The stability of hydrogen evolution activity and corrosion behavior of NiCu coatings with long-term electrolysis in alkaline solution

In this study, NiCu composite coating was electrochemically deposited on a copper electrode (Cu/NiCu) and tested for hydrogen evolution reaction (HER) in 1 M KOH solution for long-term electrolysis with the help of cathodic current–potential curves and electrochemical impedance spectroscopy (EIS) techniques. The bulk and surface composition of the coating was determined using atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analysis. The surface morphology was investigated by scanning electron microscopy (SEM). The effect of electrolysis on the corrosion behavior of the Cu/NiCu electrode was also reported. It was found that the NiCu coating had a compact and porous structure with good time stability. The HER activity of the coating was stable over 120 h electrolysis and the HER mechanism was not modified during the operation. The corrosion tests showed that the corrosion resistance of the Cu/NiCu electrode changed when a cathodic current was applied to the electrolysis system.     

The stability of NiCoZn electrocatalyst for hydrogen evolution activity in alkaline solution during long-term electrolysis

The long-term stability of NiCoZn coating for hydrogen evolution reaction (HER) was investigated in 1 M KOH solution under 100 mA cm⁻² current density at room temperature. The effect of electrolysis on the corrosion behavior of NiCoZn coating was also studied. The alloy prepared on a copper electrode (Cu/NiCoZn) was etched in a concentrated alkaline solution (30% NaOH) to produce a porous and electrocatalytic surface suitable for use in the HER. The bulk and surface compositions of coating before and after alkaline leaching were determined by atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analysis. The surface morphologies of freshly prepared and aged electrodes were investigated by scanning electron microscopy (SEM). Their catalytic activity towards the HER was assessed by recording cathodic current–potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the NiCoZn coating has a compact and porous structure. The long-term operation at 100 mA cm⁻² current density showed that the electrochemical activity of Cu/NiCoZn electrode increased slightly with increasing electrolysis time. The activation of electrode related to the removal of any existing corrosion products and accumulations from the pores and formation of cracks during hydrogen gas evolution. The corrosion tests showed that the corrosion resistance of Cu/NiCoZn electrode changed after electrolysis.     

The Ni-deposited carbon felt as substrate for preparation of Pt-modified electrocatalysts: Application for alkaline water electrolysis

A Ni-modified carbon felt (C) electrode (C/Ni) was used as a substrate for preparation of Pt-modified electrode in view of its possible application as electrocatalytic material for the hydrogen evolution activity. The prepared electrode was characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and cyclic voltammetry (CV) techniques. The hydrogen evolution activity of the electrode was assessed by cathodic current–potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the modification of Ni-deposited C by loading low amount of Pt could enhance the hydrogen evolution activity of the electrode.     

Enhancement of hydrogen evolution at cobalt-zinc deposited graphite electrode in alkaline solution

Thin Co layers were electrochemically deposited on a graphite electrode at different deposition current densities and thicknesses. After determining the best deposition conditions for hydrogen evolution (deposition current density and thickness), co-deposits of Co with Zn were prepared on the graphite electrode. The binary coatings prepared on the graphite electrode (CoZn) were etched in a concentrated alkaline solution (30% NaOH) to produce a porous and electrocatalytic surface suitable for use in the hydrogen evolution reaction (HER). After the leaching process, a low amount of Pt was deposited onto the etched CoZn deposit in order to further improve the catalytic activity of the electrode for the HER. The HER activity is assessed by recording cathodic current-potential curves, electrochemical impedance spectroscopy (EIS) and electrolysis techniques. Chemical composition of layers after alkaline leaching was determined by energy dispersive X-ray (EDX) analysis. The surface morphologies of coatings were investigated by scanning electron microscopy (SEM). It was found that, the HER activity of coatings depends on the metal ratio of Co and Zn, deposition current density and the thickness of coatings. The alkaline leached CoZn coating has a compact and porous structure as well as good electrocatalytic activity for the HER in alkaline media. Moreover, deposition of a low amount of Pt over the CoZn can further enhance its hydrogen evolution activity.     

