Synthesis and characterisation of the garnet-related Li ion conductor, Li5Nd3Sb2O12

In this paper the synthesis, conductivity, and structure of the garnet-related Li ion conductor, Li₅Nd₃Sb₂O₁₂, are reported. As for the related Li₅La₃M₂O₁₂ (M = Nb, Ta) materials, this phase shows high Li ion conductivity, with a conductivity at 300 °C of 9.2 × 10⁻³ S cm⁻¹. Structural studies using neutron diffraction indicate a cubic unit cell, space group Ia-3d, with Li located in two partially occupied sites. One of the sites is the traditional garnet structure tetrahedral site, while the other Li site is considerably more distorted. Although the latter is nominally a six coordinate site, a close inspection suggests that the coordination could be described as distorted tetrahedral, with the remaining two bonds being significantly longer (≈2.6 Å).     

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.     

Effect of preparative parameters on the electrical conductivity of Li2SO4-Al2O3 composites

The effect of various preparative parameters, such as the size and form of alumina and also the time of sintering, on the electrical conductivity of the Li₂SO₄-Al₂O₃ composite system has been investigated. The sintering time appears to be an insignificant preparative parameter. The role of different phases of Al₂O₃ on the electrical conductivity of the composite clearly establishes that the maximum enhancement is achieved for γ-Al₂O₃. The 50 m/o Al₂O₃ composition was found to exhibit the highest conductivity, an enhancement of three orders of magnitude at 500°C. The experimental data indicates higher conduction in the space charge layer near the surface to be the possible mechanism of conductivity enhancement.     

Effect of ZrO2 addition on crystallization behaviour, porosity and chemical-mechanical properties of a CaO-TiO2-P2O5 microporous glass ceramic

2-6 mol% ZrO₂ was added to a base glass composition of P₂O₅ 31.25, CaO 43.75, TiO₂ 25 (mol%) at the expense of TiO₂. The prepared glasses were crystallized to bulk glass ceramics containing the major phases of β-Ca₃(PO₄)₂ and CaTi₄(PO₄)₆. DTA was utilized to determine the appropriate phase separation-nucleation and crystallization temperatures. The crystalline products and resulting microstructures were examined by XRD and SEM. The β-Ca₃(PO₄)₂ phase was dissolved out by leaching the resulting glass ceramics in HCl, leaving a porous skeleton of CaTi₄(PO₄)₆. It was shown that ZrO₂ addition resulted in reduction of volume porosity and mean pore diameter while the specific surface area was increased. The smallest median pore diameter and largest surface area were 8.6 nm and 32 m² g⁻¹ respectively obtained for the specimen containing 6 mol% ZrO₂. The ZrO₂ addition also improved the chemical durability and bending strength of porous glass ceramics.     

Sol-gel synthesis and structural characterisation of binary TiO2-P2O5 glasses

An improved method for the sol-gel synthesis of binary (TiO₂)_0.5(P₂O₅)_0.5 glasses has been developed. Elemental analysis of the products showed that the loss of phosphorous upon drying and heat treatment is low. The structure of the heat-treated glasses was studied using neutron diffraction and high-energy X-ray diffraction, analysis of which revealed a structure consisting of PO₄ tetrahedra and TiO₆ octahedra sharing corners in a three-dimensional amorphous network. The Reverse Monte Carlo method was used to produce a structural model which illustrated that the structure of the glass is, at the near-neighbour level, closely analogous to the superstructure of crystalline TiP₂O₇. No significant atomic-scale structural differences were observed between glasses prepared by acid- or base-catalysed sol-gel reactions.     

Crystal structure and ionic conductivity of ruthenium diphosphate ARu2(P2O7)2, A=Li, Na, and Ag, with a tunnel structure

Crystal structure and ionic conductivity of ruthenium diphosphates, ARu₂(P₂O₇)₂ A=Li, Na, and Ag, were investigated. The structure of the Ag compound was determined by single crystal X-ray diffraction techniques. It crystallized in the triclinic space group P−1 with a=4.759(2) Å, b=6.843(2) Å, c=8.063(1) Å, α=90.44(2)°, β=92.80(2)°, γ=104.88(2)°, V=253.4(1) Å³. The host structure of it was composed of RuO₆ and P₂O₇ groups and formed tunnels running along the a-axis, in which Ag⁺ ions were situated. The ionic conductivities have been measured on pellets of the polycrystalline powders. The Li and Ag compounds showed the conductivities of 1.0×10⁻⁴ and 3.5×10⁻⁵ S cm⁻¹ at 150 °C, respectively. Magnetic susceptibility measurement of the Ag compound showed that it did not obey the Curie-Weiss law and the effective magnetic moment decreased as temperature decreased due to the large spin-orbital coupling effect of Ru⁴⁺ ions.     

