Influence of thermal treatment on the structure and adsorption properties of layered zinc hydroxychloride

Layered zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O) synthesized by hydrolyzing the ZnO particles in aqueous ZnCl₂ solutions at 100 °C for 48 h was outgassed at different temperatures ranging from 100 to 250 °C for 2 h and the structure and adsorption properties of the products were examined by various means. Outgassing at 100-150 °C eliminated the H₂O molecules in interlayer of zinc hydroxychloride. The layered structure of zinc hydroxychloride was disintegrated at 175 °C by breaking the OH?Cl hydrogen-bond in interlayer to form curled thin films composed of poorly crystallized β-Zn(OH)Cl and ZnO, leading to the increment of the specific surface area from 4 to 39 m²/g. The β-Zn(OH)Cl was decomposed at 225 °C to form ZnO. The crystallinity of ZnO was increased on elevating the outgassing temperature, giving rise to the UV absorption property. The H₂O and CO₂ adsorption measurements revealed that the zinc hydroxychloride outgassed at 100-150 °C possessed a high H₂O and CO₂ adsorption selectivity, and the selectivity diminished by the formation of thin films of ZnO above 175 °C.     

Hydrothermal synthesis, crystal structure and thermal stability of Ba-titanate nanotubes with layered crystal structure

BaTi₃O₇·nH₂O nanotubes have been synthesized through a hydrothermal reaction between Na-rich trititanate nanotubes and Ba(OH)₂ within the pH range 12–8.2. These nanotubes possess the same layered crystal structure of the precursor Na_2−xH_xTi₃O₇·nH₂O. They also keep the morphology of their precursor Na-trititanate nanotubes used in the synthesis, having an external diameter of 20–25 nm. The BaTi₃O₇·nH₂O nanotubes remained fully stable up to 300 °C, while nanotubular form continues to exist up to 600 °C, together with amorphous particles.     

Crystal structure, magnetic and thermal properties of LaFeTeO6

LaFeTeO₆ was prepared by solid state reaction of La₂O₃, Fe₂O₃ and TeO₂ in 1:1:2 molar ratios and characterized by powder X-ray diffraction, thermogravimetry and magnetometry. The detailed crystal structure analysis was carried out by Rietveld refinement. LaFeTeO₆ crystallizes in a trigonal lattice with unit cell parameters: a = 5.2049(1) Å and c = 10.3457(2) Å, V = 242.73(2) Å³. The crystal structure is built from sheets of the edge shared FeO₆ and TeO₆ octahedra stacked along the c-axis. These sheets are connected together by La³⁺ ions. Thermogravimetric analysis of the compound showed it to be thermally stable up to 1323 K and continuous loss of TeO₂ was observed above 1323 K leading to the formation of LaFeO₃. High temperature XRD studies revealed a normal expansion behavior of the compound. Temperature and field dependent magnetization of LaFeTeO₆ showed paramagnetic behavior in the temperature range of 3-300 K. The effective magnetic moment per Fe³⁺ ion (5.14 μB) indicates the high spin d⁵ state of Fe³⁺ ion.     

A powder X-ray diffraction refinement of the BaNd2Ti3O10 structure

The structure parameters of BaNd₂Ti₃O₁₀ were refined based on Olsen’s model. This material has a monoclinic unit cell with space group P2₁/m. The unit cell parameters are: a=7.73030(14) Å, b=7.62578(14) Å, c=14.23174(31) Å, β=97.832(6)°. The structure can be considered as a layered perovskite-like structure, in which the perovskite block shows distortion. The various layers link in the order of (Ba_1/2O)-(Ba_1/2TiO₃)-(NdTiO₃)-(NdTiO₃).     

Crystal structure and magnetic properties of Pr- and Ti-substituted La2RuO5

Polycrystalline samples of Pr- and Ti-substituted La₂RuO₅ were prepared applying a soft-chemistry route based on the thermal decomposition of citrate-stabilized precursors. The simultaneous substitution on the La-sites by Pr and on the Ru-sites by Ti results in samples of the composition La_2−xPr_xRu_1−yTi_yO₅ with 0 ≤ x ≤ 0.75 and 0 ≤ y ≤ 0.4. The crystal structures of these compounds were analyzed by Rietveld refinement of powder X-ray diffraction patterns. For pure La₂RuO₅ a structural transition from a monoclinic room-temperature modification to a triclinic low-temperature structure was found at 161 K. This structural change is linked to a low-temperature long-range ordered spin-singlet ground state formed by Ru⁴⁺ spin-moments. Both the structural transition and the formation of the singlet ground state become progressively suppressed with higher Ti contents, while the Pr substitution has only a minor influence on the dimerization. The behavior of the Curie–Weiss temperatures can be explained assuming two almost independent magnetic sublattices corresponding to the ruthenium and the rare-earth ions, respectively. For all investigated properties, i.e. crystal structure, magnetic susceptibilities, and dimerization temperature T_d, a completely additive behavior of the effects of Pr-substitution and Ti-substitution is observed.     

