Physicochemical and electrocatalytic properties of LaNiO3 prepared by a low-temperature route for anode application in alkaline water electrolysis

LaNi_1–x Fe_xO₃ (x = 0, 0.25, 0.5) has been synthesized by the hydroxide solid solution precursor method for electrochemical characterization as oxygen anode in strongly alkaline medium. Studies were made at the oxide film, which was obtained by the oxide-slurry painting technique. The cyclic voltammetric study showed the formation of a diffusion-controlled quasireversible redox couple, Ni(ii)/Ni(iii), (E ⁰ - 430 ± 10 mV) at the oxide surface in 1 m KOH. The reaction was observed to follow approximately first-order kinetics in OH^– concentration. Values of the Tafel slope ranged between 59 and 86 mV decade^–1 with all the oxide film electrodes. The electrocatalytic activity was found to be greatest with the Ni/LaNi_0.75Fe_0.25O₃ electrode. A comparison was made between the electrocatalytic activities of LaNiO₃ prepared by the hydroxide solid solution precursor and by the hydroxide coprecipitation technique.     

A new Zn|AlCl3|MnO2 galvanic cell suitable to water-activation

The Zn|3m AlCl₃ (aq)|MnO₂ galvanic cell gives an open circuit voltage (OCV) of 2.0V. When the cell is discharged at constant current (1.5 mA cm^–2 or 50 mAg^–1), its discharge curve shows a relatively flat portion in the region 2.0–1.6 V and the cell has an energy density of 550 Wh (kg of MnO₂)^–1 with a discharge capacity of 330 mA (kg of MnO₂)^–1, these values being about 2 times and 1.5 times, respectively, larger than those of the Zn|5m ZnCl₂|MnO₂ cell. The cell also shows good discharge behaviour at higher electric currents (for example 9.5 mAcm^–2 or 240 mAg^–1), and the advantages of the Zn|AlCl₃|MnO₂ cell over the Zn|ZnCl₂|MnO₂ are clear at the higher discharge currents. The high discharge voltage, energy density, and discharge capacity of the Zn|AlCl₃|MnO₂ cell are attributed to the strong buffering effect of AlCl₃ at pH3. Due to this buffering effect, the electrolytic solution causes gradual corrosion of the zinc and, consequently, the cell is suited to water-activation.     

Double layer capacity of graphite in cryolite-alumina melts and surface area changes by electrolyte consumption of graphite and baked carbon

The double layer (d.l.) capacity of pyrolytic graphite in cryolite-alumina melts at 1010°C was found to exhibit a minimum of 20F cm^–2 at 0·9 V positive to the aluminium electrode. The d.l. capacity attained a plateau of 60F cm^–2 at 1·1–1·4 V, while it rose steeply at potentials below 0·7 V. During electrolytic consumption involving CO₂ evolution the d.l. capacity of pyrolytic graphite remained unaffected, while that of baked carbon was changed, reflecting changes in surface area. At low current densities (cds) the surface area increased substantially and the surface was noticeably roughened, while the opposite behaviour was observed at above 2.5 A cm^–2.     

The importance of site isolation and phase cooperation in propane ammoxidation on rutile-type vanadia catalysts

Propane ammoxidation to acrylonitrile over rutile-type vanadia catalysts is discussed regarding phase cooperation and site isolation effects. Compared with the pure phases, biphasic catalysts with both SbVO₄and -Sb₂O₄are considerably more selective to the formation of acrylonitrile. It is demonstrated that cooperation between the phases during the calcination of the catalyst and the use in propane ammoxidation results in spreading of antimony species from free antimony oxide to the surface of SbVO₄, forming Sb⁵⁺–V³⁺/V⁴⁺supra-surface sites being involved in the formation of acrylonitrile. Dilution and isolation of the vanadium centers in SbVO₄through the partial replacement with, e.g., Al, Ti and W improves the catalytic properties. Structure–reactivity correlations using data for a nominal Sb_0.9V_0.9-x Ti _x O _y series indicate that the activation of propane occurs on a V³⁺site and the activation of ammonia requires an Sb⁵⁺site.     

