Segregation and stability at Pt3Ni(1 1 1) surfaces and Pt75Ni25 nanoparticles

Using in situ surface X-ray diffraction we have determined the atomic structure and stability of a Pt₃Ni(1 1 1) surface in the electrochemical environment. Surface segregation leads to a pure Pt(1 1 1) skin with enrichment of Ni in the sub-surface atomic layer that determines the surface electronic structure. The Pt-skin surface exhibits inward relaxation upon the adsorption of oxygenated species and this explains the surface stability compared to pure Pt(1 1 1). Using Monte Carlo calculations it is shown that nanoparticles with the same surface composition and stochiometry are energetically stable.     

Hydrophilicity transition of the clean rutile TiO2 (1 1 0) surface

We present contact angle measurements of water on single-crystal rutile TiO₂ (1 1 0) surfaces, exposed to ambient air, or protected in dry air. Our measurements indicate that the surfaces exposed to ambient air are hydrophobic, with a contact angle of θ = 61(5)°. However, the well-protected dry surface also exhibits some hydrophobic tendency, with θ = 32(5)°. It is known that UV irradiation transforms both surfaces superhydrophilic, with θ = 0° [R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M. Shimohigoshi, T. Watanabe, Nature 388 (1997) 431-432]. We also present preliminary X-ray crystal truncation rod measurements on the hydrophobic TiO₂ (1 1 0) surface, and of the effect of UV illumination on the surface.     

Remarkable solvent effect on the structure and electrochemical properties of [M(bipyridyl)3](ClO4)3 (M = Co, Fe and Ru) films

In low dielectric constant media the electrooxidation of bipyridyl complexes of transition divalent metal cations, such us Fe(II), Co(II), and Ru(II) results in the precipitation of microcrystalline film on the electrode surface. In most solvents, the film is reversibly reduced. However, films formed in the presence of acetonitrile are electrochemically inactive over a large potential range. The morphology and crystallographic structure of solid phase formed on the electrode surface during the electrochemical oxidation of bipyridyl complexes of Co(II), Fe(II), and Ru(II) have been investigated by the scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transformation-IR/horizontal attenuated total reflectance (FT-IR/HATR) spectroscopy and elemental analysis. A correlation between the electrochemical properties and the structure of the film has been found. The electrochemically inactive films of Co(II) and Fe(II) complexes formed in the presence of acetonitrile in solution consist of densely packed column-like crystallites. They exhibit monoclinic symmetry P/2m (no. 10). The other films formed in acetonitrile free solutions, form flower-like aggregates of orthorhombic symmetry Pmmm crystals (no. 47). These films are very porous.     

Effect of halogen ions on platinum dissolution under potential cycling in 0.5 M H2SO4 solution

The effect of ppm level of chloride and fluoride ions on the dissolution of electrochemically deposited Pt with two different thickness has been studied by using electrochemical quartz crystal microbalance (EQCM) and ICP-Mass analysis in combination with atomic force microscopy (AFM). A mass loss due to dissolution of Pt as chloride complexes was observed in as low as 10 ppm [Cl⁻] at 1.06 V versus SHE. Fluoride ion did not have any effect on the dissolution of Pt in as high as 1000 ppm [F⁻]. From the comparison of EQCM, ICP-Mass and AFM images, it was revealed that amount of platinum dissolution under potential cycling greatly depended on chloride concentration and morphology of deposited Pt layers. When Pt dissolution was induced by Cl⁻ ions, the amount of dissolved Pt did not depend on the particle size of the deposited Pt. On the other hand, in the absence of Cl⁻ induced dissolution, i.e. when oxide formation was dominant, the particle size of the deposited Pt greatly affected the amount of dissolved Pt. This was explained by considering the increase of overpotential for the reduction of chloride complex due to its high stability in chloride solution.     

