Investigation of the effect of activated carbon and 3d-metal containing additives on the hydrogen sorption properties of magnesium

A comparison in the hydrogen sorption properties of mechanically activated magnesium composites with additive of 3d-metal containing compounds (Mg₂Ni_0.8Co_0.2 and NiCo₂O₄) and activated carbon derived from agricultural by-products (ACAS) is accomplished. The presence of the additives used enhances significantly the hydriding reaction and increases the absorption capacity compared to pure magnesium. The absorption capacity values of the composites studied are as follows: Mg (−44 μm)–5 wt.% ACAS–6.13 wt.%, Mg (−297 μm)–5 wt.% ACAS–5.48 wt.%, Mg(−44 μm)–15 wt.% Mg₂Ni_0.8Co_0.2–4.78 wt.% and Mg (−44 μm)–5 wt.% NiCo₂O₄–5.69 wt.% (T = 573 K, P = 1 MPa, after 60 min of hydriding). The composites preserve their hydrogen sorption capacities during prolonged cycling. The use of the additive of activated carbon instead of 3d-metal containing compounds in magnesium based composites results, on the one hand, in a higher absorption capacity which increases during cycling, but on the other hand, a poorer hydriding kinetics.     

Thermal and mechanically activated decomposition of LiAlH4

Thermal stability of as-received LiAlH₄ and milled LiAlH₄ has been investigated. The thermal decomposition mechanism of as-received LiAlH₄ depends on the temperature-time history. Apparent activation energies and enthalpies of the reactions have been obtained. During milling treatment, the high temperature and pressures locally induced by shocks lead to LiAlH₄ mechanically decomposition. The decomposition temperatures of LiAlH₄ and Li₃AlH₆ are both reduced by ∼60 °C due to particle size reduction produced by mechanical milling. Besides, the activation energy of the decomposition reaction of LiAlH₄ decreases as compared to as-received LiAlH₄. Moreover, a layer of oxide (∼5 nm) at the surface of the milled alanate Li₃AlH₆ is observed. This layer could have a drastic influence on decomposition H-kinetics.     

Photocatalytic hydrogen production over Na2Ti2O4(OH)2 nanotube sensitized by CdS nanoparticles

Na₂Ti₂O₄(OH)₂ nanotubes were obtained by hydrothermal reaction of TiO₂ with concentrated NaOH solution. CdS nanoparticles were then decorated on Na₂Ti₂O₄(OH)₂ nanotubes through partial ion-exchange method. The composite photocatalysts were characterized by X-ray diffraction (XRD), ultraviolet-visible spectra (UV-vis), transmission electron microscope (TEM), etc. The results showed that CdS nanoparticles of 5-6 nm were anchored on the surface of the Na₂Ti₂O₄(OH)₂ nanotubes. Under irradiation of visible light (λ ≥ 430 nm), the prepared CdS/Na₂Ti₂O₄(OH)₂ showed high photoactivity for hydrogen production.     

Low-temperature performance of Al4B2O9 nanowires

In this paper we report on the synthetic investigation of single-crystalline aluminum borate (Al₄B₂O₉) nanowires in large scale by a direct calcination of a precursor powder made of Na₂B₄O₇·10H₂O and Al (NO₃)₃·9H₂O at a low temperature of 850 °C. The nanowires, with the diameter of 20-40 nm and the length up to several micrometers, possess smooth surfaces and uniform sizes along the entire wire. The growth mechanism of the nanowires is attributed to a solid-liquid-solid process, which controls the nanowire morphology.     

Crystal structures of CdTi2O4(OH)2 and LaTiSbO6

The crystal structures of two PbSb₂O₆-type compounds containing titanium, CdTi₂O₄(OH)₂ and LaTiSbO₆ were refined by X-ray powder diffraction data. For both compounds structure refinements with the space group were successful and the R-factors were R_WP = 6.46% and R_P = 4.90% for CdTi₂O₄(OH)₂ and R_WP = 9.55% and R_P = 7.17% for LaTiSbO₆. These crystal structures were the same as that of the typical PbSb₂O₆-type compound in spite of the existence of protons in the interlayer or two different metal ions in the layer.     