Fabrication and characterization of NiCoZn-M (M: Ag, Pd and Pt) electrocatalysts as cathode materials for electrochemical hydrogen production

Ag, Pd and Pt-modified alkaline leached NiCoZn composite coatings were prepared on a copper specimen by electrochemical technique. The chemical composition of layers before and after leaching as well as after noble metal modification was determined by energy dispersive X-ray spectroscopy (EDX). The surface morphologies of the composite coatings were examined with the help of scanning electron microscopy (SEM). The hydrogen evolution activity of the electrodes was studied in 1 M KOH solution. For this purpose, cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques were used. Furthermore, the change of hydrogen evolution activity of the electrodes as a function of operation time in alkaline solution was also investigated. Surface morphologies showed that the composite coatings prepared to have compact and porous surface. EDX analysis confirmed the presence of Ag, Pd and Pt metals over the NiCoZn layer. The co-deposition of nickel, cobalt and zinc on copper surface and subsequently alkaline leaching of zinc rendered cathode material very active in hydrogen evolution. The modification of alkaline leached NiCoZn ternary coating by deposition of small amounts of Ag, Pd and Pt can further enhance the hydrogen evolution performance of this Raney-type electrode when compared to NiCoZn individually. The order of hydrogen evolution activity of catalysts studied is Ni < NiCoZn < NiCoZn-Pd < NiCoZn-Ag < NiCoZn-Pt. The long-term electrolysis tests showed that the Pt-modified electrode has the better time stability than the others. The superiority of Pt-modified catalyst explained by well known intrinsic catalytic activity of Pt.     

CuFe electrocatalyst for hydrogen evolution reaction in alkaline electrolysis

The development of high performance, stable catalyst with non-precious metals for electrochemical hydrogen evolution reaction for alkaline electrolysis is in demand. Here-in, we report the synthesis of CuFe layered double hydroxide (LDH) electrocatalyst on nickel foam via facile hydrothermal method. In alkaline electrolysis with 1 M NaOH electrolyte, CuFe LDH as cathode requires an overpotential of 159 mV to generate current density of 10 mA cm⁻². Which is ca. 51 mV and 7 mV lower than NiFe LDH and NiRu LDH. CuFe LDH exhibits significant electrocatalytic activity for HER. The higher catalytic activity of CuFe LDH compared to NiFe LDH may be achieved with higher proton adsorption by Cu compared to Ni. Also, the efficient charge transfer with interconnected LDH layers, favourable three dimensional structure facilitating easy electrolyte transfer to the active sites and hydrogen gas diffusion. This work may help in developing low cost and efficient hydroxide catalyst.     

The effect of 3D silver nanodome size on hydrogen evolution activity in alkaline solution

Three-dimensional (3D) Ag nanodomes (AgNDs) having different sizes (400, 800, 1200 and 1600 nm) were fabricated using combination of nanosphere lithography and soft lithography. The surface structures of 3D assembled latex particles, nanovoids and metal nanodomes (ND) were examined using scanning electron microscopy (SEM). Their heights and widths analyses were performed with the help of atomic force microscopy (AFM). The effect of diameter of the NDs on their hydrogen evolution activity was examined in 6 M KOH solution at 298 K using electrochemical techniques. Their activities were compared with the activity of bulk Ag electrode. The preparation of 3D-AgNDs having various diameters and examination of their size effects on the water splitting activity have not been studied yet and are being reported firstly. It was found that very well-structured and very uniformly distributed NDs can be fabricated using this procedure. AgNDs exhibit higher hydrogen evolution activity with respect to bulk Ag. Their hydrogen evolution activity depends on their diameters; 1200 nm NDs were the best among them. The current density at ?1.40 V(Ag/AgCl) which is proportional to the rate of hydrogen releasing reaction increases from 0.70 mA cm^?2 to 44.13 mA cm^?2 at this ND electrode with respect to the bulk Ag electrode. At the same 3D-AgNDs electrode and potential, the resistance against the HER reduces from 148.7 Ω cm² to 1.12 Ω cm² (99.6%) by comparing with the bulk Ag electrode. The average surface roughness factors of bulk Ag, 400 nm, 800 nm, 1200 nm and 1600 nm AgNDs are 8, 123, 100, 291 and 176, respectively. The superior hydrogen evolution performance of this electrode is related to its well-structured surface and large real surface area.     