On the fractal study of LiMn2O4 electrode surface

Fractal dimension of a LiMn₂O₄ electrode prepared by sol-gel method was determined using electrochemical techniques based on the phenomenon of “diffusion towards electrode surface”. A simple discussion was made on the methodology to understand what is really estimated as the fractal dimension. It was demonstrated that the value of fractal dimension determined based on electrochemical methods is strongly dependent on the electrochemical system situation. This is generally true for all real electrodes involving insertion/extraction processes. This comes from the fact that surface morphology of the electrode is subject of significant changes during the electrochemical experiment.     

Double channel electrode flow cell application to the study of HO2 production on MnxCo3−xO4 (0 ≤ x ≤ 1) spinel films

We conducted a study on the electroreduction of O₂ in alkaline solution at room temperature on pure thin oxide electrodes of composition Mn_xCo_3−xO₄ (0 ≤ x ≤ 1) using the double channel electrode flow cell (DCEFC). The oxides were prepared at 150 °C and deposited by spray pyrolysis onto titanium substrates. The oxygen reduction reaction (orr) occurs through “interactive” and “parallel” pathways, and the ratio of O₂ molecules reduced to OH⁻ ions with respect to those reduced to HO₂⁻ ions depends on the oxide stoichiometry and on the applied overpotential. The formation of HO₂⁻ increases when the manganese concentration increases. The results obtained for the orr show that the number of electrons transferred per O₂ molecule decreases from 3 to 2 and the ratio k₁/k₂ (the rate constants for direct reduction to OH⁻ and indirect reduction to HO₂⁻) increases, respectively, in the overpotential studied range (−0.05 to −0.6 V). The Mn³⁺ ions placed in the B-sites of the spinel structure seem to be the active centres, where hydrogen peroxide is formed.     

Synthesis and spectroscopic investigation of the pyrazole complexes. The X-ray structure of [ReOBr3(OAsPh3)(pzH)]

The [ReOX₃(OAsPh₃)(AsPh₃)] complexes react with pyrazole in dry tetrahudrofuran to give new monomeric oxo rhenium(V) complexes – [ReOX₃(OAsPh₃)(pzH)]. This paper presents synthesis and spectroscopic characterisation of [ReOX₃(OAsPh₃)(pzH)] compounds and X-ray structure of the bromine analogue.     

Electrochemical lithium insertion in (PO2)4(WO3)2m (2 ≤ m ≤ 10): Relation among the electrochemical insertion process and structural features

In this work it is presented a review of the main results obtained during the electrochemical lithium insertion in the family of monophosphate tungsten bronzes (PO₂)₄(WO₃)_2m (2 ≤ m ≤ 10). This family of oxides is a good system in order to study the relation among the electrochemical processes observed in the course of lithium insertion and the changes of bronzes structures. By means of X-ray diffraction experiments, the nature of Li_x(PO₂)₄(WO₃)_2m phases has been elucidated and a correlation with the reversible/irreversible processes observed during the electrochemical insertion has been established. The electrical properties of the inserted Li_x(PO₂)₄(WO₃)_2m phases were measured and a relation with the amount of lithium inserted and m was also found.     

On the spinel formation in Co1 − xO/Co2TiO4 composites via reactive sintering, exsolution and oxidation

The formation mechanism and microstructural development of the spinel phases in the Co_1 − xO/Co₂TiO₄ composites upon reactive sintering the Co_1 − xO and TiO₂ powders (9:1 molar ratio) at 1450 °C and during subsequent cooling in air were studied by X-ray diffraction and analytical electron microscopy. The Co₂TiO₄ spinel occurred as inter- and intragranular particles in the matrix of Ti-doped Co_1 − xO grains with a rock salt-type structure during reactive sintering. The submicron sized Co₂TiO₄ particles were able to detach from grain boundaries in order to reach an energetically favorable parallel orientation with respect to the host Co_1 − xO grains via a Brownian-type rotation/coalescence process. Upon cooling in air, secondary Co₂TiO₄ nanoparticles were precipitated and the Ti-doped Co_1 − xO host was partially oxidized as Co_3 − δO₄ spinel by rapid diffusion along the {1 1 1} and {1 0 0}-decorated interphase interface and the free surface of the composites.     

