Graphite intercalation in the graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-R (R = H<Subscript>2</Subscript>O,C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH,C<Subscript>2</Subscript>H<Subscript>5</Subscript>COOH) systems

The electrochemical behavior of graphite in polar solvent-H₂SO₄ electrolytes is studied in a wide range of H₂SO₄ concentrations. The results demonstrate that, with decreasing H₂SO₄ concentration, the charging curves become smoother and shift to higher potentials, the stage index increases, and intercalation compounds are more difficult to obtain. At H₂SO₄ concentrations of 50% and lower, graphite polarization is accompanied by a significant overoxidation, as evidenced by the anomalously small intercalate layer thicknesses: 7.75–7.85 Å. Anodic polarization of graphite in electrolytes consisting of H₂SO₄ and a polar solvent (H₂O and C₂H₅OH) follows the same mechanism as in the case of the formation of graphite bisulfate. In going from water to C₂H₅OH, a less polar solvent, the intercalation threshold increases from 30 to 70% H₂SO₄. It is shown using a set of characterization techniques that, in the graphite-H₂SO₄-R (R = H₂O, C₂H₅OH) systems, the solvent is not intercalated into graphite. Stage I–III ternary graphite intercalation compounds (TGICs) are synthesized for the first time in the graphite-H₂SO₄-C₂H₅COOH system: stage I TGICs at H₂SO₄ concentrations above 70%, stage II in the range 30–70% H₂SO₄, and stage III at H₂SO₄ concentrations down to 10%. The intercalate layer thickness in the TGICs is 7.94 Å. The mechanism of TGIC formation in this system is shown to differ from those in mixtures of H₂SO₄ and other organic acids. Thermal analysis in combination with spectroscopic analysis of gaseous products provides clear evidence for intercalation of propionic acid into the TGIC and indicates that the thermal stability of this compound is lower than that of graphite bisulfate.Translated from Neorganicheskie Materialy, Vol. 41, No. 2, 2005, pp. 162–169.Original Russian Text Copyright © 2005 by Shornikova, Sorokina, Maksimova, Avdeev.     

Molybdenum dissolution in mixtures of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and concentrated HNO<Subscript>3</Subscript> and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> in the presence of tungsten

The oxidation of molybdenum and tungsten in hydrogen peroxide solutions and the effect of H₂O₂ on the selectivity of Mo and W dissolution in mixtures of concentrated nitric and sulfuric acids have been studied.     

Two-step growth of SrTiO<Subscript>3</Subscript> films on Sr-modulated Si(001) substrates

Perovskite-type SrTiO₃ (STO) films have been grown on the Sr-modulated Si(001) substrates using two-step growth method with a molecular beam epitaxy technique. About 6 Å Sr was deposited on the surface of chemically formed SiO₂/Si at 800 C, which resulted in the formation of Si(001)-Sr(2 × 1) surface. About 250-Å-thick STO films have been deposited on the Si(001)-Sr(2 × 1) surface at 350 C in the O₂ partial pressure of approximately 3 × 10^–7 Torr (first step), followed by an annealing at 600 C in a pressure of 3 × 10^–9 Torr (second step). Reflection high-energy electron diffraction patterns of grown films become elongated streaky features after the annealing, suggesting the solid-phase epitaxial growth of STO. The presence of strong STO(001) and STO(002) diffraction peaks in X-ray diffraction measurements suggests that the high-quality crystalline STO films grow on the Sr-modulated Si(001) substrates by the two-step growth method. Atomic force microscopy image shows the smooth surface with root mean square roughness of about 18 Å.     

Optical anisotropy and dielectric parameters of (Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>)Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films on a Pt(111)/Si(001) substrate

(Ba_0.5Sr_0.5)Nb₂O₆ films were synthesized on a Pt(111)/Si(001) substrate by RF gas-discharge sputtering in pure oxygen atmosphere. It was found that the films have a dominant crystallographic orientation in the [001] direction and natural unipolarity, which was revealed through analysis of dielectric and piezoelectric parameters. It was demonstrated that the optical parameters of film material in the Ba_0.5Sr_0.5, Nb₂O₆/Pt(111)/Si(001) heterostructure match those typical for a (Ba_0.5Sr_0.5)Nb₂O₆ single crystal.     