Quaternary-metal phosphide as electrocatalyst for efficient hydrogen evolution reaction in alkaline solution

Hydrogen evolution reaction (HER) is a critical process in electrocatalytic water splitting for hydrogen production. However, the development of low-cost electrocatalysts for highly efficient HER is still a huge challenge. Hence, we fabricate a multi-metal phosphide on Ni foam, FeCoNiNb_xP, through a facile hydrothermal reaction followed by phosphorization. We find that Nb promotes the formation of metal phosphides, and the main phases of the catalysts with Nb are multiphase phosphides. Importantly, the Nb incorporation significantly improves the HER activity of FeCoNiP. We show that FeCoNiNb_0.3P has the best HER activity, which only requires an overpotential of 78 mV to achieve a current density of 10 mA cm^?2 in 1 M KOH, and demonstrates excellent stability under both constant potential and varied current densities. Our findings show that the multiple-metal compounds are beneficial to the improvement of catalytic activity and provide guidance on the design of novel catalysts for applications.     

Nanocoral-like NiSe2 modified with CeO2: A highly active and durable electrocatalyst for hydrogen evolution in alkaline solution

The excessive exhaustion of conventional fossil fuels and increasingly severe environmental issues prompt us to grope for high-performance and cost-effective catalysts for hydrogen evolution reaction (HER) by electrocatalytic water splitting. In this work, nanocoral-like NiSe₂ catalysts modified with CeO₂ have been successfully prepared through one-pot hydrothermal route and utilized to electrocatalytic HER in alkaline solution. It turns out that nanocoral-like NiSe₂ (labeled as CNS-2) catalyst delivers current densities of 10 and 50 mA cm⁻² at overpotentials of only 130 and 242 mV, respectively. Additionally, CNS-2 takes on a small Tafel slope of 115 mV dec⁻¹ and low charge transfer resistance, revealing a quicker Faradaic process and more favorable HER kinetics. Furthermore, it displays considerable long-term stability during the constant hydrogen producing. The strategy of fabricating NiSe₂ modified with CeO₂ unfolds a novel angle of view for exploiting highly efficient and durable catalysts for electrocatalytic HER.     

Study of the oxygen evolution reaction on nickel-based composite coatings in alkaline media

Electrolytic Ni + Mo and Ni + Mo + Si coatings were prepared by co-deposition of nickel with silicon and molybdenum powders from a nickel bath in which Mo and Si particles were suspended by stirring. Modification of the surface of the Ni + Mo + Si electrodes was carried out by leaching out of the Si particles in alkaline solution. In this paper coatings modified in that way were denoted as Ni + Mo_Si. Electrochemical measurements were undertaken on both Ni + Mo composite coating and modified Ni + Mo_Si composite coating after thermal treatment in air (700 °C, 1 h). It was stated that composite coatings are characterized by very porous surface in comparison with nickel coating after the same thermal treatment. Apparent activity for OER on the obtained coatings was studied by means of both dc and ac electrochemical methods in 5 M KOH. In the Tafel plots determined for the OER, two well defined and the same slopes were observed for all investigated electrodes. This fact indicates that the OER on all obtained electrodes is controlled by the same mechanism. It has been stated that additional ingredients in the coating and modification of the surface cause an increase in electrochemically active surface area and improve electrochemical characteristics of the coatings in OER.     