Solid solution between Al-ettringite and Fe-ettringite (Ca6[Al1 − xFex(OH)6]2(SO4)3·26H2O)

The solid solution between Al- and Fe-ettringite Ca₆[Al_1 − xFe_x(OH)₆]₂(SO₄)₃·26H₂O was investigated. Ettringite phases were synthesized at different Al/(Al + Fe)-ratios (= X_Al,total), so that X_Al increased from 0.0 to 1.0 in 0.1 unit steps. After 8 months of equilibration, the solid phases were analyzed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA), while the aqueous solutions were analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). XRD analyses of the solid phases indicated the existence of a miscibility gap between X_Al,total = 0.3-0.6. Some of the XRD reflections showed two overlapping peaks at these molar ratios. The composition of the aqueous solutions, however, would have been in agreement with both, the existence of a miscibility gap or a continuous solid solution between Al- and Fe-ettringite, based on thermodynamic modeling, simulating the experimental conditions.     

Corrosion protection of carbon steel by thin films of poly(3-alkyl thiophenes) in 0.5 M H2SO4

Poly(3-octyl thiophene) (P3OT) and poly(3-hexylthiophene) (P3HT) dissolved in toluene were deposited onto 1018 carbon steel and corroded in 0.5 M H₂SO₄. P3OT and P3HT films were chemically deposited by drop casting onto 1018-type carbon steel with two surface finishing, i.e. abraded with 600-emery paper and with alumina (Al₂O₃) particles of 1.0 μm in diameter (mirror finish). Their corrosion resistance was estimated by using potentiodynamic polarization curves, linear polarization resistance (LPR), and electrochemical impedance spectroscopy, EIS, techniques. In all cases, polymeric films protected the substrate against corrosion, but the protection was improved if the surface was polished with Al₂O₃ particles of 1.0 μm in diameter. The polymer which gave the best protection was P3HT because the amount of defects was much lower than that for the P3OT films. The polymers did not act only as a barrier layer against aggressive environment, but they improved the passive film properties by decreasing the critical current necessary to passivate the substrate, increasing the pitting potential and broadening the passive interval.     

Open-circuit-potentials of gas/electrode/YSZ boundary versus molten carbonate reference electrode at medium temperatures: II. Potential response of Au, Pt and Ni-cermet electrodes in CH4 + O2 and H2 + O2 gas mixtures

Values of open-circuit-potentials (OCP) have been determined for pairs of electrodes: Au and Pt, Ni-Ce_0.8Sm_0.2O_1.9 cermet and Au, Pt and Sm_0.5Sr_0.5CoO₃ composite at the YSZ electrolyte, in the uniform atmospheres of xCH₄ + yO₂ + (1 − x − y)Ar gas mixtures with variable x and y coefficients, at 600 °C. The determined dependencies of OCP values on the initial gas mixture compositions have been compared with the respective dependencies calculated for equilibrium or quasi-equilibrium compositions of these gas mixtures. The OCP values for the pair of Pt and Au electrodes have been measured also in the xH₂ + yO₂ + (1 − x − y)Ar uniform gas mixtures but no distinct difference of the OCP values has been observed in this atmosphere. For some pairs of electrodes investigated in xCH₄ + yO₂ + (1 − x − y)Ar atmospheres the measured OCP values have shown differences up to ca 0.9-1.0 V. These differences were stable within large range of compositions of this gas mixture. Within this gas composition range one of the electrodes conserves the potential of oxygen electrode determined by oxygen partial pressure in the initial gas mixture and is insensitive to reaction occurring in the gas phase. These results are discussed on the basis of equilibria or some quasi-equilibria, that establish in the C-H-O gas mixture and the solid carbon deposition is considered. For a given pair of dissimilar electrodes, their selective sensibility to the electrochemical process of oxygen electrode has been confirmed. Within large range of gas mixture concentrations, in the Pt-Au electrode pair Au has shown behavior of the oxygen electrode, whereas the OCP values of the Pt electrode are within the range of hydrogen electrode, also at gas compositions corresponding to the solid carbon stability. With this pair the OCP differences of ca. 600 mV have been obtained. Among three electrodes studied the cermet Ni-Ce_0.8Sm_0.2O_1.9 electrode shows the best electrocatalytic properties resulting in the OCP values following exactly the respective equilibrium dependence. In the pair Ni-Ce_0.8Sm_0.2O_1.9 and Au a stable potential difference of ca. 900 mV have been established. Unexpectedly, Pt electrode in the pair with the Sm_0.5Sr_0.5CoO₃ composite electrode plays role of the oxygen electrode quite insensitive to other components of the equilibrated initial gas mixture. This surprising fact seems indicate that in conditions of the experiments performed the electrocatalytic behavior of the electrode depends not only of the material of this electrode but also on the properties of the second electrode in the given pairs of electrodes.     

