Long-term electrolytic hydrogen permeation in nickel and the effect of vanadium species addition

Nickel cathodes have been found to become deactivated under long-term polarization in the H₂ evolution region during alkaline water electrolysis. The cause of deactivation was examined using steady state polarization and measurement of hydrogen permeation through nickel foil in 8 mol/l KOH at 70 °C and 100 mA/cm². The long-term (over 50 h) permeation behaviour was explained by formation and growth of a nickel hydride phase. The rise in hydrogen overpotential was ascribed to an increase of the hydrogen surface coverage on the newly formed hydride. The effect of an electrolyte additive (a vanadium salt) on the hydrogen overpotential and permeation rate was also investigated. Upon addition of dissolved V₂O₅, the permeation rate was found to increase quickly and then slowly decrease to a steady value close to that measured for hydride-free nickel. Meanwhile, the hydrogen overpotential was observed to recover back to nearly its initial value for fresh nickel. The exhibited behaviour was attributed to decomposition of the hydride phase, after deposition of a vanadium-bearing compound. The prolonged contact between Ni and V was proposed as the main reason for hydride decomposition. The addition of more vanadium had no further result on the hydrogen overpotential.     

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.     

Electrochemical generation of hydrogen peroxide using surface area-enhanced Ti-mesh electrodes

Ti-mesh electrodes coated with Ti were obtained by using an electrophoretic deposition (EPD) method. The Ti coating was porous and showed a good adherence to the Ti-mesh surface, due to sintering of Ti particles during thermal treatment at 900 °C. The Ti-coated mesh electrode has a BET surface area of 3.5 m²/g, about four times larger than that of the bare electrode. The surface area-enhanced Ti-mesh electrode was applied in electrical generation of hydrogen peroxide. It was shown that the rate of hydrogen peroxide generation increased drastically compared to the fresh electrode, since the larger electrode surface area enhanced not only current density, but also the oxygen mass transfer rate.     

Study of the hydrogen absorption in Pd in alkaline solution

Hydrogen adsorption/absorption in palladium thin deposits on gold electrode, in 0.1 M NaOH solution, was studied. The contributions of adsorption and absorption to the total charge of hydrogen are separated from the total isotherms at different deposit thicknesses. The adsorbed hydrogen charge increases to a plateau of ∼73.5 μC cm⁻², which corresponds to the surface coverage ratio by adsorbed hydrogen of 0.36. The absorbed hydrogen charge agreed with that obtained from the permeation experiments at 50 μm Pd foil, at potentials between +100 and +300 mV vs. RHE. EIS was carried out at thin Pd deposits. The kinetics of hydrogen sorption is slower in alkaline solutions than in acids and the isotherms are shifted towards more negative potentials.     

Hydrogen evolution reaction on Ni-P alloys: The internal stress and the activities of electrodes

The hydrogen evolution reaction (HER) was studied on Ni-P electrodes prepared by electrodeposition at temperatures varying from 23 °C to 65 °C. The activities for the HER of the electrodes first decreased slowly with the increasing temperature of the Ni-P preparation. A sudden decrease in the HER activity occurred on the electrode prepared at 65 °C. Similar dependence was found for the variation of the amounts of absorbed hydrogen with the electrodeposition temperature of the Ni-P electrodes. The behavior of Ni-P electrodes prepared from Ni-P powders was quite different. (Ni-P powder was prepared by peeling off the Ni-P layer and by milling the leaves of the Ni-P alloy in a vibrating ball mill.) The Ni-P powder electrodes displayed little activity independently of the temperature of the Ni-P powder preparation. It was followed from the results that the high activity for the HER of the layer Ni-P electrodes prepared at T ≤ 53 °C was caused by the internal stress in the layer. The stress originated during the electrodeposition of the Ni-P layer by co-deposited and absorbed hydrogen.     

