reaches 363 mAh g⁻¹ at 293 K and 216 mAh g⁻¹ at 233 K, respectively. The high rate dischargeability of the alloy electrodes increases with increase in x. When the discharge current density is 1200 mA g⁻¹, the high rate dischargeability of the alloy electrodes increases from 22.0% to 50.4% with x increasing from 0.05 to 0.30. The cycling stability of the electrodes decreases gradually with increase in magnesium content.     

Catalytic Activation of Methane Using n-Pentane as Co-reactant over Zn/H-ZSM-11 Zeolite

The catalytic conversion of methane (C1) into higher hydrocarbons using n-pentane (n-C5) as co-reactant over Zn/H-ZSM-11 zeolite material was studied. The aromatics yield was very high, achieving values of over 40 mol% at 500 °C and w/f = 30 g h mol_-1 with a C1/(C1+C5) molar fraction (XC1) = 0.30. Contact time and time-on-stream effects on the product distribution were analyzed in detail in order to obtain information about the evolution of different species. The C1 conversion was as high as 30 mol% without CO _x reaction products.     

Characterizations of TiO2/SiO2/Ni–Cu–Zn Ferrite Composite for Magnetic Photocatalysts

The TiO₂/SiO₂/Ni–Cu–Zn ferrite composite for magnetic photocatalysts with high photocatalytic activity is successfully prepared in this study. The composite are composed of spherical or elliptical Ni–Cu–Zn ferrite nanoparticles about 20–60 nm as magnetic cores, silica as barrier layers with thickness of 15 nm between the magnetic cores and titania shells with thickness approximately 1.5 nm. Photodegradation examination of TiO₂/SiO₂/ Ni–Cu–Zn ferrite composite was carried out in methylene blue (MB) solutions illuminated under a Xe arc lamp with 35 W and color temperature of 6000 K. The results indicated that about 47.1% of MB molecules adsorbed on the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite within 30 min mixing due to it higher pore volume of 0.034 cm³/g, and after 6 h Xe lamp irradiation, 83.9% of MB 16.1% was photodegraded. Compared with the TiO₂ /Ni–Cu–Zn ferrite composite, the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite with silica barrier layer prohibited the photodissolution and enhanced the photocatalytic ability. The magnetic photocatalyst shows high photocatalytic efficiency that the apparent first‐order rate constant k_obs is 0.18427 h^?1, and good magnetic property that the saturation magnetization (M_s) of is 37.45 emu/g, suggesting the magnetic photocatalyst can be easily recovered by the application of an external magnetic field.     

Effects of Zn and Pb as alloying elements on the electrochemical behaviour of brass in borate solutions

The electrochemical behaviour of brasses with various Zn content (5.5–38) and brass (Cu–38Zn) with different Pb content (1.3–3.3) in borate solution, pH 9.0, was investigated. The effects of applied potential and the presence of aggressive Cl^– ions were also studied. Different electrochemical methods such as open-circuit potential measurements, polarization techniques and electrochemical impedence spectroscopy (EIS) were used. Increase in zinc content decreases the corrosion rate of brass in borate solution exponentially. Long immersion of leaded brasses and alloys with different Zn content improves their stability due to the formation of a passive film. The passive film formation under open-circuit and potentiostatic conditions proceeds via dissolution–precipitation mechanism. The addition of a low concentration of Cl^– ion (0.01 M) to the borate solution increases the corrosion rate of Cu–38Zn due to dezincification. Increase in Cl^– ion concentration (0.01–0.2 M) decreases the corrosion rate of the brass exponentially due to formation of insoluble CuCl. For Cl^– ion concentrations >0.2 M the corrosion rate of the brass increases again due to the formation of the soluble CuCl₂ ^– complex.