The double hydroxide of Al with Li: mechanism of formation and reversible thermal behavior

All the polymorphic modifications of Al(OH)₃ and the oxide-hydroxide of Al, boehmite, on hydrothermal treatment in Li⁺ containing solutions transform into the layered double hydroxide of Al with Li having the nominal composition [LiAl₂(OH)₆](CO₃)_1/2·1.5H₂O, suggesting that these compounds form via a dissolution-reprecipitation mechanism. The oxide residue obtained by the thermal decomposition of this layered double hydroxide also partially reconstructs the layered double hydroxide on soaking in water lending further evidence to the dissolution-reprecipitation mechanism. Under hydrothermal conditions, in water, the layered double hydroxide undergoes delithiation to yield aluminum hydroxide phases other than gibbsite, suggesting again that delithiation too proceeds by a dissolution-reprecipitation mechanism.     

Synthesis, crystal structure, and properties of novel perovskite oxychalcogenides, Ca2CuFeO3Ch (Ch = S, Se)

Two new perovskite oxychalcogenides, Ca₂CuFeO₃S and Ca₂CuFeO₃Se, have been synthesized in evacuated quartz tubes. They crystallize in P4/nmm space group with lattice parameters a = 3.8271(1), c = 14.9485(2) Å and a = 3.8605(1), c = 15.3030(2) Å for Ca₂CuFeO₃S and Ca₂CuFeO₃Se, respectively. They appear to be the first layered chalcogenide perovskites involving calcium and are structural analogs of the corresponding Sr and Ba compounds. The new compounds exhibit semiconducting properties with energy gap decreasing from the oxysulfide to the oxyselenide. Possibility of introducing Ca²⁺ into structures of known layered oxychalcogenides and oxypnictides is discussed.     

The effect of (Li,Ce) and (K,Ce) doping in Aurivillius phase material CaBi4Ti4O15

The effect of (Li,Ce) or (K,Ce) doping on the structures and properties of bismuth layer-structured ferroelectric (BLSF) CaBi₄Ti₄O₁₅-based ceramics was studied. In Ca_1−x(K,Ce)_x/2Bi₄Ti₄O₁₅ and Ca_1−x(Li,Ce)_x/2Bi₄Ti₄O₁₅ (0 ≤ x ≤ 0.9) compounds, the effect of the substitution on the lattice parameters was given. The XRD patterns of Ca_1−x(K,Ce)_x/2Bi₄Ti₄O₁₅ and Ca_1−x(Li,Ce)_x/2Bi₄Ti₄O₁₅ ceramics showed that the compounds were Aurivillius phases. SEM micrographs show that the grains of CBT-based ceramics were plate-like. Auger electron spectroscopy (AES) results showed that Li⁺ was present in bismuth layer-structured ferroelectrics. Based on the AES analysis and the comparisons with A-site (K,Ce) substitution, Li substitution of A-site cations in BLSF is possible. For x = 0.15 compositions, (Li,Ce) or (K,Ce) dopants can improve the high temperature resisitivity and piezoelectric constant d₃₃ of the doped ceramics.     

Design of magnetic and fluorescent Mg-Al layered double hydroxides by introducing Fe3O4 nanoparticles and Eu ions for intercalation of glycine

We describe a novel route for the preparation of magnetic and fluorescent magnesium-aluminum layered double hydroxides by introducing Fe₃O₄ nanoparticles and Eu³⁺ ions. From the powder X-ray diffraction results, it was found that the Fe₃O₄ nanoparticles were highly dispersed in the inner void of octahedral lattice, and the Eu³⁺ ions substituted for the Al³⁺ ions and entered into hydrotalcite lattice through isomorphous replacement. Moderate introduction of Fe₃O₄ nanoparticles and Eu³⁺ ions did not change the lamellar structure of magnesium-aluminum layered double hydroxides. Glycine can also be intercalated into this magnetic and fluorescent layered double hydroxides by ion-exchange method. After intercalation of glycine, the basal spacing of magnetic and fluorescent layered double hydroxides increased from 7.6 to 8.8 Å, indicating that glycine was successfully intercalated into the interlayer space of layered double hydroxides. Magnetic measurements reveal that these novel layered double hydroxides possess paramagnetic property at room temperature, and the emission and excitation spectra indicate the layered double hydroxides exhibit fluorescent property.     