Proton Conductivity and Thermal Properties of Ba(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

We have grown single crystals of barium dihydrogen phosphate and studied its thermal transformations during heating to 500°C and its electrotransport properties. Ba(H₂PO₄)₂ (Pccn) has been shown to undergo no phase transitions up to its dehydration temperature. The thermal decomposition of Ba(H₂PO₄)₂, accompanied by dehydration, involves two steps, with maximum rates at ~265 and 370°C, and results in the formation of barium dihydrogen pyrophosphate and barium metaphosphate, respectively. The total enthalpy of the endothermic dehydration events is–244.6 J/g. Using impedance spectroscopy, we have studied in detail the proton conductivity of polycrystalline and single-crystal Ba(H₂PO₄)₂ samples in a controlled atmosphere. Adsorbed water has been shown to have a significant effect on the proton conductivity of Ba(H₂PO₄)₂ up to 130°C. The proton conductivity of the Ba(H₂PO₄)₂ single crystals has been shown to be anisotropic. The conductivity anisotropy correlates with specific structural features of the salt. Higher conductivity values, 3 × 10^–9 to 2 × 10^–7 S/cm in the range 60–160°C, have been observed in the [100] crystallographic direction, exceeding the conductivity along [010] by an order of magnitude. The activation energy for proton conduction is 0.80 eV.     

Reaction of Np(VI) with H<Subscript>2</Subscript>O<Subscript>2</Subscript> in carbonate solutions

The kinetics and stoichiometry of the reaction of Np(VI) with H₂O₂ in carbonate solutions were studied by spectrophotometry. In the range 1–0.02 M Na₂CO₃, the reaction 2Np(VI) + H₂O₂ = 2Np(V) + O₂ occurs, as Δ[Np(VI)]/Δ[H₂O₂] ≈ 2. In Na₂CO₃ + NaHCO₃ solutions, the stoichiometric coefficient decreases, which is caused by side reactions. The reduction at low (1 mM) concentrations of Np(VI) and H₂O₂ follows the first-order rate law with respect to Np(VI), which suggests the formation of a Np(VI) peroxide-carbonate complex, followed by intramolecular charge transfer. Addition of Np(V) in advance decreases the reaction rate. An increase in the H₂O₂ concentration leads to the reaction deceleration owing to formation of a complex with two peroxy groups. In a 1 M Na₂CO₃ solution containing 1 mM H₂O₂, the first-order rate constant k increases with a decrease in [Np(VI)] from 2 to 0.1 mM. For solutions with [Np(VI)] = [H₂O₂] = 1 mM, k passes through a minimum at [Na₂CO₃] = 0.5–0.1 M. The activation energy in a 0.5 M Na₂CO₃ solution is 48 kJ mol⁻¹.     

Behavior of Np(VI) and Np(V) Ions in NaHCO<Subscript>3</Subscript> Solutions Containing H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The behavior of Np(VI) and Np(V) in NaHCO₃ and NaHCO₃ + Na₂CO₃ solutions containing H₂O₂ was studied spectrophotometrically. In 0.75–1.0 M NaHCO₃, hydrogen peroxide oxidizes Np(V) to Np(VI). The kinetics curves of Np(V) oxidation into Np(VI) have a complex shape and are characterized either by an induction period of up to tens of minutes or by a period of steady-state Np(VI) concentration, followed by an increase in the Np(VI) concentration. When Np(VI) initially exists in the solution, the induction period is lacking. The process character changes when the bicarbonate concentration decreases, or when Na₂CO₃ is added. In 1.0 M Na₂CO₃, 0.5 M NaHCO₃ + 0.5 M Na₂CO₃, or 0.01–0.5 M NaHCO₃, hydrogen peroxide completely reduces Np(VI) into Np(V). The probable mechanisms of this process were discussed. Accumulation of Np(VI) in NaHCO₃ solutions can be accounted for by assuming that Np(VI) itself participates in the transformations. Initially, the reaction of Np(VI) with H₂O₂ yields the excited *Np(V) ion. Then it reacts with another H₂O₂ molecule and forms a carbonate-peroxide complex. In the collision of the latter with unexcited Np(V), two electrons from two Np(V) ions are transferred onto the O ₂ ^2? ligand with formation of two Np(VI) ions.     

