Ba0.15WO3: A bronze with an original pentagonal tunnel structure

The structure of a new barium tungsten bronze, Ba_0.15WO₃, has been established by X-ray diffraction and high-resolution microscopy studies. This bronze is orthorhombic, space group Pbm2 or Pbmm, with a = 8.859(3) Å, b = 10.039(8) Å, and c = 3.808(2)Å. The “WO₃” framework is built up from corner-sharing WO₆ octahedra forming pentagonal tunnels where the barium ions are located. Structural relationships with hexagonal tungsten bronze and tetragonal tungsten bronze structures are discussed.     

SrMn3O6: an incommensurate modulated tunnel structure

The crystallographic structure of a mixed valent manganite SrMn₃O₆ with a 1D modulated structure is reported. The SrMn₃O₆ structure can be described with the basic subcell space group Pnma (a=9.1334(5) Å; b=2.8219(2) Å; c=12.0959(7)Å), but transmission electron microscopy revealed that the study of the real structure requires a 4D-formalism approach with superspace group P2₁/a(αβ0)00 (unique axis c), with a modulation wave vector q having the approximate components (0.52a*+0.31b*). The crystallographic structure is closely related to those of Na_xFe_xTi_2−xO₄ and Pb_1.5BaMn₆Al₂O₁₆, comprising of unusual “figure-of-eight”-shaped tunnels, made up of strings of edge- and corner-sharing (Fe/Ti)O₆ or (Mn/Al)O₆ octahedra, with the other cations situated in the tunnel cavities. Structural refinement was performed on X-ray and neutron powder diffraction data using the 4D formalism. All atoms in the crystal are affected by a displacive modulation wave, and a saw tooth function is employed to model the displacement and occupancy of the Sr sites. Magnetic susceptibility measurements reveal a sharp antiferromagnetic transition with T_N∼46 K.     

The characterization of Ba3Re2O9 and Sr3Re2O9

The compounds Ba₃Re₂O₉ and Sr₃Re₂O₉ were prepared by the solid state reaction of the corresponding alkaline-earth oxide with ReO₃ at 750 to 900°C in sealed, evacuated, fused silica tubes. The two compounds are isostructural, having the nine-layer ABO₃ structure with vacant central octahedra. The unit cell parameters are given. The magnetic susceptibility for Ba₃Re₂O₉ indicates Curie-Weiss behavior with a Re⁶⁺ moment having localized electrons. The magnetic data for Sr₃Re₂O₉ suggest delocalized electron behavior from its temperature-independent susceptibility. Both compounds appear to have semiconducting properties, but the strontium analog is a better conductor. Both compounds are unstable when heated in air above 400°C. They are readily decomposed by chemical oxidizing agents.     

Ternary tungsten oxides with the Mo5O14 structure

Following the discovery of a ternary GeW oxide with the Mo₅O₁₄ structure, a large number of ternary MWO systems were surveyed to investigate the frequency of occurrence of this structure type. Samples were prepared by heating tungsten oxides and the appropriate ternary element or a suitable compound of the ternary element in evacuated silica ampoules at 1373°K for 1 week. The compositions investigated were close to M_0.02W_0.98O_2.80. Oxides with the Mo₅O₁₄ structure were found in many systems across the whole of the periodic table, from Li to Bi. Some aspects of the formation of these phases and the way in which they could affect the course of reduction of WO₃ to W metal are discussed.     

Synthesis and crystal structure of the palladium oxides NaPd3O4, Na2PdO3 and K3Pd2O4

NaPd₃O₄, Na₂PdO₃ and K₃Pd₂O₄ have been prepared by solid-state reaction of Na₂O₂ or KO₂ and PdO in sealed silica tubes. Crystal structures of the synthesized phases were refined by the Rietveld method from X-ray powder diffraction data. NaPd₃O₄ (space group Pm3¯n, a=5.64979(6) Å, Z=2) is isostructural to NaPt₃O₄. It consists of NaO₈ cubes and PdO₄ squares, corner linked into a three-dimensional framework where the planes of neighboring PdO₄ squares are perpendicular to each other. Na₂PdO₃ (space group C2/c, a=5.3857(1) Å, b=9.3297(1) Å, c=10.8136(2) Å, β=99.437(2)°, Z=8) belongs to the Li₂RuO₃-structure type, being the layered variant of the NaCl structure, where the layers of octahedral interstices filled with Na⁺ and Pd⁴⁺ cations alternate with Na₃ layers along the c-axis. Na₂PdO₃ exhibits a stacking disorder, detected by electron diffraction and Rietveld refinement. K₃Pd₂O₄, prepared for the first time, crystallizes in the orthorhombic space group Cmcm (a=6.1751(6) Å, b=9.1772(12) Å, c=11.3402(12) Å, Z=4). Its structure is composed of planar PdO₄ units connected via common edges to form parallel staggered PdO₂ strips, where potassium atoms are located between them. Magnetic susceptibility measurements of K₃Pd₂O₄ reveal a Curie-Weiss behavior in the temperature range above 80 K.     