Thermodynamic parameters evolution versus plastic strain during HER on nickel in sulphuric acid

The dependence of the hydrogen evolution reaction (HER) on plastic strain has been studied on polycrystalline pre-strained nickel electrodes in H₂SO₄ 1 M using linear voltametry. A thermodynamic approach is proposed to determine the influence of temperature and plastic strain on HER characteristic parameters as symmetry coefficients, activation enthalpies, number of active sites, on the different steps of the HER mechanism. A direct correlation is established between crystallographic defects associated with dislocations emerging at the surface of nickel electrodes, in terms of density and distribution of defects, and the efficiency of electrochemical processes occurring during HER: hydrogen adsorption and desorption.     

Effect of hydrogen charging on the stability of SAE 10B22 steel surface in alkaline solutions

The influence of hydrogen charging into a quenched and tempered boron steel membrane electrode (SAE 10B22) was studied using borate buffer (pH 8.4) and NaOH solutions (pH 12.7), with or without the addition of 0.01 M EDTA. At the hydrogen input side, hydrogen charging influenced cyclic voltammograms increasing the anodic charge of iron(II) hydroxide formation, and decreasing the donor density of passive films. These results suggest that the hydrogen ingress caused instability of metallic surface, increasing the surface area activity.     

Changes on iron electrode surface during hydrogen permeation in borate buffer solution

Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E_oc) and in the passive region (+0.30 V_ECS) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L⁻¹ H₃BO₃ + 0.075 mol L⁻¹ Na₂B₄O₇ (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell.     

Application of elimination voltammetry in the study of electroplating processes on the graphite electrode

The electrode reaction mechanism of electrolytical coating by nickel on paraffin impregnated graphite electrode (PIGE) was investigated by cyclic voltammetry (CV) and elimination voltammetry with linear scan (EVLS). The EVLS, a relatively new method of processing electrochemical signals obtained by voltammetry, is able to eliminate some individual chosen currents from total voltammetric currents measured at different scan rates. During the electrodeposition of metals on the graphite electrode, hydrogen evolved from aqueous acidic solutions interferes with the plating process. The elimination of kinetic current arising due to hydrogen evolution enables one to study other processes proceeding at the electrode. Cyclic voltammograms for metal coating deposition/dissolution on the graphite electrode were measured at three scan rates (12.5, 25 and 50 mV/s) and the EVLS functions were calculated for one or two eliminated currents. The results indicate the occurrence of surface reactions with the adsorption of intermediates on graphite. The application of EVLS provides deeper insight into the mechanism of electrode reaction during metal deposition.     

Preparation of high surface area nickel electrodeposit using a liquid crystal template technique

We show in this work that template electrodeposition of nickel at room temperature from a nickel sulphamate bath prepared in a new hexagonal liquid crystalline phase of water-Triton X-100-poly (acrylic acid) results in a highly porous surface. The roughness factor value of about 3620 obtained for this coating is the highest value reported in the literature for any electrodeposited nickel. The scanning electron microscopy (SEM) and scanning tunneling microscopy (STM) pictures show the formation of porous deposit with granular features in between the pores. The single electrode double layer capacitance value measured for the deposit is 338 mF cm⁻², which translates into a specific capacitance of 50 F g⁻¹ without any post-thermal treatment of the electrode, suggesting its utility in super capacitors. Electrochemical studies using cyclic voltammetry (CV), Tafel plots and electrochemical impedance spectroscopy (EIS) and comparison of these results with some existing high surface area Ni catalysts show that the material has potential application as an excellent hydrogen evolving cathode.     