Microporous titanosilicate AM-2: Rb-exchange and thermal behaviour

Rb-exchange and thermal stability of the microporous titanosilicate AM-2 were analysed by powder X-ray diffraction, thermo-gravimetric analysis, and chemical analysis of the mother liquid after exchange. The dehydration and thermal stability of the exchanged structure were monitored with in situ high temperature powder X-ray diffraction. Crystal structures were refined with Rietveld methods at 25 and 400 °C. The AM-2 structure was found to incorporate Rb⁺ by replacing K⁺. After four exchange cycles and 166 h reaction time at 90 °C, the chemical composition was refined to K_0.18Rb_1.82TiSi₃O₉·H₂O. Extrapolation suggests that higher exchange ratios may be obtained after further cycles. H₂O was expelled by heating, leading to a dehydrated structure at 360 °C. Dehydration was associated with a change of space group symmetry from orthorhombic P2₁2₁2₁ to monoclinic P2₁, which proved to be reversible after rehydration. This change of symmetry leaves the AM-2 characteristic structural topology uninfluenced and causes only minor distortions. The monoclinic AM-2 structure breaks down above 600 °C to become X-ray amorphous, and at 750 °C a wadeite-type phase (K_xRb_2−xTiSi₃O₉) crystallises. This transformation is irreversible and leads to immobilisation of Rb⁺.     

Control of growth orientation and shape for epitaxially grown In2O3 nanowires on a-plane sapphire

Vertically aligned indium oxide nanowires were grown on a-plane sapphire substrate by the method of catalyst-assisted carbothermal reduction. The morphology and crystal structure of the nanowires are determined by X-ray diffraction, transmission electron microscopy and field-emission scanning electron microscopy. Two types of In₂O₃ nanowires were found by controlling the growth conditions. The nanowires with a hexagonal cross-section were shown to grow in [1 1 1] direction, whereas those with a square cross-section grow in [0 0 1] direction. In addition to the temperature effects, the concept of supersaturation in Au catalyst is proposed to explain the formation of these two types of nanowires. Besides, tapering, which is explained with the interplay between the vapor-liquid-solid and vapor-solid growth mechanisms, is observed in the nanowires.     

The effect of growth conditions on the properties of ZnO nanorod dye-sensitized solar cells

In this article, we report ZnO nanorod samples grown on transparent conductive SnO₂:F (FTO) glass substrates by two different growth routes through hydrothermal method in a closed autoclave. One route is one-step continuous growth for 10 h. The other route is discrete multi-step growth for total 48 h. In this process, fresh solution was repeatedly introduced in every step. The structural, photoluminescence (PL) and photovoltaic properties of the as-prepared nanorod arrays were investigated. The nanorod arrays obtained through multi-step growth show longer rods, higher aspect ratio, larger spacing, better crystalline quality. The PL spectrum of nanorod arrays obtained through multi-step growth shows a strong and sharp near-band-gap emission (UV) peak and a weak green-yellow emission (GY) peak (I_UV/I_GY = 7.7), which also implies its good crystallinity and high optical quality. Dye-sensitized solar cells based on ZnO nanorod arrays were fabricated, and those grown with discrete multi-step procedure present better photovoltaic properties duo to its special morphology and better crystal quality.     

New rare-earth double-layered-perovskite oxyfluorides, RbLnTiNbO6F (Ln = La, Pr, Nd)

New Dion-Jacobson-type double-layered oxyfluoride perovskites, RbLnTiNbO₆F (Ln=La, Pr, Nd), have been synthesized. Rietveld refinement of X-ray powder diffraction data (space group P4/mmm) shows the compounds to be isostructural with RbSrNb₂O₆F. Curie-Weiss behavior is observed in the Pr, Nd compounds. This series further illuminates the substitutional variations, both cationic and anionic, that can be achieved within the RbLaNb₂O₇ structure type.     