Electrodeposition of NiCu bimetal on 3D printed electrodes for hydrogen evolution reactions in alkaline media

In this study, hydrogen evolution electrodes are prepared by a 3D printing method using conductive PLA filament. To improve their conductivity and electrochemical performance, Nickel–Copper (NiCu) binary coating is deposited on 3D printed (3DP) electrodes in a solution bath with different volume ratios. Electrodes have been prepared as NixCux, NixCu2x, and NixCu3x according to Ni and Cu volume ratio (Ni–Cu; 10-10, 10–20, and 10–30 mL, respectively). Surface morphologies of the samples are measured using FE-SEM, EDX and XRD techniques. Electrochemical characterizations are investigated by LSV, CV and EIS. According to the results, the current density of NiCu coated 3DP electrodes is higher than the uncoated 3DP electrode. The results show that the resistance values of the electrodes are decreased from 0.262 kΩ to 0.187 kΩ in NixCu3x electrode.     

Electrochemical determination of niobium cathode as an efficient electrocatalyst for hydrogen generation in acidic media

Hydrogen gas (H₂) is notified as a renewable energy carrier. It is wanted to discover a low-cost electrocatalyst for the hydrogen evolution reaction (HER) to substitute the high-cost Pt in electrolysis cell. Niobium electrocatalyst nominated to substitute noble materials for electrocatalytic H₂ production and its electrochemical manner was estimated in H₂SO₄ acid of various concentrations utilizing a steady-state polarization and electrochemical impedance spectroscopy (EIS). The influences of acid concentration, cathodic potential and temperature on the H₂ creation were examined. The outcomes display that HER on Nb electrode proceeds by the Volmer-Heyrovsky mechanism. EIS tests, under open circuit and under cathodic polarization, were performed and the fitting has been done utilizing a suggested model for the electrode/electrolyte interface. Apparent activation energies (E_a) were estimated to be ca. 10.5 kJ mol^?1 for the HER on Nb. Thus, Nb is a good electrocatalyst for the cathodic H₂ manufacturing.     

Precise determination of Tafel slopes by DEMS. Hydrogen evolution on tungsten-based catalysts in alkaline solution

High-purity hydrogen generation for primary energy production is one of the main goals of the renewable energy consumption model. In this regard, water electrolyzers (WE) are projected to fulfil this requirement since they can be coupled to renewable sources, which provide the necessary energy to generate the water splitting reaction. Nowadays, no-noble materials are usually employed as low-cost catalysts to overcome the hydrogen evolution reaction (HER). However, kinetics and mechanistic studies of the HER from faradaic currents is becoming more challenging due to the overlap of by-side reactions such as catalyst oxides reduction. Herein, for the first time ionic currents from differential electrochemical mass spectrometry (DEMS) are employed to overcome this issue. Thus, the m/z = 2 signal is followed during the hydrogen evolution on tungsten-based catalysts in basic medium and accurate Tafel slopes are achieved and the rate determining step (RDS), as well as the reaction mechanism can be easily attained.     

Preparation and study of electrocatalytic activity of Ni-Pd(OH)2/C nanocomposite for hydrogen evolution reaction in alkaline solution