Electrochemical stability of thin film LiMn2O4 cathode in organic electrolyte solutions with different compositions at 55 °C

A survey of the electrochemical stability of electrostatic spray deposited thin film of LiMn₂O₄ was performed in LiClO₄-EC-PC, LiBF₄-EC-PC, and LiPF₆-EC-PC solutions at 55 °C. The solution resistance, the surface film resistance, and the charge-transfer resistance were all found to depend on the electrolyte composition. Among the LiX-salts studied, the lowest charge transfer-resistance, and surface layer resistance were obtained in LiBF₄-EC-PC solution. There is no major influence of the electrolyte solution compositions upon lithium ion transport in the LiMn₂O₄ bulk at 55 °C. The diffusion coefficient of lithium in the solid phase varied within 10⁻¹⁰-10⁻⁸ cm² s⁻¹ in the three solutions. In general, it seems that in LiBF₄ solutions, the surface chemistry is the most stable in the three solutions examined, and hence the electrode impedance in LiBF₄ solutions was the lowest. In LiPF₆ solutions, HF seems to play an important role, and thus, the electrode impedance is relatively high due to the precipitation of surface LiF.     

A simple and clean process for the synthesis of M(C17H35COO)2 (M = Zn, Pb)

This paper presents a cleaner production process for producing metal stearates particles using solid-state reaction at low temperatures. Zinc stearate and lead stearate were synthesized using PbO, ZnO and stearate acid as the reactants. The products were characterized by XRD, TG, DSC and FTIR techniques. The results showed this process yielded the products in excellent yield. Compared with precipitation or saponifying process, metal stearates prepared in this way appear of shorter process, lower cost, and no production of polluted water and higher yields.     

A study of the electrical properties of carbon nanotube-NiFe2O4 composites: Effect of the surface treatment of the carbon nanotubes

Novel carbon nanotube-NiFe₂O₄ composite materials have been prepared for the first time by in situ chemical precipitation of metal hydroxides in ethanol in the presence of carbon nanotubes (CNTs) and followed by hydrothermal processing. The obtained composite powders were characterized using XRD, TEM and EDS. The effect of surface oxidation treatment of CNTs on their properties was investigated by FTIR, zeta potential and hydrodynamic radius distribution characterization. Electrical conductivity measurements show that surface oxidation treatment of CNTs can improve the electrical conductivity of the composites more pronouncedly than pristine CNTs do. With 10 wt.% addition of surface treated CNTs, the electrical conductivity is increased by 5 orders of magnitude. The surface oxidized CNTs are crucial for this significant increase in electrical conductivity, which provides strong adhesion between the nanotubes and the matrix to give a homogeneous carbon nanotube-NiFe₂O₄ composite.     

A study on mechanism of charging/discharging at amorphous manganese oxide electrode in 0.1 M Na2SO4 solution