Photocatalytic properties of TiO2-P2O5 glass ceramics

Binary TiO₂-P₂O₅ glasses with 69 mol% and 76 mol% TiO₂ were prepared and converted into glass ceramics by heat-treatments. XRD measurements show that the main crystalline phases precipitated in the glass ceramics are anatase-type TiO₂ crystals or (TiO)₂P₂O₇ crystals, depending on the concentration of titanium constituent. Photocatalytic activities of the glass ceramics were evaluated by the decomposition of methylene blue (MB) and measuring the water contact angle. It is found that the glass ceramics containing anatase crystals exhibit both photocatalytic oxidation activity and highly photo-induced hydrophilicity under UV irradiation with intensity of 1.0 mW/cm².     

Microwave synthesis and electrochemical characterization of mesoporous carbon@Bi2O3 composites

An efficient and quick microwave method has been employed to prepare worm-like mesoporous carbon@Bi₂O₃ composites for the first time. As-prepared products have been characterized by X-ray diffraction, N₂ adsorption-desorption, scanning electron microscopy, transmission electron microscopy and inductive coupled plasma atomic emission spectroscopy. The electrochemical measurement shows the worm-like mesoporous carbon@Bi₂O₃ composites exhibits excellent capacitance performance and the maximum specific capacitance reaches 386 F g⁻¹, three times more than the pure worm-like mesoporous carbon.     

Structural and magnetic properties of a mechanochemically activated Ti-Fe2O3 solid mixture

The mechanochemical effects on the reactivity and properties of a titanium/hematite powder mixture with molar ratio of 1/2 are investigated. Crystalline-phase structure, composition, hyperfine and magnetic behaviors were analyzed as a function of activation time by means of X-ray diffraction, scanning electron microscopy, Mössbauer spectroscopy and vibrating sample magnetometry. The results showed that at relatively short activation times metallic Ti reduces part of the ferric ions, yielding a complex product formed mainly by a mix of two solid solutions Fe_3−xTi_xO₄ (titanomagnetites), both with very different x values (0 < x < 1). Also metallic iron and superparamagnetic hematite particles were detected by Mössbauer spectroscopy. As the mechanical treatment extends the composition of the reactive mixture changes, prevailing in the end the solid solution with higher x value. In contrast, when these activated samples are thermally treated the fraction of the solid solution which is richer in Ti diminishes. This fact produces a significant variation of the saturation magnetization of the obtained material.     

Temperature-dependent oxygen release, intercalation behaviour and catalytic properties of V2O5·xNb2O5 compounds

In order to investigate the catalytic properties, V_2,38Nb_10,7O_32,7, VNb₉O₂₅ and solid solutions of V₂O₅ in TT-Nb₂O₅ were prepared by thermal decomposition of freeze-dried oxalate precursors. The samples were characterised by X-ray diffraction and surface area determination. The crystalline samples are capable of the intercalation of sodium and lithium ions from solution. Above a temperature of about 500 °C, in dependence on the oxygen partial pressure a reversible release and uptake of oxygen without a structural variation takes place. The catalytic properties have been evaluated for the oxidative dehydrogenation (ODH) of propane and propene. There are only small differences in the catalytic activity of the different crystalline samples. Because of the relative high starting temperature, a selective catalytic oxidation of propane to propene is hardly observed.     

Ferroelectric and piezoelectric properties of tungsten substituted SrBi2Ta2O9 ferroelectric ceramics

Tungsten substituted samples of compositions SrBi₂(W_xTa_1−x)₂O₉ (x = 0.0, 0.025, 0.050, 0.075, 0.10 and 0.20) were synthesized by solid-state reaction method and studied for their microstructural, electrical conductivity, ferroelectric and piezoelectric properties. The X-ray diffractograms confirm the formation of single phase layered perovskite structure in the samples with x up to 0.05. The temperature dependence of dc conductivity vis-à-vis tungsten content shows a decrease in conductivity, which is attributed to the suppression of oxygen vacancies. The ferroelectric and piezoelectric studies of the W-substituted SBT ceramics show that the remanent polarization and d₃₃ values increases with increasing concentration of tungsten up to x ≤ 0.05. Such compositions with low conductivity and high P_r values should be excellent materials for highly stable ferroelectric memory devices.     