Phase equilibrium relations in the binary systems LiPO3CeP3O9 and NaPO3CeP3O9

The LiPO₃CeP₃O₉ and NaPO₃CeP₃O₉ systems have been investigated for the first time by DTA, X-ray diffraction, and infrared spectroscopy. Each system forms a single 1:1 compound. LiCe(PO₃)₄ melts in a peritectic reaction at 980°C. NaCe(PO₃)₄ melts incongruently, too, at 865°C. These compounds have a monoclinic unit cell with the parameters: a = 16.415(6), b = 7,042(6), c = 9.772(7)Å; β = 126.03(5)°; Z = 4; space group $\text{C}{}_2\text{c}$ for LiCe (PO₃)₄; and a = 9.981(4), b = 13.129(6), c = 7.226(5) Å, β = 89.93(4)°, Z = 4, space group $\text{P2}{}_1\text{n}$ for NaCe(PO₃)₄. It is established that both compounds are mixed polyphosphates with chain structure of the type |M^I_IM^III_II (PO₃)₄|_∞M^I_I: alkali metal, M^III_II: rare earth.     

The Na2O-SrO-B2O3 diagram in the B-rich part and the crystal structure of NaSrB5O9

The subsolidus phase relations in the B-rich part of the ternary system, Na₂O-SrO-B₂O₃, are investigated by the powder X-ray diffraction method. Four ternary compounds: NaSrBO₃, NaSr₄B₃O₉, Na₃SrB₅O₁₀ and NaSrB₅O₉ were found in it, the two lasts are new. NaSrB₅O₉ crystallizes in the monoclinic space group P2₁/c, with the lattice parameters a=6.4963(1) Å, b=13.9703(2) Å, c=8.0515(1) Å, β=106.900(1)°. Na₃SrB₅O₉ is also monoclinic, space group C2, a=7.290(1) Å, b=13.442(2) Å, c=9.792(1) Å, β=109.60(1). NaSrB₅O₉ is isostructural with another pentaborate NaCaB₅O₉, and its structure was refined by Rietveld method based on the structural model of NaCaB₅O₉. The fundamental building units are [B₅O₉]³⁻ anionic groups, forming complex thick anionic sheets, extending parallel to the ac plane. The Na and Sr atoms are all eight-coordinated with O atoms, forming trigonal dodecahedra. The [NaO₈] polyhedra are distributed between the B-O sheets, while the [SrO₈] polyhedra located in the sheets and connect with each other by edges to form infinite chains along the c-axis.     

The hollandite-related structure of Ba2Ti9O20

The crystal structure of Ba₂Ti₉O₂₀ has been determined by comparison of experimental high-resolution electron micrographs with images simulated using structural models deduced from the micrographs in conjunction with crystallochemical principles. The structure consists of lamellae of hollandite-type structure alternating with BaTiO₃-like units, which effectively immobilize the Ba ions. This material should be relatively more leach resistant to attack by aqueous sodium chloride solutions. The structure determination clarifies the observation that this material has unique properties as a microwave resonator, compared with other barium and alkali titanate structures.     

Thermal stability and crystal structure of β-Ba3YB3O9

A new compound, β-Ba₃YB₃O₉, has been attained through solid phase transition from α-Ba₃YB₃O₉ at high temperatures. Differential thermal analysis (DTA) revealed the phase transition at about 1120°C, the melting temperature at about 1253°C. Its crystal structure has been determined from powder X-ray diffraction data. The refinement was carried out using the Rietveld method and the final refinement converged with R_p=10.5% and R_wp=13.7%. This compound belongs to the hexagonal space group R-3, with lattice parameters a=13.0441(1) Å and c=9.5291(1) Å. There are 6 formulas per unit cell and 7 atoms in the asymmetric unit. The structure of β-Ba₃YB₃O₉ is built up from Ba(Y)O₈, BaO₆ and YB₆O₁₈ units formed by one YO₆ octahedron and six BO₃ triangles with shared O atoms.     