Electrodeposition behavior of nickel and nickel-zinc alloys from the zinc chloride-1-ethyl-3-methylimidazolium chloride low temperature molten salt

The electrodeposition of nickel and nickel-zinc alloys was investigated at polycrystalline tungsten electrode in the zinc chloride-1-ethyl-3-methylimidazolium chloride molten salt. Although nickel(II) chloride dissolved easily into the pure chloride-rich 1-ethyl-3-methylimidazolium chloride ionic melt, metallic nickel could not be obtained by electrochemical reduction of this solution. The addition of zinc chloride to this solution shifted the reduction of nickel(II) to more positive potential making the electrodeposition of nickel possible. The electrodeposition of nickel, however, requires an overpotential driven nucleation process. Dense and compact nickel deposits with good adherence could be prepared by controlling the deposition potential. X-ray powder diffraction measurements indicated the presence of crystalline nickel deposits. Non-anomalous electrodeposition of nickel-zinc alloys was achieved through the underpotential deposition of zinc on the deposited nickel at a potential more negative than that of the deposition of nickel. X-ray powder diffraction and energy-dispersive spectrometry measurements of the electrodeposits indicated that the composition and the phase types of the nickel-zinc alloys are dependent on the deposition potential. For the Ni-Zn alloy deposits prepared by underpotential deposition of Zn on Ni, the Zn content in the Ni-Zn was always less than 50 atom%.     

Micromolar determination of sulfur oxoanions and sulfide at a renewable sol-gel carbon ceramic electrode modified with nickel powder

The sol-gel technique was used to fabricate nickel powder carbon composite electrode (CCE). The nickel powder successfully used to deposit NiO_x thin film on conductive carbon ceramic electrode for large surface area catalytic application. Repetitive cycling in potential range −0.2 to 1.0 V was used to form of a thin nickel oxide film on the surface carbon composite electrode. The thin film exhibits an excellent electro-catalytic activity for oxidation of SO₃²⁻, S₂O₄²⁻, S₂O₃²⁻, S₄O₆²⁻ and S²⁻ in alkaline pH range 10-14. Optimum pH values for detection of all sulfur derivatives is 13 and catalytic rate constants are in range 2.4 × 10³-8.9 × 10³ M⁻¹ s⁻¹. The hydrodynamic amperometry at rotating modified CCE at constant potential versus reference electrode was used for detection of sulfur derivatives. Under optimized conditions the calibration plots are linear in the concentration range 10 μM-15 mM and detection limit 1.2-34 μM and 0.53-7.58 nA/μM (sensitivity) for electrode surface area 0.0314 cm². The nickel powder doped modified carbon ceramic electrode shows good reproducibility, a short response time (2.0 s), remarkable long term stability, less expense, simplicity of preparation, good chemical and mechanical stability, and especially good surface renewability by simple mechanical polishing and repetitive potential cycling. This sensor can be used into the design of a simple and cheap chromatographic amperometry detector for analysis of sulfur derivatives.     

Electroless immobilization and electrochemical characteristics of nickel hexacyanoruthenate film at an aluminum substrate

The surface of an aluminum (Al) electrode was modified with a thin film of nickel hexacyanoruthenate (NiHCR) as a novel electrode material. The modification procedure of Al surface, includes two consecutive procedures: (i) the electroless deposition of metallic nickel on the Al electrode surface from NiCl₂ solution, and (ii) the chemical transformation of deposited nickel to nickel hexacyanoruthenate films in solution of 20 mM K₃[Ru(CN)₆] + 0.5 M KNO₃. Cyclic voltammogram of the modified Al electrode showed a well-defined redox reaction due to [Ni^IIRu^III/II(CN)₆]^1−/2− system. The effects of different supporting electrolytes and solution pH were studied on the electrochemical characteristics of the modified electrode. The diffusion coefficients of K⁺ and Na⁺ cations in the film (D), the transfer coefficient (α), and the charge transfer rate constant at the modifying film/electrode interface (k_s), were calculated in the presence of both K⁺ and Na⁺ cations. The stability of the modified electrode was investigated under various experimental conditions.     

