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.     

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.     

Synthesis of CuO nanoflower and its application as a H<Subscript>2</Subscript>O<Subscript>2</Subscript> sensor

CuO three-dimensional (3D) flower-like nanostructures were successfully synthesized by a simple method at 100°C with Cu(NO₃)₂·3H₂O and NH₃·H₂O for 6 h in the absence of any additives. We found that NH₃·H₂O amount was critical for CuO morphology evolution. The phase analysis was carried out using X-ray diffraction (XRD) and the result confirmed that the CuO nanoflowers were single-phase. The morphological investigations by field emission scanning electron microscope (FESEM) revealed that the CuO nanoflowers were mono-dispersed in a large quantity and consisted of nanosheets. And then, CuO nanoflowers were successfully used to modify a gold electrode to detect H₂O₂ with cyclic voltammetry (CV) and amperometric (AC). It was found that CuO nanoflowers may be of great potential for H₂O₂ electrochemical sensing.     

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.     

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.     

Niobium pentoxide as promoter in the mixed MgH<Subscript>2</Subscript>/Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system for hydrogen storage: a multitechnique investigation of the H<Subscript>2</Subscript> uptake

Nb₂O₅ is known as good promoter for adsorption/desorption kinetics of hydrogen in magnesium hydride. In this article the interaction with hydrogen of bare Nb₂O₅, the oxidic component of the mixed MgH₂/Nb₂O₅ system, is investigated in various conditions (i.e. employing atomic, molecular and nascent hydrogen). The state of the hydrogen-Nb₂O₅ system was monitored using various techniques including: X-ray Diffraction, Electron Paramagnetic Resonance, Diffuse Reflectance UV-Vis Spectroscopy, Thermal Desorption Spectroscopy -Mass Spectrometry, Differential Scanning Calorimetry and Thermal Programmed Desorption. Niobium (V) oxide is not at all inert while interacting with hydrogen. This oxide is partially reduced by hydrogen, which is incorporated in the solid and released as both molecular hydrogen and water. This peculiar behaviour, reminiscent of some properties of the bronze family, suggests an active chemical role played by Nb₂O₅ in the mixed MgH₂/Nb₂O₅ system.     

The calculation of liquid-vapor phase equilibrium in H<Subscript>2</Subscript>O-H<Subscript>2</Subscript>O<Subscript>2</Subscript> two-component system

The dependences of total pressure and equilibrium composition of vapors on temperature and mole fraction of hydroperoxide in solution are calculated for a water-hydroperoxide two-component two-phase system. It is assumed that the relaxation to concentration equilibrium in gas at the surface of solution is attained quite rapidly compared to the half-life of hydroperoxide. Three independent approximate methods are used to calculate the total pressure. The ideal gas approximation for the gas phase is not used in two of these methods. Approximation formulas are suggested, which explicitly express the dependence of pressure and composition of gas on relative concentration of hydroperoxide in solution and on temperature. The accuracy of the methods and the range of their validity are discussed.     

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.     

Visualizing grain boundaries in monolayer MoSe<Subscript>2</Subscript> using mild H<Subscript>2</Subscript>O vapor etching

Beyond graphene, two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant attention owing to their potential in next-generation nanoelectronics and optoelectronics. Nevertheless, grain boundaries are ubiquitous in large-area as-grown TMD materials and would significantly affect their band structure, electrical transport, and optical properties. Therefore, the characterization of grain boundaries is essential for engineering the properties and optimizing the growth in TMD materials. Although the existence of boundaries can be measured using scanning tunneling microscopy, transmission electron microscopy, or nonlinear optical microscopy, a universal, convenient, and accurate method to detect boundaries with a twist angle over a large scale is still lacking. Herein, we report a high-throughput method using mild hot H₂O etching to visualize grain boundaries of TMDs under an optical microscope, while ensuring that the method is nearly noninvasive to grain domains. This technique utilizes the reactivity difference between stable grain domains and defective grain boundaries and the mild etching capacity of hot water vapor. As grain boundaries of two domains with twist angles have defective lines, this method enables to visualize all types of grain boundaries unambiguously. Moreover, the characterization is based on an optical microscope and therefore naturally of a large scale. We further demonstrate the successful application of this method to other TMD materials such as MoS₂ and WSe₂. Our technique facilitates the large-area characterization of grain boundaries and will accelerate the controllable growth of large single-crystal TMDs.