Etching behavior of CdTe in aqueous H<Subscript>2</Subscript>O<Subscript>2</Subscript>-HI-C<Subscript>6</Subscript>H<Subscript>8</Subscript>O<Subscript>7</Subscript> solutions

This paper examines the dissolution behavior of the (111)A, (111)B, (110), and (100) surfaces of CdTe single crystals in aqueous H₂O₂-HI-C₆H₈O₇ (citric acid) solutions. We have determined the dissolution rate of the crystals as a function of temperature and solution concentration, located the composition regions of polishing and selective etchants, and studied the microstructure and roughness of surfaces polished with optimized etchants. The etching behavior of CdTe is shown to depend on its crystallographic orientation.     

Electrical and Magnetic Properties of Ultrathin Polycrystalline Fe Films Grown on SiO<Subscript>2</Subscript>/Si(001)

Ultrathin polycrystalline Fe films have been grown on the oxidized surface of a Si(001) substrate. The resistivity and magnetic hysteresis of Fe films have been measured in the range of thickness from 2.5 to 10 nm. Based on the analysis of the data obtained, it is suggested that there is a transition to the structurally continuous film at a thickness of ~6 nm. It is found that Fe grains in this film acquire the preferred (111) orientation during this transition.     

Synthesis,crystal structure,and proton conductivity of KFe(H<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

KFe H₂P₂O7)₂ is synthesized at 443 K in molten polyphosphoric acids containing K and Fe ions, and its crystal structure is determined: triclinic unit cell with a = 4.9974(6) Å, b = 7.4766(9) Å, c = 7.8185(9) Å, = 82.29(2)°, = 83.37(2)° , = 74.13(2)° ; Z = 1, sp. gr. P . The structure is made up of infinite ribbons formed by corner-shared PO₄ tetrahedra and FeO₆ octahedra, with the K atoms in between. Neighboring ribbons are linked by hydrogen bonds. The proton conductivity of potassium iron(III) dihydrogen diphosphate is rather low.Translated from Neorganicheskie Materialy, Vol. 41, No. 1, 2005, pp. 74–77. Original Russian Text Copyright © 2005 by Chudinova, Murashova, Ilyukhin, Tarnopolskii, Yaroslavtsev.     

Dielectric properties of Be(IO<Subscript>3</Subscript>)<Subscript>2</Subscript>⋅4H<Subscript>2</Subscript>O crystals

The article studies the dielectric properties, dc conductivity and ac conductivity of Be(IO₃)₂⋅4H₂O single crystals. The dielectric constant ε has been defined for the three directions of the vectors a, b and c in the crystals in the temperature interval 280–340 K and frequency range 100 Hz–10⁶ Hz. The crystals show strongly expressed anisotropy, at 20 ^∘C and frequency 100 Hz ε_a = 235, ε_b = 30 and ε_c = 85. The frequency dependence of ε is evidence of the presence of low-frequency relaxation polarization in the crystals. The activation energies of the three directions in the crystals have been derived from the temperature dependence of dc conductivity, and they are 1.03 eV, 0.836 eV and 1.2 eV respectively.     

Reduction of Np(V) with Fe(II) in weakly acidic solutions containing H<Subscript>2</Subscript>C<Subscript>2</Subscript>O<Subscript>4</Subscript>

The kinetics of the reaction of Np(V) with Fe(II) in dilute perchloric and nitric acid solutions containing H₂C₂O₄ was studied by spectrophotometry. In the range pH 1–2, the reaction rate is described by the equation d[Np(V)]/dt = k[Np(V)][Fe(II)][H₂C₂O₄]²[H⁺]^−1.6, k = 182 mol^−1.4 l^1.4 s⁻¹. The activation energy in the range 25–45°C is 26 kJ mol⁻¹. The reaction mechanism involves formation of Fe(II) and Np(V) oxalate complexes, followed by their reaction with the participation of the H⁺ ion.     