Separation of hydrogen adsorption and absorption on Pd thin films

Hydrogen sorption at Pd films of 20-80 nm deposited on a polycrystalline gold electrode was studied in sulfuric and perchloric acid. Assuming that the hydrogen adsorption does not vary with the Pd films thickness, hydrogen adsorption/absorption charges in Pd were separated in the two contributions in the hydrogen-poor α-Pd-H phase. The results are compared to those obtained at Pd monolayers on Au(1 1 1). The adsorption on polycrystalline Pd begins at potentials more negative than on 0.8 ML Pd on Au(1 1 1) and is not much affected by the nature of anion (sulfate or perchlorate), contrary to the thin layers on Au(1 1 1). The absorption charge in α-PdH phase in the potential range of 0.08-0.15 V was found to be similar to that at a 25 μm Pd foil in this potential range while at more positive potentials it is larger. In the presence of crystal violet which adsorbs at the electrode surface it was found that some residual H adsorption exists. There is more hydrogen absorbed in Pd in the presence of crystal violet in the hydrogen-poor α phase but in the hydrogen-rich β phase the amount of hydrogen is the same.     

Study of structural and electrochemical characteristics of Co-based hypo-hyper d-electrocatalysts for hydrogen evolution

Structural and electrochemical characteristics of hypo-hyper d-electrocatalytic materials aimed for preparation of electrodes for hydrogen evolution were studied. The basic catalytic material was prepared of 10% amorphous Co (grain size <2 nm), 18% amorphous TiO₂ and Vulcan XC-72, by sol-gel procedure. A number of modifications were applied aimed at improving the materials performances: (i) TiO₂ was transformed into anatase by heating at 480 °C for 1 h, (ii) multiwalled carbon nanotubes (MWCNT) were used as a catalyst support instead of Vulcan XC-72 and (iii) Mo was added to Co phase in a quantity of 25 at.% (Mo:Co = 1:3).Both, material's intrinsic catalytic activity and surface area were affected by these modifications. As a result, the electrocatalytic activity for hydrogen evolution was improved, e.g. transformation of TiO₂ into anatase form lowers the HER overpotential (η) for 15 mV at 60 mA cm⁻². Introduction of MWCNTs lowered η for 30 mV, while addition of Mo to metallic phase for 40 mV.The complete modification of all three catalyst's components (10% MoCo₃ + 18% anatase + MWCNTs) was the most effective with 60 mV decrease of overpotential.Characterization was made by XRD, SEM, IR and XPS methods. Surface area was measured by means of cyclic voltammetry.     

Liquid-phase synthesized mesoporous electrochemical supercapacitors of nickel hydroxide

Electrochemical supercapacitive (ES) properties of liquid-phase synthesized mesoporous (pore size distribution centered ∼12 nm) and of 120 m²/g surface area nickel hydroxide film electrodes onto tin-doped indium oxide substrate are discussed. The amounts of inner and outer charges are calculated to investigate the contribution of mesoporous structure on charge storage where relatively higher contribution of inner charge infers good ion diffusion into matrix of nickel hydroxide. Effect of different electrolytes, electrolyte concentrations, deposit mass and scan rates on the current-voltage profile in terms of the shape and enclosed area is investigated. Specific capacitance of ∼85 F/g at a constant current density of 0.03 A/g is obtained from the discharge curve.     

Hydrogen permeation through sol–gel-coated iron during galvanostatic charging

One-layer sol–gel silica–zirconia and two-layer silica–zirconia and zirconia coatings were deposited on one side of iron membranes by spin-coating, densified in air and annealed up to 800 °C in vacuum. Hydrogen permeation through the membranes, coated and uncoated, polarised cathodically under galvanostatic control in 0.1 M NaOH solution was studied using the electrochemical permeation technique. During the initial period, the effect of the sol–gel coatings was insignificant. However, the coatings quite efficiently prevented the iron surface become more active to hydrogen entry during a long-lasting cathodic polarisation. In addition, the electrochemical-corrosion behaviour of the coated iron and the effect of the sol–gel coatings on the effective diffusivity of hydrogen in the coated membranes were studied. On the basis of the polarisation curves and the hydrogen permeation data it was proved that the sol–gel coatings blocked the iron surface for the hydrogen evolution reaction and, consequently, for the hydrogen entry into iron. The effective coating coverage was determined by comparison of the hydrogen fluxes permeating the coated and uncoated membranes. Finally the real concentration of hydrogen beneath the uncoated iron sites and the amount of hydrogen stored in a membrane were evaluated.     