A new catalyst (Ni-Pd(OH)₂/C) for hydrogen evolution reaction (HER) was prepared by coelectrodeposition of Pd(OH)₂/C nanoparticles and Ni on a Cu substrate in two steps. Furthermore, the effect of Mo ions in alkaline solution (1 M NaOH) on the electrocatalytic activity of Ni-Pd(OH)₂/C nanocomposite was studied as an in-situ activator for the HER. The various electrochemical methods were employed to study the HER activity of the investigated new catalyst, including linear sweep voltammetry (LSV), the steady-state polarization Tafel curves, electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA). The electrochemical measurements showed that the Ni-Pd(OH)₂/C nanocomposite as a catalyst for the HER has an excellent catalytic activity with good stability in alkaline solution. Furthermore, the rate constants of the forward and backward reactions of Volmer and Heyrovský steps were estimated using Tafel-impedance data and revealed that the proton discharge electrosorption or Volmer reaction (k₁= (6.8 ± 0.7) × 10⁻⁸ mol cm⁻² s⁻¹) was the rate determining step (RDS) of the HER on the surface of Ni-Pd(OH)₂/C nanocomposite. Also, it was observed that the presence of Mo ions in alkaline solution could significantly increase the HER activity of Ni-Pd(OH)₂/C nanocomposite. The comparison of RDS rate constant value with surface roughness (R_f) of Ni-Pd(OH)₂/C catalyst showed that its high activity toward the HER originated from both increase in the surface roughness (∼20%) and increase in synergistic effect (∼80%).     

Effect of copper addition on cobalt-molybdenum electrodeposited coatings for the hydrogen evolution reaction in alkaline medium

Co–Mo materials have been reported as electrocatalysts that present good performance in alkaline electrolytes. In this paper, the addition of copper into Co–Mo catalysts was evaluated for the hydrogen evolution reaction (HER). It was observed that the electrochemical activity of the Co–Mo for the HER benefited from the addition of copper. The overpotentials required to reach a current density of −10 mA cm⁻² were of −156 mV and −119 mV for Co₆₇Mo₃₃ and Co₅₆Mo₂₁Cu₂₃, respectively. Besides the increased surface area resulting from the addition of copper, it was observed that the improved intrinsic activity for Co₆₁Mo₃₂Cu₇, compared to Co₆₇Mo₃₃, is related to a thermodynamic favoring of the hydrogen adsorption and desorption stages. Large quantities of copper do not favor the HER; therefore, the increased catalytic activity depends on a balance between the intrinsic catalytic activity and the increase of the electroactive area.     

Pulse-activation engineering induced lattice transformation of layered double hydroxides for efficient alkaline hydrogen evolution

In order to accelerate water dissociation kinetics and improve hydrogen evolution reaction (HER) in alkaline electrolyzer, pulse-activation engineering was proposed to induce lattice transformation of layered double hydroxides (LDHs) electrocatalysts. Physicochemical characterizations and density functional theory (DFT) calculations confirmed that FeOOH crystals diminished with a pulse potential of 1000 cycles (cls) in non-Faradaic region (?0.8～0 V) and transformed into more stable CoFeLDH nanosheet arrays in Fe-rich system. The above transformation effectively reduced H¹ adsorption energy to accelerate water decomposition for efficient hydrogen evolution reaction. This was because pulse-activation accelerated electron transfer from Co²⁺ to Fe^(3+δ)+ through intermittent input negative potential, reducing the high oxidation state of Fe^(3+δ)+ in FeOOH to generate more stable CoFeLDH. The optimized pulse-activation with CoFeLDH electrocatalyst after 1000 cls decreased the overpotential of alkaline hydrogen evolution by 36%, from 225 mV to 144 mV at ?10 mA cm^?2.     

Exploring the effect of ion concentrations on the electrode activity and stability for direct alkaline seawater electrolysis

Studying the electrode activity and stability changes caused by the increasing ion concentration during the alkaline seawater electrolysis is crucial to exploit industrial-level seawater electrolyser. Herein, the concentration of hydroxide ion (OH⁻), chlorine ion (Cl⁻), and the other ions in alkaline seawater (OIAS) is investigated to understand the activity and stability for nickel foam (NF) electrodes as both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrodes. As a whole, the activity of HER electrode is mainly dropped with the increasing concentration of OH⁻, while the OER electrode is enhanced with the increasing concentration of OH⁻ and Cl⁻. However, the all (OH⁻, Cl⁻ and OIAS) increasing ion concentrations decrease the HER electrode stability, while the Cl⁻ reduces, the OH⁻ and OIAS enhances the stability of OER electrode. Moreover, the chloride evolution reaction (ClER) in 6 M NaOH with seawater can be ignored even though the concentration of salts in alkaline seawater reach to saturation.     