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Stability limits of graphite intercalation compounds in the systems graphite-HNO<Subscript>3</Subscript>(H<Subscript>2</Subscript>SO<Subscript>4</Subscript>)-H<Subscript>2</Subscript>O-KMnO<Subscript>4</Subscript>

The formation of binary graphite intercalation compounds (GICs) with nitric and sulfuric acids in the presence of a strong oxidant has been studied by x-ray diffraction and potentiometry in a wide range of acid concentrations. The redox potential of the oxidizing solution and the intercalation ability of the acid are shown to influence the stage number (the number of graphite layers between two successive intercalate layers) of the forming GIC and the concentration ranges of GIC formation. The (\(E_{H_2 } \))-H ₀ (redox potential of the oxidizing solution-Hammett function of the acid) stability fields of graphite nitrate and graphite bisulfate are presented. Our results are the first to demonstrate that KMnO₄ extends the concentration ranges of GIC formation and reduces the threshold acid concentration for the synthesis of binary GICs (to 40%).     

Preparation of lamellar-stacked TS-1 and its catalytic performance for the ammoximation of butanone with H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A SiO₂ particle was prepared with different alkali sources, and then lamellar-stacked TS-1 catalysts were hydrothermally synthesized using the SiO₂ particle as a silica source. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectra, nitrogen adsorption–desorption and UV–vis absorption spectra were used to characterize the TS-1 catalysts. The effect of the alkali source during the preparation of the SiO₂ particle on the textural properties and catalytic performance of the TS-1 catalyst was thoroughly investigated. The TS-1 catalyst that was prepared with a SiO₂ particle using tetrapropylammonium hydroxide (TPAOH) as an alkali source (TS-1-TPAOH) possessed more meso- and macro-pores and a higher framework Ti content than the catalyst that was prepared with a SiO₂ particle using NH₃·H₂O as an alkali source (TS-1-NH₃·H₂O). As a result, the TS-1-TPAOH catalyst had a better catalytic performance for butanone ammoximation with H₂O₂ than conventional TS-1 and TS-1-NH₃·H₂O catalysts. Furthermore, the influences of reaction conditions, including reaction temperature, reaction time, the amount of catalyst and the molar ratio between H₂O₂ and butyl ketone oxime on the catalytic performance of the TS-1-TPAOH catalyst were evaluated. The unique structure of the lamellar-stacked TS-1 catalyst can effectively avoid the diffusing of large reactant molecules into zeolite channels and has potential applications in other oxidation reactions.     

Crystal structure of a complex of Pu(VI) nitrate with triphenylphosphine oxide, [PuO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(OP(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of [PuO₂(NO₃)₂(TPPO)₂] (TPPO = OPPh₃) isostructural to the related compounds of uranyl and neptunyl were isolated, and the structure of this complex was determined. Contrary to the complexes [AnO₂(TPPO)₄](ClO₄)₂ studied previously, the interatomic distances and volumes of coordination polyhedra of An in these compounds somewhat decrease in the series U-Np-Pu. This difference was attributed to a change in the number of TPPO ligands in the compounds and weakening of their interaction with oxygen atoms of the AnO ₂ ²⁺ groups in passing from [AnO₂(TPPO)₂](ClO₄)₂ to [AnO₂(No₃)₂(TPPO)₂].     

Vertical α-FeOOH nanowires grown on the carbon fiber paper as a free-standing electrode for sensitive H<Subscript>2</Subscript>O<Subscript>2</Subscript> detection

Highly sensitive,selective,and stable hydrogen peroxide (H2O2) detection using nanozyme-based catalysts are desirable for practical applications.Herein,vertical α-FeOOH nanowires were successfully grown on the surface of carbon fiber paper (CFP) via a low-temperature hydrothermal procedure.The formation of vertical α-FeOOH nanowires is ascribed to the structure-directing role of sodium dodecyl sulfate.The resulting free-standing electrode with one-dimensional (1D)nanowires offers oriented channels for fast charge transfer,excellent electrical contact between the electrocatalyst and the current collector,and good mechanical stability and reproducibility.Thus,it can serve as an efficient electrocatalyst for the reduction and sensitive detection of H2O2.The relation of the oxidation current of H2O2 with the concentration is linear from 0.05 to 0.5 mM with a sensitivity of-0.194 mA/(mM.cm2) and a low detection limit of 18 μM.Furthermore,the portability in the geometric tailor and easy device fabrication allow extending the general applicability of this free-standing electrode to chemical and biological sensors.     

Viscosity of H<Subscript>2</Subscript>O in the Critical Region

It has been well established that thermodynamic and transport properties of fluids exhibit singular behavior near the critical point. In this article, the theoretical predictions for the enhancement of the viscosity near the critical point are reviewed. It is then shown how these predictions can be used to obtain a representative equation for the viscosity of H₂O in the critical region. Contribution of the National Institute of Standards and Technology, not subject to U.S. copyright.     