Electrochemical behavior of activated-carbon capacitor material loaded with nickel oxide

In order to enhance specific capacitance and energy density of carbon-based supercapacitor, some nanometer-scale amorphous particles of nickel oxide were loaded into activated-carbon by suspending the activated-carbon in a Ni(NO₃)₂ solution followed by neutralization. A hybrid type electrochemical capacitor was made and tested, in which the activated-carbon loaded with nickel oxide was used as cathode material and activated-carbon was used as anode material. Although the BET surface area of the activated-carbon decreased upon nickel oxide loading compared to that of the starting material, its specific capacitance increased 10.84%, from 175.40 to 194.01 F g⁻¹ and the potential of oxygen evolution on the composite material electrode was 0.076 V higher than that of the pure activated-carbon electrode, in the electrolyte of 6 mol/L KOH solution, so the hybrid capacitor had larger energy density. Similar to the pure activated-carbon electrode, no obvious change appears on the specific capacitances of the composite material electrode at various discharge currents and the composite material electrode exhibiting good power characteristics.     

Hydrogen spillover phenomenon: Enhanced reversible hydrogen adsorption/desorption at Ta2O5-coated Pt electrode in acidic media

The current study is concerned with the preparation and characterization of tantalum oxide-loaded Pt (TaO_x/Pt) electrodes for hydrogen spillover application. XPS, SEM, EDX and XRD techniques are used to characterize the TaO_x/Pt surfaces. TaO_x/Pt electrodes were prepared by galvanostatic electrodeposition of Ta on Pt from LiF-NaF (60:40 mol%) molten salts containing K₂TaF₇ (20 wt%) at 800 °C and then by annealing in air at various temperatures (200, 400 and 600 °C). The thus-fabricated TaO_x/Pt electrodes were compared with the non-annealed Ta/Pt and the unmodified Pt electrodes for the hydrogen adsorption/desorption (H_ads/H_des) reaction. The oxidation of Ta to the stoichiometric oxide (Ta₂O₅) increases with increasing the annealing temperature as revealed from XPS and X-ray diffraction (XRD) measurements. The higher the annealing temperature the larger is the enhancement in the H_ads/H_des reaction at TaO_x/Pt electrode. The extraordinary increase in the hydrogen adsorption/desorption at the electrode annealed at 600 °C is explained on the basis of a hydrogen spillover-reverse spillover mechanism. The hydrogen adsorption at the TaO_x/Pt electrode is a diffusion-controlled process.     

Behaviour of heavy metals in the partial oxidation of heavy fuel oil

The behaviour of heavy metals in the partial oxidation of heavy fuel oils under a pressure of up to 100 bar (10 MPa) has been investigated. The tests were carried out in a 5 MW HP POX (High Pressure Partial Oxidation) test plant, that is operated by the IEC (Department of Energy Process Engineering and Chemical Engineering, TU Bergakademie Freiberg) in cooperation with Lurgi GmbH. In several test campaigns preheated oil with a viscosity of up to 300 cSt (= 300 mm²/s) at the burner inlet has been gasified. The heavy metals nickel Ni, iron Fe and vanadium V occur in heavy residual oils in considerable concentration and may seriously impact the gasification itself and the synthesis gas conditioning and usage. While iron is largely recovered in the gasification residue, the recovery rates of nickel and vanadium depend on the process conditions. Volatile nickel compounds were detected in the raw synthesis gas. It was found that an incomplete carbon conversion enables the capture of nickel Ni and vanadium V in the solid residue phase and can thus mitigate the problem of volatile metal compounds in the raw synthesis gas.