Direct electrolysis of Bunsen reaction product HI/H2SO4/H2O/toluene mixture for hydrogen production: Pt electrode characterization

In chemical cycles to produce hydrogen, the H₂S splitting cycle and the sulfur-iodine (SI) water splitting cycle both share the Bunsen reaction and HI decomposition. Therefore, they have to overcome the same challenges in the technology development, one of them being the complex and difficult separations of the mixed hydroiodic acid and sulfuric acid solution after the Bunsen reaction. To avoid the separations, this paper studies the electrolysis of the HI/H₂SO₄/H₂O/toluene mixture, focusing on the electrochemical characterization of the Pt electrode by using linear sweep voltammetry (LSV) and cyclic voltammetry (CV). The results show that hydrogen is identified from the gas generated from the cathode in electrolysis. Iodide oxidation is the main reaction in the anode chamber and no significant side reactions are observed. Iodine deposition on the anode surface increases the resistance to iodide diffusion to the anode. However, it can be mitigated by adding toluene in or applying stirring to the anolyte HI/H₂SO₄ solution. The Pt cathode and sulfuric acid catholyte also work stably.     

Development of durable and efficient electrodes for large-scale alkaline water electrolysis

A new type of electrodes for alkaline water electrolysis is produced by physical vapour depositing (PVD) of aluminium onto a nickel substrate. The PVD Al/Ni is heat-treated to facilitate alloy formation followed by a selective aluminium alkaline leaching. The obtained porous Ni surface is uniform and characterized by a unique interlayer adhesion, which is critical for industrial application. IR-compensated polarisation curves prepared in a half-cell setup with 1 M KOH electrolyte at room temperature reveals that at least 400 mV less potential is needed to decompose water into hydrogen and oxygen with the developed porous PVD Al/Ni electrodes as compared to solid nickel electrodes. High-resolution scanning electron microscope (HR-SEM) micrographs reveal Ni-electrode surfaces characterized by a large surface area with pores down to a few nanometre sizes. Durability tests were carried out in a commercially produced bipolar electrolyser stack. The developed electrodes showed stable behaviour under intermittent operation for over 9000 h indicating no serious deactivation in the density of active sites.     

Growth of iron diselenide nanorods on graphene oxide nanosheets as advanced electrocatalyst for hydrogen evolution reaction

Advanced electrocatalysts for the fabrication of sustainable hydrogen from water splitting are innermost to energy research. Herein, we report the growth of iron diselenide (FeSe₂) nanorods on graphene oxide (GO) sheets using two-step process viz., simple hydrothermal reduction and followed by wet chemical process. The orthorhombic phase of FeSe₂ incorporated GO nanosheet was developed as a low-cost and efficient electrocatalyst for hydrogen evolution reaction (HER) by water splitting. The phase purity, crystalline structure, surface morphology and elemental composition of the synthesized samples have been investigated by UV–visible absorption spectroscopy (UV–vis), fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray analysis (EDS). Voltammetry and Tafel polarization methods have been utilized to assess the performance of various weight ratio of GO nanosheet in FeSe₂ nanorods towards H₂ evolution. Detailed electrochemical investigations revealed that the 30% FeSe₂/GO composite showed a tremendous electrocatalytic HER activity in acidic medium with high cathodic current density of 9.68 mA/cm² at η = 250 mV overpotential and with a Tafel slope of 64 mV/dec. The 30% FeSe₂/GO composite offers a high synergistic effect towards HER activity, which is mainly due to high electrochemical active catalytic sites, low charge-transfer resistance and enhanced electrocatalytic performances of H₂ production. The present analysis revealed the possible application of FeSe₂/GO composite as a promising low-cost alternative to platinum based electrocatalysts for H₂ production.