Synthesis,crystal structure,and absorption spectra of a complex neptunium(v) chromate,Na<Subscript>3</Subscript>[NpO<Subscript>2</Subscript>(CrO<Subscript>4</Subscript>)<Subscript>2</Subscript>](H<Subscript>2</Subscript>O)<Subscript>5</Subscript>

A new Np(V) chromate complex with outer-sphere sodium cations, Na₃[NpO₂(CrO₄)₂](H₂O)₅ (I), was synthesized from aqueous solution. Its composition and structure were determined by single crystal X-ray diffraction. The structure of I is based on anionic chains of the composition [NpO₂(CrO4)2] _n ³ⁿ⁻, running along [010] and forming layers parallel to the (101) plane. The Na⁺ ions and water molecules of crystallization are arranged between the layers. The coordination polyhedra of the Np atoms (pentagonal bipyramids) are combined pairwise by sharing common equatorial edges formed by two bridging oxygen atoms of bidentate chelate-bridging CrO₄ groups. The absorption spectra of I in the IR and visible ranges are presented.     

Oxidation of Pu(IV) to Pu(VI) with an XeO<Subscript>3</Subscript> + H<Subscript>2</Subscript>O<Subscript>2</Subscript> Mixture in a Perchloric Acid Solution

In a perchloric acid solution, XeO₃ does not oxidize Pu(IV), but the addition of H₂O₂ leads to the accumulation of Pu(VI). It is assumed that Pu(IV) forms a complex with XeO₃. The reaction of the complex with hydrogen peroxide generates OH radicals, which oxidize Pu(IV) to Pu(V). The latter disproportionates to Pu(IV) and Pu(VI).     

Etching Behavior of Undoped and Doped CdTe in Aqueous H<Subscript>2</Subscript>O<Subscript>2</Subscript>-HBr-Ethylene Glycol Mixtures

The mechanism and kinetics of undoped and doped CdTe dissolution in aqueous H₂O₂-HBr-ethylene glycol mixtures are investigated. The results are used to construct the dissolution rate-etchant composition diagrams for the materials studied and to identify the rate-limiting step of the dissolution process. Dissolution in polishing etchants is shown to be diffusion-limited. Doping has a significant effect on the dissolution behavior of CdTe.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 775–781.Original Russian Text Copyright © 2005 by Z. Tomashik, Stratiichuk, V. Tomashik, Feichuk, Shcherbak.     

Internal Pressure in Binary Mixtures of Methylpyridine Isomers with H<Subscript>2</Subscript>O and D<Subscript>2</Subscript>O

Internal pressures and their excesses were calculated in the strict thermodynamic way for binary mixtures of 2-,3-,4-methylpyridine, 2,6-dimethylpyridine, and 2,4,6-dimethylpyridine with water and heavy water at T =  296.15 K. The excess internal pressure approach proved to be useful in studies of relatively subtle thermodynamic effects. Positive correlation was found between the association energy of the 1:1 water–amine complexes and the maximum values of the excess internal pressure. It was shown that the differences caused by the exchange of H₂O by D₂O in the mixtures are evident in the excess internal pressure isotherms. The larger excesses for the D₂O mixtures may indicate that the difference in energy between the O–D· · ·N and O–D· · ·O bonds is higher than that between the O–H· · ·N and O–H· · ·O ones. That probably leads to different phase properties of the studied systems.     

Optoelectronic and thermoelectric response of Ca<Subscript>5</Subscript>Al<Subscript>2</Subscript>Sb<Subscript>6</Subscript> to shift of band gap from direct to indirect

The structural, optoelectronic and thermoelectric properties of Ca₅Al₂Sb₆ under applied external pressures have been studied using the full potential linear augmented plane wave method. WIEN2k code is used with considering the generalized gradient approximation (GGA), modified Becke–Johnson (MBJ) and modified Becke–Johnson?+?spin orbit (mBJ?+?SO) functionals based on density functional theory (DFT). From electronic results, the size of the band gap decreases with increasing pressure and the nature of the band gap shift from direct to the indirect. In high pressure (>35.7 GPa by mBJ?+?SO), the band gap is also completely disappeared and the nature of compound is changed to the metallic. The calculated anisotropic optical properties such as the static dielectric function, increase with decreasing the size of band gap and increasing of pressure. As a novel result, the thermoelectric performance of n-type and p-type doping of Ca₅Al₂Sb₆ is related to the value of pressure. According to the thermoelectric results, the n-type one has the highest ZT in comparison with the p-type Ca₅Al₂Sb₆ material.