Comparing measured and Expert-N predicted N2O emissions from conventional till and no till corn treatments

Agricultural soils are a major source of the greenhouse gas nitrous oxide (N₂O). Nitrous oxide emission models can be used to predict the effectiveness of N₂O mitigation strategies; however, these models require rigorous testing before they can be used with confidence. Expert-N, a modular process based N₂O emission model, was tested to determine its ability at predicting nitrogen (N) cycling in the soil–plant–atmosphere system under Canadian agroclimatic conditions. Ancillary data and N₂O emissions were collected/measured from a corn cultivated clay-loam soil that was under different tillage and red clover treatments. The treatments were conventional till (CT) with and without red clover (rc) underseeded in the previous year's wheat crop (CT-Crc and CT-C, respectively), and no till (NT) with and without red clover underseeded in the previous year's wheat crop (NT-Crc and NT-C, respectively). Expert-N provided good estimates of N₂O emissions, and predictions correlated well (positive) with the measured emissions (r ² 0.55–0.83). There was no statistically significant difference between measured and predicted daily emissions. The predicted emissions, integrated over the growing season (25 May–4 October, 1995), were 0.56, 0.57, 0.62, and 0.62 kg N₂O-N ha^–1 for CT-C, CT-Crc, NT-C, and NT-Crc, respectively. The measured emissions over the same period were 1.29, 1.07, 0.96, and 1.04 kg N₂O-N ha^–1 for CT-C, CT-Crc, NT-C, and NT-Crc, respectively. The modelled emissions underestimated the integrated measured emissions by 35–55%; however, the integrated measured emissions had an estimated uncertainty of ±35%. The model provided good predictions of the soil temperatures, moisture contents, and soil nitrate levels with no significant difference from the measured data. Correlations between modelled and measured values for these soil properties in the first 30 cm soil layer were positive and high with r ² 0.71–0.93.     

Synthesis of ternary Li–Mn–O phase at a temperature of 260 ∘C and electrochemical lithium insertion into the oxide

A lithium–manganese oxide, Li _x MnO₂ (x=0.30.6), has been synthesized by heating a mixture (Li/Mn ratio=0.30.8) of electrolytic manganese dioxide (EMD) and LiNO₃ in air at moderate temperature, 260 C. The formation of the Li–Mn–O phase was confirmed by X-ray diffraction, atomic absorption and electrochemical measurements. Electrochemical properties of the Li–Mn–O were examined in LiClO₄-propylene carbonate electrolyte solution. About 0.3 Li in Li _x MnO₂ (x=0.30.6) was removed on initial charging, resulting in characteristic two discharge plateaus around 3.5V and 2.8V vs Li/Li⁺. The Li _x MnO₂ synthesized by heating at Li/Mn ratio=0.5 demonstrated higher discharge capacity, about 250mAh (g of oxide)^–1 initially, and better cyclability as a positive electrode for lithium secondary battery use as compared to EMD.     

Properties of massive Ag/YBCO contacts obtained by explosive compaction with subsequent heat treatment

Axisymmetric explosive compaction with a shock-wave pressure of 2 GPa was used to obtain low-resistance Ag/YBCO (YBa₂Cu₃O_7–x) contacts. Measurements were made of compressive strength at 300 K and microhardness and electrical resistivity within the temperature interval 300–77 K for annealed specimens of Ag/YBCO. Ultimate compressive strength was 0.12 GPa. The microhardness of the ceramic near the Ag/YBCO interface was 3.1 GPa. Contact resistance at the temperature of liquid nitrogen <1·10^–8 ·cm² (contact area 1.0 cm²).IGiL, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk. Translated from Fizika Goreniya i Vzryva, No. 1, pp. 130–134, January–February, 1995.     