Cluster formation in Ag2O-P2O5-CdCl2 glass system

Ag₂O-P₂O₅ and Ag₂O-P₂O₅-20 wt% CdCl₂ glasses were prepared by melt quenching method and characterized with the help of several experimental techniques. Powder X-ray diffraction study indicated that the glasses are amorphous in nature. DSC studies showed that CdCl₂ doped glass is chemically more durable. Electrical conductivity and ionic transference number measurements have shown that both the glasses are ionic conductors with Ag⁺ ions as the charge carriers. The electrical conductivity of the doped glass is found to be higher than the undoped one. Structures of the glasses have been proposed on the basis of IR spectral analysis. From SEM studies it has been inferred that addition of 20 wt% CdCl₂ modifies the morphology of Ag₂O-P₂O₅ glass and in its presence formation of clusters composed of nanofibers occur.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

Synthesis by an ionic liquid-assisted method and optical properties of nanoflower Y2O3

Flower-like Y₂O₃ nano-/microstructured phosphors without metal activators have successfully been fabricated by an ionic liquid (IL)-assisted method involving temperature (600 °C) annealing. In this paper, the effect of IL concentration on the morphology of the product has been investigated. The IL plays a crucial role in the formation of various morphologies of Y₂O₃. The structural and morphological features of the obtained samples have been characterized by means of X-ray powder diffraction (XRD) analysis, photoluminescence spectra (PL), Fourier-transform infrared (FT-IR) spectra and X-ray photoelectron spectra (XPS). The photoluminescence spectra of the products exhibit an intense bluish-white emission (ranging from 405 to 430 nm and centered at 418 nm). The luminescent mechanisms have been ascribed to the carbon impurities in the Y₂O₃ host. The effect of the ILs cation and the counter anions on the Y₂O₃ morphology of these nanostructures was studied experimentally. It was observed that Y₂O₃ morphology and PL of these nanostructures were strongly influenced by the type of cation and anion. As the length of the subsidiary chain of cation section of IL (imidaziole ione) reduces, the thickness of the nano-sheets increases. It is expected that the present method may easily be extended to similar nano-/microstructures of other oxide materials. Such investigations are currently underway.     

Hydrothermal synthesis of nanocrystalline VO2 from poly(diallyldimethylammonium) chloride and V2O5

Novel vanadium dioxide nanorods were fabricated from V₂O₅ in the presence of a reducing agent, the poly(diallyldimethylammonium chloride) (PDDA) via a hydrothermal method at 180 °C for 48 h. The samples produced were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (FTIR), nitrogen adsorption (BET) and thermogravimetry (TG/DTG). The nanorods obtained are approximately 50 nm wide and from 300 to 500 nm long and presents high surface area (42 m² g⁻¹). The nanocrystalline B phase VO₂ is not produced by hydrothermal treatment in the absence of the PDDA polyelectrolyte.     

Microwave dielectric properties and microstructures of the 11Li2O-3Nb2O5-12TiO2 ceramics with B2O3 addition

The effects of B₂O₃ addition, as a sintering agent, on the sintering behavior, microstructure and microwave dielectric properties of the 11Li₂O-3Nb₂O₅-12TiO₂ (LNT) ceramics have been investigated. With the low-level doping of B₂O₃ (≤2 wt.%), the sintering temperature of the LNT ceramic could be effectively reduced to 900 °C. The B₂O₃-doped LNT ceramics are also composed of Li₂TiO₃ss and “M-phase” phases. No other phase could be observed in the 0.5-2 wt.% B₂O₃-doped ceramics sintered at 840-920 °C. The addition of B₂O₃ induced no obvious degradation in the microwave dielectric properties but increased the τ_f values. Typically, the 0.5 wt.% B₂O₃-doped ceramics sintered at 900 °C have better microwave dielectric properties of ?_r = 49.2, Q × f = 8839 GHz, τ_f = 57.6 ppm/°C, which suggest that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

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.     