In the present work, the mechanism of charging/discharging at the amorphous manganese oxide electrode was investigated in 0.1 M Na₂SO₄ solution with respect to amount of hydrates and valence (oxidation) states of manganese using a.c.-impedance spectroscopy, anodic current transient technique and cyclic voltammetry. For this purpose, first the amorphous manganese oxide film was potentiostatically electrodeposited, followed by heat-treatment at 25–400 °C to prepare the electrode specimen with different amounts of hydrates and oxidation states of manganese. For as-electrodeposited electrode with the most hydrates, the anodic current transient clearly exhibited a linear relationship between the logarithm of current density and the logarithm of time, with a slope of −0.5, indicating that the charging/discharging is purely limited by Na⁺/H⁺ ion diffusion. From the analyses of the impedance spectra combined with anodic current transients measured on the hydrated electrode heat-treated at 25–150 °C, it was found that as the amount of hydrates decreases, the depth of cation diffusion in the electrode becomes shallower and the ratio of charge-transfer resistance to diffusion resistance also increases. This suggests that a transition occurs of pure diffusion control to a mixed diffusion and charge-transfer reaction control. For the dehydrated electrode heat-treated at 200–400 °C, the charging/discharging purely proceeds by the charge-transfer reaction. The reversibility of the redox reaction increases with increasing amount of hydrates and oxidation states of manganese, which provides us the higher power density. On the other hand, the pseudocapacitance decreases in value with increasing heat-treatment temperature, thus causing the lower energy density.     

Influence of halide ions on the adsorption of diphenylamine on iron in 0.5 M H2SO4 solutions

Halide ions are found to enhance the inhibition performance of amines due to enhanced adsorption of amines by the adsorbed halide ions on the metal surface. In this work, the synergistic action of halide ions on the corrosion inhibition of iron in 0.5 M H₂SO₄ by diphenylamine has been found out by electrochemical impedance and polarization methods. Analysis of impedance data has been made with equivalent circuit with constant phase angle element for calculation of double layer capacitance values. Experiments have been carried out in the concentration range of 100-1000 ppm of diphenylamine in the presence of 0.5-1.0 × 10⁻³ M of halide ions. Diphenylamine is found to be a cathodic inhibitor and the inhibition efficiency of about 65% is obtained at 1000 ppm. The anodic and cathodic Tafel slopes in the presence of diphenylamine alone and with halide ions are 65 ± 5 and 105 ± 5 mV, respectively. Diphenylamine inhibits corrosion by adsorption and the surface coverage values are increased considerably in the presence of halide ions. In the presence of iodide ions, the inhibition efficiency of diphenylamine at 100 ppm is increased to more than 90%. In the case of other halide ions, the inhibition efficiency of diphenylamine in increased to 80% at 1000 ppm. The order of synergism of halide ions is I⁻ ? Br⁻ > Cl⁻. The highest synergistic effect of iodide ions is due to chemisorption with metal surface due to its larger size and ease of polarizability.     

Electrochemical properties of La1−xSrxFeO3 (x = 0.2, 0.4) as negative electrode of Ni-MH batteries

La_(1−x)Sr_xFeO₃ (x = 0.2,0.4) powders were prepared by a stearic acid combustion method, and their phase structure and electrochemical properties were investigated systematically. X-ray diffraction (XRD) analysis shows that La_(1−x)Sr_xFeO₃ perovskite-type oxides consist of single-phase orthorhombic structure (x = 0.2) and rhombohedral one (x = 0.4), respectively. The electrochemical test shows that the reaction at La_(1−x)Sr_xFeO₃ oxide electrodes are reversible. The discharge capacities of La_(1−x)Sr_xFeO₃ oxide electrodes increase as the temperature rises. With the increase of the temperature from 298 K to 333 K, their initial discharge capacity mounts up from 324.4 mA h g⁻¹ to 543.0 mA h g⁻¹ (when x = 0.2) and from 147.0 mA h g⁻¹ to 501.5 mA h g⁻¹ (when x = 0.4) at the current density of 31.25 mA g⁻¹, respectively. After 20 charge-discharge cycles, they still remain perovskite-type structure. Being similar to the relationship between the discharge capacity and the temperature, the electrochemical kinetic analysis indicates that the exchange current density and proton diffusion coefficient of La_(1−x)Sr_xFeO₃ oxide electrodes increase with the increase of the temperature. Compared with La_0.8Sr_0.2FeO₃, La_0.6Sr_0.4FeO₃ electrode is a more promising candidate for electrochemical hydrogen storage because of its higher cycle capacity at various temperatures.