Effect of sodium and potassium sulphates on zinc electrowinning

In order to evaluate the intrinsic effect of high concentrations of sodium and potassium sulphates in zinc electrowinning solutions, measurements of coulombic efficiency were carried out under mass transfer-controlled conditions in synthetic solutions of very high purity. A solution composition of 1 mol dm^–3 ZnSO₄+1.5 mol dm^–3 H₂SO₄ was employed with and without additions of 0.5 mol dm^–3 Na₂SO₄ and/or 0.25 mol dm^–3 K₂SO₄. With temperature and current density similar to plant practice (37° C, 650 A m^–2) and electrode rotation rates of 10 and 45 s^–1, the coulombic efficiency for three successive batch tests (200 mg zinc) increased by an average of 1.2% (from an average of 96.0%) for additions of 0.5 mol dm^–3 Na₂SO₄+0.25 mol dm^–3 K₂SO₄. The results were evaluated in terms of available theories, solution purity and predicted changes in solution composition (zinc and hydrogen ion activities) and physical properties following additions of Na₂SO₄/K₂SO₄. It was concluded that in the plant situation the increase in coulombic efficiency would probably be offset by an increase in cell voltage of about 2%, the net effect on power efficiency being a decrease of about 1%. The zinc deposit morphology and preferred orientation were also studied. The addition of sodium and/or potassium sulphate to the solution resulted in rougher, darker zinc deposits, a slight grain refining effect, and a change from random to predominantly basal (002), (004) crystal orientation (at 45 s^–1).     

Behavior of Water and Oxygen Molecules on the Surface of Tin Dioxide Films

Polycrystalline films of compositions SnO₂, SnO_1.93F_0.07, 0.93SnO₂ · 0.07Sb₂O₃, and 0.97SnO₂ · 0.03CuO, which are of interest for use in gas-sensitive sensors, are prepared by the hydropyrolytic method from metal chlorides on a 22-XC ceramic substrate. The films prepared are studied using mass spectrometry, differential thermal analysis (DTA), and thermogravimetric analysis (TGA) at different temperatures. The results of mass spectrometric investigations demonstrate that, except for water (18 amu), no compounds in the mass range 10–70 amu are desorbed from all the films. The differential thermal and thermogravimetric analyses have revealed that desorption of water molecules from the film surface occurs in the temperature range 50–125°C and the oxidation processes associated with the oxygen chemisorption proceed beginning from a temperature of 125°C.     

Impedance spectroscopy of the Ti(IV)/Ti(III) redox couple in the molten LiCl-KCl eutectic melt at 470°C

The electrochemical oxidation of Ti³⁺ ions in LiCl-KCl eutectic melt at 470°C occurs in two different ways according to the current densities. In our experimental conditions (concentration of Ti³⁺ ions 0.11 mol kg^–1) for potentials lower than –0.48 V (vs chlorine electrode) and current densities lower than 10 mA cm^–2 soluble Ti⁴⁺ ions are formed, whereas, for higher potentials solid K₂ TiCl₆ precipitates at the electrode resulting in a partial passivation of the electrode. Both reactions have been studied by means of impedance measurements which have shown the reversibility of the electrochemical reaction (k ₀=0.25 cm s^–1; =0.3) and the porosity of the K₂ TiCl₆ layer electrochemically formed. The thickness of this layer has been estimated from the amount of electricity involved in the reaction and from the resistance and the capacitance characterising the deposit, measured at high frequencies. This comparison shows that the deposit is composed of a very thin (0.1 m) barrier layer covered by a very thick (70 m) porous external layer.Paper presented at the EUCHEM Conference on Molten Salts 1988, St Andrews, Scotland, 6 July 1988.     

Preparation and characterization of thin films of LaNiO3 for anode application in alkaline water electrolysis

LaNiO₃ electrodes were prepared, in the form of thin films on platinum by the methods of spray pyrolysis and sequential coating of mixed metal nitrate solutions followed by thermal decomposition. The films were adherent and of p-type semiconducting. Cyclic voltammetric studies indicated the formation of a quasireversible surface redox couple, Ni(iii)/Ni(ii), on these films before the onset of oxygen evolution in 1 m KOH. The anodic Tafel slopes were 40 and 65 mV decade^–1, on the sprayed LaNiO₃ film and on the film obtained by a layer method, respectively. The reaction order with respect to OH^– was found to be 2.2 on the sprayed oxide film and 1.2 on the layer film. The sprayed oxide film was found to be electrocatalytically more active. It is suggested that the oxygen evolution reaction proceeds on both the film electrodes via the formation of the physisorbed H₂O₂ as an intermediate in the rate determining step.     