Synthesis and crystal structure of Cu<Subscript>2</Subscript>{(UO<Subscript>2</Subscript>)<Subscript>3</Subscript>[(S,Cr)O<Subscript>4</Subscript>]<Subscript>5</Subscript>}(H<Subscript>2</Subscript>O)<Subscript>17</Subscript>

Cu₂{(UO₂)₃[(S,Cr)O₄]₅}(H₂O)₁₇ crystals were prepared by evaporation of aqueous solutions. The crystal structure was solved by the direct method and refined to R ₁ = 0.064 (wR ₂ = 0.177) for 8120 reflections with ¦F _hkl¦ 4 ¦F _hkl¦. Rhombic system, space group Pbca, a = 18.0586(8), b = 19.9898(9), c = 20.5553(8) Å, V = 7420.2(6) ų. The structure is based on {(UO₂)₃[(S,Cr)O₄]₅}^4– anionic layers, formed by combination of UO₇ pentagonal bipyramids and TO₄ tetrahedra through common vertices. The { (UO₂)₃ [(S,Cr)O₄]₅}^4– layers are parallel to the (010) plane. The Cu²⁺ (H₂O)₆ octahedra and additional water molecules are located in the interplanar space and provide binding of the layers in the structure by hydrogen bonds. Based on the occupancy of tetrahedral positions, more accurate chemical formula of the compound should be written as Cu₂{(UO₂)₃[(S_0.804 Cr_0.196)O₄]₅} (H₂O)₁₇.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 408–411.Original Russian Text Copyright © 2004 by Krivovichev, Burns.     

Plutonium dioxide catalyzed reaction between H<Subscript>2</Subscript> and O<Subscript>2</Subscript>

The kinetic characteristics of the reaction between H₂ and O₂ were calculated to more adequately simulate the radiolysis of water adsorbed on PuO₂. The rate constants of this reaction were determined via comparison of the calculated results with the published experimental data. It was found that, with the amount of the adsorbed water increasing from 2 × 10^?4 to 5 × 10^?3%, the rate constant of the reaction decreases from 6.0 × 10^?4 to 1.7 × 10^?5 mol^?1 s^?1. At the water content over 5 × 10^?3%, the rate constant is ≤1 × 10^?5 mol^?1 s^?1. A new mathematical model of the radiation-chemical and physicochemical processes occurring in the PuO₂-H₂O system was presented; the amounts of hydrogen and oxygen yielded by α-radiolysis of the adsorbed water were calculated, taking into account the reaction between H₂ and O₂.     

Enhanced photocatalytic performance of SrTiO<Subscript>3</Subscript> crystals with (100), (110) and (111) orientations treated by N<Subscript>2</Subscript> (H<Subscript>2</Subscript>) plasma

The nitrogen/hydrogen (N₂/H₂) plasma-treated strontium titanate (SrTiO₃) crystals with different orientations of (111), (110) and (100) were obtained using microwave plasma chemical vapor deposition, which was proved to be a simple and effective strategy to fundamentally improve the photocatalytic performance. It is found that plasma-treated SrTiO₃ crystals exhibit different photocatalytic properties in relation to crystalline anisotropy, plasma types and microwave power. The N: SrTiO₃ samples display higher photocatalytic activity compared to the untreated sample and N₂/H₂-treated sample. The (111) N: SrTiO₃ which is treated using N₂ plasma of 600 W shows the best photocatalytic performance in the current research. The dopants of nitrogen can serve as electron donors, which introduce impurity states in various positions in the band gap of SrTiO₃ and lead to different degrees of modification in electrical conductivity. The enhancement for photocatalytic properties and the effects of N₂ plasma treatment on the charge separation and transfer efficiency will be discussed.     