Effects of geometric structure, orientation and size on structural stability and thermal behavior of zinc oxide nanowires

The structural stability, orientation effect and melting characteristic of zinc oxide (ZnO) nanowires are simulated by using the molecular dynamics with many-body tightbinding potential. The structural stability is affected by the geometric shape of the cross section of a nanowire. The nanowire with a hexagonal cross section is more stable than that with another cross section type, namely, a rectangular, triangular, rhombohedral, octagonal, and circular cross section. The structural stability and melting temperature of a nanowire is sensitive to its diameter because of the surface energy and unfavorable coordination. Remarkably, it is observed that hexagonal ZnO nanowires transform to metastable circular-type structures at temperatures lower than the melting point.     

Synthesis of ZnO flowers and their photoluminescence properties

Flower-like ZnO nano/microstructures have been synthesized by thermal treatment of Zn(NH₃)₄²⁺ precursor in aqueous solvent, using ammonia as the structure directing agent. A number of techniques, including X-ray diffraction (XRD), field emission scan electron microscopy (FESEM), transmission electron microscopy (TEM), thermal analysis, and photoluminescence (PL) were used to characterize the obtained ZnO structures. The photoluminescence (PL) measurements indicated that the as-synthesized ZnO structures showed UV (∼375 nm), blue (∼465 nm), and yellow (∼585 nm) emission bands when they were excited by a He-Gd laser using 320 nm as the excitation source. Furthermore, it has been interestingly found that the intensity of light emission at ∼585 nm remarkably decreased when the obtained ZnO nanocrystals were annealed at 600 °C for 3 h in air. The reason might be the possible oxygen vacancies and interstitials in the sample decreased at high temperature.     

Reversible thermal behavior of the layered double hydroxides (LDHs) of Mg with Ga and In

The layered double hydroxides (LDHs) of Mg with Ga and In decompose completely on heating to 500 °C to yield poorly ordered oxide residues. In the Mg-Ga system, the oxide residue has a rock-salt structure with Ga incorporated in the MgO matrix. In the Mg-In system, the oxide residue is X-ray amorphous. These oxide residues revert back to the original LDH either on standing in a water-saturated atmosphere or on hydrothermal treatment in a Na₂CO₃ solution. In contrast, the LDHs of Co with Ga and In yield the thermodynamically stable spinel oxides and the decomposition is irreversible. These results have implications for the synthesis of ‘oxide’ catalysts by thermal decomposition of the LDHs.     

Reinvestigation of the binary diagram Na3PO4-FePO4 and crystal structure of a new iron phosphate Na3Fe3(PO4)4

A new iron(III) phosphate Na₃Fe₃(PO₄)₄ has been synthesized and characterized. It decomposes before melting at 860°C into FePO₄ and Na₃Fe₂(PO₄)₃. The structure of the compound was determined by single-crystal X-ray diffraction. The unit cell is monoclinic with the following parameters: a=19.601(8) Å, b=6.387(1) Å, c=10.575(6) Å and β=91.81(4)°; Z=4; space group: C2/c. Na₃Fe₃(PO₄)₄ exhibits a layered structure involving corner-linkage between FeO₆ octahedra, and corner- and edge-sharing between FeO₆ octahedra and PO₄ tetrahedra. The Na⁺ cations occupying the interlayer space are six- and seven-fold coordinated by oxygen atoms. The relationship between the structure of Na₃Fe₃(PO₄)₄ and the previous reported hydrate K₃Fe₃(PO₄)₄·H₂O will be discussed.     

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.     

Formation and stability of anatase phase of phosphate incorporated and carbon doped titania nanotubes

Phase transformation analysis of the phosphate containing and carbon doped titania nanotubes, prepared by a simple anodization method, reveals complete transformation from amorphous to anatase phase in air between 360 and 400 °C. Activation energies for formation of anatase phase are evaluated and compared for the two types of titania nanotubes. A detailed analysis of the phase transformation characteristics and stability of the anatase phase is reported.     

Effects of borosilicate glass addition on the structure and dielectric properties of ZnTiO3 ceramics

ZnTiO₃ powders and borosilicate glass were made by sol-gel method, and then mixed for co-firing at low temperatures. The results show that the borosilicate glass was liquefied to improve the density of the ceramic during sintering. However, Zn₄O(BO₂)₆ and TiO₂ were formed if too much borosilicate glass was added (over 10 wt.%). The microwave dielectric properties of the ZnTiO₃ co-fired with borosilicate glass were also improved dramatically. With 5 wt.% borosilicate glass addition, ZnTiO₃ ceramics can be sintered at 850 °C and shows excellent microwave properties: 22.2 for dielectric constant, and 52,460 for Q × f value at a frequency of 6 GHz.