Structure and lithium ion conductivity of garnet-like Li5La3Sb2O12 and Li6SrLa2Sb2O12

Oxides with the nominal chemical compositions Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were prepared by solid-state reaction. The structures were refined by the Rietveld method using powder X-ray diffraction data. The synthesis of Li₅La₃Sb₂O₁₂ resulted in the well known garnet-related structure plus 5 wt.% of La₂LiSbO₆ in the bulk. In contrast to that, Li₆SrLa₂Sb₂O₁₂ could be synthesised in single garnet-related type phase. Lithium ion conductivities of Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were studied by the ac impedance method. The grain-boundary contribution to the total (bulk + grain-boundary) resistance is very small and about 5 and 3% for Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂, respectively, at 24 °C and decreases further with increase in temperature. Among the investigated compounds, Li₅La₃Sb₂O₁₂ exhibits the highest total (bulk + grain-boundary) and bulk ionic conductivity of 7.8 × 10⁻⁶ and 8.2 × 10⁻⁶ S cm⁻¹, respectively, at 24 °C. The structural data indicate that the coupled substitution Li + Sr ⇒ La leads to a closure of the bottle neck like O-O distances of the shared edges of neighbouring Li octahedra and therefore reduces the mobility of Li ions in Li₆SrLa₂Sb₂O₁₂. Scanning electron microscope (SEM) images of the Li₆SrLa₂Sb₂O₁₂ compound revealed well crystallised large homogeneous grains (∼4.8 μm) and the grains were in good contact with the neighbouring grain, which leads to a smaller grain-boundary contribution to the total resistance.     

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.     

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.     

Sol-gel preparation and properties of TiO2-P2O5 bulk glasses

Monolithic transparent and colorless, or Ti³⁺-free TiO₂-P₂O₅ glasses containing very large amounts of TiO₂ (up to 93 mol%) were successfully prepared by heat-treating the xerogels, which were made from titanium tetraisopropoxide and triethyl phosphate, through the sol-gel reaction. The density and refractive index n_632.8 nm of the sol-gel-derived glasses were higher than the melt-derived glasses of the corresponding compositions. The glasses of TiO₂ content of larger than 80 mol% seemed somewhat porous, but n_632.8 nm of these glasses was very high as 2.2-2.3. Higher density and higher n_632.8 nm than the melt-derived glasses were considered to be due to more abundance of six-fold coordinated Ti⁴⁺ ions.     

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.     

Subsolidus phase equilibria and the Li5Nd4FeO10 phase in the Li2O-Nd2O3-Fe2O3 system

A survey of the subsolidus phase equilibria in the system Li₂O-Nd₂O₃-Fe₂O₃ was made at subsolidus temperatures in the range 1000-1050 °C. A ternary phase was identified. The phase is centered on Li₅Nd₄FeO₁₀, with a cubic lattice a = 11.9494 Å. The compound melts incongruently at 1105 °C. The magnetic susceptibility was measured in the temperature range 4-300 K. The compound is paramagnetic in the temperature range 150-300 K and follows the Curie-Weiss law. At about T_N = 10 K, a long-range magnetic ordering is observed.     

Influence of Sm2O3 on the crystallization and luminescence properties of boroaluminosilicate glasses

Sm₂O₃-doped SiO₂-B₂O₃-Al₂O₃-BaO glasses were prepared by melting method in order to study the influence of Sm₂O₃ on the crystallization behavior and luminescence properties. Differential scanning calorimetry (DSC), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy were used to characterize the rare earth glasses and the crystalline phases after heat-treatment. The course of phase separation and devitrification of the glasses were also investigated. The results show that the thermal stability of the glasses decreases with the increase of content of Sm₂O₃. The crystalline phase changed from SmAl_2.07(B₄O₁₀)O_0.6 to SmBO₃. Divalent Sm²⁺ ions were detected in the crystallization product after heat-treatment. The valence transformation from Sm³⁺ to Sm²⁺ in the crystal suggests the samarium atoms entering the barium sites. The charge carried in vacancy defect induced by the substitution led to the partial reduction process. The reduction of Sm³⁺ ions was promoted by the increasing of Sm₂O₃ content or the extending of heat-treated holding time in boroaluminosilicate glass.