High performance films obtained from PVA/Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>/H<Subscript>2</Subscript>O and PVA/CH<Subscript>3</Subscript>COONa/H<Subscript>2</Subscript>O systems

The atactic poly(vinyl alcohol) (a-PVA) aqueous solutions with Na₂SO₄ or CH₃COONa were cast to prepare films and then the Na₂SO₄ or CH₃COONa in the films was removed. Both films prepared by removing Na₂SO₄ or CH₃COONa in water had a water-resistance property. The degree of crystallization of the films increased with an increase of the contents of Na₂SO₄ and CH₃COONa in the solutions up to 0.05 and 0.1 wt%, respectively. However, the melting temperature (226–228°C) was independent of the content of Na₂SO₄ and CH₃COONa in the solutions. The draw ratio and tensile modulus of the films prepared from the solutions with 0.01 wt% Na₂SO₄ and 0.1 wt% CH₃COONa were 1.3–1.6 times more than that of the films obtained from an aqueous solution. Namely, in case of the films obtained from a-PVA/H₂O/Na₂SO₄ and a-PVA/H₂O/CH₃COONa systems, both the drawability and mechanical properties as well as the degree of crystallization were higher than those for the film obtained from an aqueous a-PVA solution.     

Study on simultaneous detection of CO and H<Subscript>2</Subscript> with (Pd,Fe)-modified SnO<Subscript>2</Subscript> and Pt-loaded SnO<Subscript>2</Subscript> sensors

The (Pd, Fe)-modified SnO₂ (S1) and Pt-loaded SnO₂ (S2) are synthesized via a sol–gel method. As S1 has better selectivity to CO against H₂ while S2 to H₂ against CO at 400 °C. Thus S1 and S2 can be used to detect the concentration of CO and H₂, respectively. However, neither S1 nor S2 can detect the concentration of CO and H₂ when they coexist. In this paper, S1 and S2 sensors are used simultaneously for mixed gas of CO and H₂ detection, and the respective concentration of CO and H₂ is calculated. The calculation process is explained as follows: the response of S1 (R₁) and S2 (R₂) to a fixed concentration of mixed gas of CO and H₂ is obtained in experiment, respectively. So we can calculate the concentration of CO and H₂ by using simultaneous equations with the independent variable R₁ and R₂. Contrast real values with calculated values of CO and H₂ concentration, the error margin are all less than 5%, which indicates that this method may be a promising candidate for enhancing the selectivity of semiconductor-based gas sensor to two or more gases.     

Ab initio study of antiferroelectric PbZrO<Subscript>3</Subscript> (001) surfaces

We have carried out first-principles total-energy calculations of bulk and (001) surfaces of PbZrO₃. The ground state for bulk PbZrO₃ is determined to be the antiferroelectric orthorhombic phase, with the ferroelectric rhombohedral and paraelectric cubic phases being 0.14 and 0.39 eV per formula unit higher in energy, respectively. PbO- and ZrO₂-terminated (001) surfaces, either clean or when hydroxyl species were adsorbed were considered. Surface relaxations, in-plane antiferroelectric distortions and modifications to the electronic structure due to the surfaces, and hydroxyl adsorbates on the surfaces were investigated. We find that while clean surfaces retained bulk-like behavior, hydroxyl adsorbates induce significant changes to the surface geometry as well as introduce electronic states in the band gap possibly rendering the surfaces metallic.     

Manifestation of Nd ions on the structure,Raman and IR spectra of (TeO<Subscript>2</Subscript>-MoO-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>) glasses

The structure of [80TeO₂ + (20–x)MoO + xNd₂O₃] glasses, with x = 0, 4, 6, 10 and 12 mol%, is studied in this work. Raman scattering in the spectral range (−2000 to 3500 cm⁻¹) and IR absorption spectra have been measured for crystalline TeO₂ and glasses, and their assignments were discussed and compared. Many vibrational modes were found active in both Raman and IR and their assignments for crystalline TeO₂ and for the glasses were discussed in relation to the tetragonal structure of crystalline α -TeO₂. Nd₂O₃ was found to completely eliminate diffuse scattering and enhance the Raman scattering intensity. Anti-stokes Raman bands in the range −1460 cm^{− 1} to −1975 cm^{− 1} were observed for both (30Li₂O + 70B₂O₃+ xNd₂O₃) glasses and [80TeO₂ + (20−x)MoO + xNd₂O₃] glasses and were attributed to some emission processes due to the doping of the glasses with Nd₂O₃.