Effect of B2O3-Bi2O3-SiO2-ZnO glass on the sintering and microwave dielectric properties of 0.83ZnAl2O4-0.17TiO2

The 0.83ZnAl₂O₄-0.17TiO₂ (ZAT) ceramics were synthesized by solid state ceramic route. The effect of 27B₂O₃-35Bi₂O₃-6SiO₂-32ZnO (BBSZ) glass on the microwave dielectric properties of ZAT was investigated. The crystal structure and the microstructure of the ceramic-glass composites were studied by X-ray diffraction and scanning electron microscopic techniques. The low frequency dielectric loss was measured at 1 MHz. The dielectric properties of the sintered samples were measured in the microwave frequency range by the resonance method. Addition of 0.2 wt% of BBSZ improved the dielectric properties with quality factor (Q_u × f) > 120,000 GHz, temperature coefficient of resonant frequency (τ_f) = −7.3 ppm/°C and dielectric constant (?_r) = 11.7. Addition of 10 wt% of BBSZ lowered the sintering temperature to about 950 °C with Q_u × f > 10,000 GHz, ?_r = 10 and τ_f = −23 ppm/°C. The reactivity of 10 wt% BBSZ added ZAT with silver was also studied. The results show that ZAT doped with suitable amount of BBSZ glass is a possible material for low-temperature co-fired ceramic (LTCC) application.     

Thermal shock resistance of the porous Al2O3/ZrO2 ceramics prepared by gelcasting

Porous Al₂O₃/ZrO₂ ceramics with porosity varying from 6% to 50% were fabricated by gelcasting using polystyrene (PS) as pore-forming agent. The effects of sintering temperature on porosity, strength as well as pore size were investigated. The flexural strength of these porous ceramics at room temperature significantly decreases as the porosity increases. Thermal shock resistance of these ceramics was improved by increasing the porosity. Both the critical difference temperature (ΔT_c) and residual strength of high porosity ceramics were higher than those of low porosity ceramics. These improvements can be attributed to the pores in the specimens which relax the thermal shock stress and arrest the propagation of microcracks effectively, which is confirmed by XRD analysis of specimens which encountered different thermal shock temperature difference.     

Preparation and characterization of CuO nanorods by thermal decomposition of CuC2O4 precursor

Synthesis of copper oxide (CuO) nanorods was achieved by thermal decomposition of the precursor of CuC₂O₄ obtained via chemical reaction between Cu(CH₃COO)₂·H₂O and H₂C₂O₄·2H₂O in the presence of surfactant nonyl phenyl ether (9)/(5) (NP-9/5) and NaCl flux. Transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), selected-area electron diffraction (SAED) and high-resolution TEM (HRTEM) were used to characterize the structure features and chemical compositions of the as-made nanorods. The results showed that the as-prepared nanorods is composed of CuO with diameter of 30-100 nm, and lengths ranging from 1 to 3 μm. The mechanism of formation of CuO nanorods was also discussed.     

Improvement in the hydrogen-storage properties of Mg by the addition of metallic elements Ni, Fe, and Ti, and an oxide Fe2O3

Pure Mg was employed as a starting material instead of MgH₂ in this work. The magnesium prepared by mechanical grinding under H₂ (reactive mechanical grinding) with transition elements or oxides showed relatively high hydriding and dehydriding rates when the content of additives was about 20 wt.%. Ni, Fe and Ti were chosen as metallic transition elements to be added. Fe₂O₃ was selected as an oxide to be added. Samples Mg–14Ni–2Fe₂O₃–2Ti–2Fe were prepared by reactive mechanical grinding, and their hydrogen storage properties were examined and compared with those of a pure Mg sample prepared by reactive mechanical grinding under the same conditions. The Mg–14Ni–2Fe₂O₃–2Ti–2Fe sample showed much better hydrogen storage properties than the pure Mg sample. The as-milled Mg–14Ni–2Fe₂O₃–2Ti–2Fe sample did not require the activation. This sample absorbs 4.26 wt.% H for 5 min, and 4.41 wt.% H for 10 min, and 4.56 wt.% H for 60 min at n = 2. It desorbs 1.13 wt.% H for 10 min, 2.67 wt.% H for 30 min, and 3.32 wt.% H for 60 min at n = 2.     