Imaging gold clusters on TiO2(110) at elevated pressures and temperatures

Variable temperature scanning tunneling microscopy (STM) has been used to image oxide-supported nanoclusters of Au at temperatures from 300 to 450 K and oxygen pressures from 10^–10 to 4 Torr. Oxygen-induced morphological changes of the TiO₂(1×2) reconstruction are apparent at room temperature and prolonged exposure (3×10³ L (langmuir)) at 10^–4 Torr oxygen. Gold clusters with diameters smaller than 4 nm are unstable toward sintering at ca. 450 K and oxygen pressures >10^–1 Torr. Oxygen at pressures >10^–4 Torr weakens the interaction between the gold cluster and the titania support. Increasing the sample temperature to >300 K facilitates disruption of the cluster–support interaction.     

The Percolation Concept of Glass Structure in Relation to the Electrochromic Effect

The electrochromic effect is studied in glasses of the WO₃–P₂O₅–Li₂O system. It is found that there is a critical WO₃ concentration (x _c 0.15) below which the electrochromic effect is not observed. In the framework of the percolation theory, the critical concentration that corresponds to the threshold of the formation of a continuous electron-conducting network is too small to be appropriate for the network with an octahedral structure. This concentration can be explained in terms of the structural model of closely packed spheres, which is very similar to the structural Goodman model. The Goodman model offers a satisfactory explanation of both the formation of infinite (V–O–V or Bi–O–Bi) chains and a manifestation of the electrochromic effect at a low metal (V or Bi) oxide content of 1 mol %.     

Calculation of the Viscosity of Glass-Forming Melts: VI. The R2O–B2O3–SiO2and RO–B2O3–SiO2Ternary Borosilicate Systems

A method for calculating the viscosity from composition and temperature for melts in the R _m O _n –B₂O₃–SiO₂systems is proposed. The change in the concentrations of structural groups depending on the melt composition is taken into account in calculations. The results of calculations are compared with the experimental data available in the literature on the viscosity of 1200 melts with the use of the SciGlass information system. The root-mean-square deviation between the experimental and calculated characteristic temperatures varies from 30 K (for the glass transition temperature and the Littleton point) to 50 K (for a viscosity of 10⁴P).     

A DRIFTS study of the morphology and surface adsorbate composition of an operating methanol synthesis catalyst

The nature of the species adsorbed on a Cu/ZnO/Al₂O₃ catalyst while it was producing methanol has been elucidated in this study using DRIFTS. The species are carbonates, formate, CO, oxygen atoms ( 2% of a monolayer) and methoxy on the Cu and methoxy on the ZnO. The frequencies observed for the C-O stretch on Cu, 2076, 2092, 2105 and 2132 cm^–1, have revealed the morphology of the copper component of the operating catalyst. The surface of the copper is predominantly the (111) face ( 65%) (the 2076 cm^–1 peak) with the (755) (the 2092 cm^–1 peak) and the (311) (the 2105 cm^–1 peak) faces occupying roughly 20% and 15%, respectively, of the copper area. The 2132 cm^–1 peak derives from CO adsorbed on Cu⁺ site on the copper which is 2% of a monolayer.     

Synthesis and electrochemical characterization of a new Se-doped spinel material for lithium secondary batteries

A new Se-doped spinel material, LiAl_0.18Se_0.02Mn_1.8O₄ powder with a phase-pure polycrystalline was synthesized by a sol–gel method. The material in the 3 V region (2.4 3.5 V) and both the 3 and 4 V region (2.4 4.4 V) initially deliver a discharge capacity of 81 and 178 mA h g^–1 which increase with cycling to reach 110 and 204 after 50 cycles, respectively. The material shows excellent cycleability in the 4 V region (3.0 4.4 V) with almost no capacity loss. The structural integrity of the Se-doped spinel was characterized by charge–discharge cycling tests and X-;ray diffraction.     