Synthesis and photoluminescence properties of SrLu2O4:Eu superfine phosphor

Superfine powder SrLu₂O₄:Eu³⁺ was synthesized with a precursor prepared by an EDTA - sol-gel method at relatively low temperature using metal nitrate and EDTA as starting materials. The heat decomposition mechanism of the precursor, formation process of SrLu₂O₄:Eu³⁺and the properties of the particles were investigated by thermo-gravimetric (TG) - differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) analyses. The results show that pure SrLu₂O₄:Eu³⁺ superfine powder has been produced after the precursor was calcinated at 900 °C for 2 h and has an elliptical shape and an average diameter of 80-100 nm. Upon excitation with 250 nm light, all the SrLu₂O₄:Eu³⁺ powders show red and orange emissions due to the 4f-4f transitions of Eu³⁺ ions. The highest photoluminescence intensity at 610 nm was found at a content of about 6 mol% Eu³⁺. Splitting of the ⁵D₀-⁷F₁ emission transition revealed that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite by substituting Lu³⁺ ions.     

Hydrothermal synthesis, characterization and magnetic properties of NaVGe2O6 and LiVGe2O6

Supercritical fluids are shown to be an excellent reaction media for the synthesis of novel solid state phases at intermediate temperatures. LiVGe₂O₆ and NaVGe₂O₆ have the common pyroxene structure composed of VO₆ linear chains. NaVGe₂O₆ crystallizes in the monoclinic space group C2/c with four formula units having cell dimensions a = 9.960(4) Å, b = 8.853(10) Å, c = 5.4861(10) Å, β = 106.403(3)°. The structure was refined until R = 0.0290 and R_w = 0.0370. For LiVGe₂O₆ in space group P2₁/c: a = 9.8508(7) Å, b = 8.754(3) Å, c = 5.3948(13) Å, β = 108(3)°, R = 0.0240 and R_w = 0.0250. The compounds contain edge-shared VO₆ octahedral chains and corner-shared GeO₄ tetrahedral chains. The presence of these VO₆ chains results in spin-Peierls distortion. Structural and physical characterization of the compounds are reported.     

Solution combustion synthesis of MgAl2O4 using fuel mixtures

The paper reveals a new perspective concerning the rational fuel selection and the logical elaboration of the recipes for the MgAl₂O₄ solution combustion synthesis. It was shown that Mg(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O exhibit different behavior with respect to urea, glycine and β-alanine. Urea proved to be the most adequate fuel for Al(NO₃)₃·9H₂O, while β-alanine proved to be the most appropriate fuel for Mg(NO₃)₂·6H₂O. Considering that there is a predilection of metal nitrates with respect to these fuels, in the case of MgAl₂O₄ combustion synthesis best results were achieved when fuel mixtures (urea and β-alanine, urea and glycine) were used. The use of fuel mixtures allowed the formation of pure, nanocrystalline MgAl₂O₄ directly from the combustion reaction, without any subsequent annealing step. The use of a single fuel (urea, glycine or β-alanine) led to the formation of an amorphous powder, which required further annealing in order to achieve the formation of crystalline MgAl₂O₄.     

Low-temperature firing and microwave dielectric properties of ZnO-Nb2O5-TiO2-SnO2 ceramics with CuO-V2O5

The effects of CuO-V₂O₅ addition on the sintering temperature and microwave dielectric properties of ZnO-Nb₂O₅-TiO₂-SnO₂ were investigated. The CuO-V₂O₅ addition lowered the sintering temperature of ZnO-Nb₂O₅-TiO₂-SnO₂ ceramics effectively from 1150 to 860 °C due to the liquid-phase effect of Cu₂V₂O₇ and Cu₃(VO₄)₂, as observed by XRD. The microwave dielectric properties were found to strongly correlate with the sintering temperature and the amount of CuO-V₂O₅ addition. The maximum Qf values decreased with increasing CuO-V₂O₅ content, due to the formation of the second phase, Cu₃(VO₄)₂ and CuNbO₃. Zero τ_f value can be obtained by properly adjusting the sintering temperature. At 860 °C, ZnO-Nb₂O₅-TiO₂-SnO₂ ceramics with 1.5 wt.% CuO-V₂O₅ gave excellent microwave dielectric properties: ?_r = 42.3, Qf = 9000 GHz and τ_f = 8 ppm/°C.     

Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.