Synthesis,characterization and catalytic properties of two novel vanado-aluminosilicates with EU-1 and ZSM-22 structures

The synthesis in the presence of alkali ions of two novel vanadium containing zeolites V-Al-EU-1 and V-Al-ZSM-22 is reported. Both V⁴⁺- and V⁵⁺-ions are present in as-synthesized samples. Cyclic voltammograms of the samples reveal the presence of two types of V⁵⁺ in the calcined samples. A weak shoulder at 980 cm^–1 is observed in the IR spectra of the calcined samples. On extraction with acid a sharp band appears at 960 cm^–1. The acid washed samples are more active in the hydroxylation of phenol and the oxidation of toluene (with H₂O₂) than the calcined samples.     

Good temperature stability of K0.5Na0.5NbO3 based lead-free ceramics and their applications in buzzers

(K_0.5−xLi_x)Na_0.5(Nb_1−ySb_y)O₃ (KLNNSx–y, x = 0–4 mol% and y = 0–8 mol%) lead-free piezoelectric ceramics were prepared by the conventional mixed oxide method. The denser microstructure and better electrical properties of the ceramics were obtained as compared to the pure K_0.5Na_0.5NbO₃ ceramic. The temperature stability of the electrical properties of the ceramics was also investigated. The experimental results show that the KLNNS2.5–5 ceramic exhibits good electrical properties (k_p  49%, k₃₁  30% and , tan δ  0.019), and possesses good temperature stability in the temperature range of −40 to 85 °C. The related mechanisms for improved electrical properties and temperature stability were also discussed. Moreover, buzzers based on the KLNNS2.5–5 ceramic have been fabricated and their characterization is presented. These results show that the KLNNS2.5–5 ceramic is a promising lead-free material for practical application in buzzers.     

Zinc removal from dilute solutions using a rotating cylinder electrode reactor

Mine residue recycling processes produce dilute zinc solutions suitable for metal recovery. The rotating cylinder electrode reactor behaviour sequentially followed charge transfer and diffusion control mechanisms, even with solutions contaminated with metals or organic substances. Zinc removal at low pH (0) and low concentration (2 mg dm^–3) is demonstrated. Under galvanostatic operation, the zinc deposition current efficiency in the charge transfer control region attains values up to 77.3%, whereas in the diffusion control region it decreases rapidly to values as low as 0.1%. When a potentio-static mode is used, less energy is required to deposit zinc, even at low current efficiency. The results and possible problems for continuous reactor operation under conditions of powder formation are identified and discussed using knowledge from other zinc industries such as electrowinning, plating and batteries.List of symbols A _c cylinder electrode active surface (cm²) - A _d disc electrode active surface (cm²) - c _H analytical sulfuric acid concentration (mol cm^–3) - c _Zn analytical zinc sulphate concentration (mol cm^–3) - d cylinder electrode diameter (cm) - D zinc diffusion coefficient (cm² s^–1) - F Faraday constant (96 500 C mol^–1) - I total current (A) - I _H hydrogen production current (A) - I ₁ zinc deposition limiting current (A) - j critical hydrogen current density (A cm^–2) - k zinc mass transfer coefficient (cm s^–1) - K Wark's rule constant - n number of electrons exchanged in the zinc deposition reaction - Re Reynolds number (d ²/2) - Sc Schmidt number (/D) - Sh Sherwood number (kd/D) - t time (s) - V electrolyte volume in the RCER (cm³) - solution kinematic viscosity (cm² s^–1) - zinc deposition current efficiency - rotation speed (rad s^–1)     

A Study of Ionic Conductivity of Glasses in the PbCl2–PbO · B2O3 and PbCl2–2PbO · B2O3 Systems

The steady-state electrical conductivity of oxychloride glasses in the PbCl₂–PbO · B₂O₃ and PbCl₂–2PbO · B₂O₃ systems is investigated. In the temperature range from 190 to 380°C, the dependence of log on the reciprocal of the temperature exhibits a linear behavior. The nature of charge carriers is studied using the Hittorf technique. It is demonstrated that protons and chlorine ions are charge carriers in solid glasses. The concentration dependence of the transport numbers of chlorine ions is examined by the Tubandt method. The contribution of the electronic component to the total electrical conductivity is estimated with the use of the Liang–Wagner technique. The concentration dependences of the electrical conductivity and the transport numbers of chlorine ions are interpreted in terms of the microinhomogeneous glass structure associated with the selective interaction of components during synthesis of glasses.