Surface electron donor properties of Dy2O3, Y2O3 and their mixed oxides with alumina catalyst

The limit of electron transfer in electron affinity from the oxide surface to the electron acceptor (EA) are reported from the adsorption of EA on Dy₂O₃, mixed oxides of Dy₂O₃ with alumina and mixed oxides of Y₂O₃ with -alumina. The extent of electron transfer is understood from magnetic measurements.     

Layer structure: The oxides A3Ti5MO14

Five new oxides, K₃Ti₅MO₁₄, Rb₃Ti₅MO₁₄ (M = Ta, Nb), and Tl₃Ti₅NbO₁₄, have been synthesized. The structure of these oxides consists of octahedral layers similar to those observed for Na₂Ti₃O₇ and held together by monovalent ions; the sheets consist of blocks of 2 × 3 edge-sharing octahedra, which are then joined to each other by the corners of the octahedra. The relative disposition of the layers is similar to that observed for Tl₂Ti₄O₉. These oxides can be considered as the member n = 3 of a series of closely related structures with formula A_nB_2nO_4n+2, where n indicates the number of octahedra which determines the width of the blocks of 2 × n octahedra.     

The structures of lithium inserted metal oxides: Li2FeV3O8

Neutron diffraction powder profile analysis has been used to determine the structure of Li₂FeV₃O₈. The compound is prepared from FeV₃O₈, which has the VO₂(B) structure type, by a lithium insertion reaction employing n-BuLi. Only minimal distortion of the host lattice occurs on Li insertion. The Li ions occupy five coordinate square pyramidal sites with an average LiO bond distance of 2.04 Å. These five coordinate sites occur commonly in the capped perovskite cavities of crystallographic shear structures based on ReO₃.     

Sm2O3Ga2O3 and Gd2O3Ga2O3 phase diagrams

Four definite compounds exist in the Sm₂O₃Ga₂O₃ binary phase diagram, namely: Sm₃GaO₆, Sm₄Ga₂O₉, SmGaO₃, and Sm₃Ga₅O₁₂. The $\text{3}\text{1}$ compound is orthorhombic (space group Pnna - Z.4) with the cell parameters: a = 11.40₀Å, b = 5.51₅Å, c = 9.07Å and belongs to the oxysel family. Sm₃GaO₆ and SmGaO₃ melt incongruently at 1715 and 1565°C; Sm₄Ga₂O₉ and Sm₃Ga₅O₁₂ have a congruent melting point at 1710 and 1655°C. With regard to the Gd₂O₃Ga₂O₃ system three definite compounds have been identified: Gd₃GaO₆, Gd₄Ga₂O₉, and Gd₃Ga₅O₁₂. Only the garnet melts congruently at 1740°C with the following composition: Gd_3.12Ga_4.88O₁₂. Gd₃GaO₆, and Gd₄Ga₂O₉ melt incongruently at 1760 and 1700°C. GdGaO₃ is only obtained by melt overheating which may yield an equilibrium or a metastable phase diagram.     

The crystal structure of La3Ru3O11: A new cubic KSbO3 derivative oxide with no metal-metal bonding

La₃Ru₃O₁₁ was prepared by the reaction of La₂O₃, RuO₂, and NaClO₃ in a KCl flux under vacuum at 950°C. The crystal structure of this new cubic KSbO₃ derivative oxide was determined from single-crystal X-ray diffraction data collected on an automated diffractometer with MoKα radiation. Principal crystallographic data: Cubic, space group Pn3; a = 9.451(2), Å; V = 844.2ų; d_X = 7.049 g cm^?3. Final discrepancy indices R = 0.036, R_w = 0.042. La₃Ru₃O₁₁ is isomorphous with Bi₃Ru₃O₁₁, but is notably different in showing no direct bonding between ruthenium atoms; the closest RuRu contact in this new oxide is 2.994(1) Å.     

A new promising scintillator Ba3InB9O18

We report on the synthesis, crystal structure and scintillation property of a new compound Ba₃InB₉O₁₈. This compound crystallizes in space group P6₃/m with unit cell of dimensions a=7.1359(3) Å, c=16.6151(8) Å and V=732.697 Å³ with two Ba₃InB₉O₁₈ molecular formula. Its crystal structure is made up of planar B₃O₆ groups parallel to each other along the 〈0001〉 direction, regular InO₆ octahedra, irregular BaO₆ hexagons and BaO₉ polyhedra to form an analog structure of Ba₃YB₉O₁₈. DTA and TGA curves for Ba₃InB₉O₁₈ show that it is a chemically stable and congruent melting compound. Its X-ray excited luminescence spectra show an intense emission band in the range of 360-500 nm with a maximum at 400 nm. Light yield for Ba₃InB₉O₁₈ is about 75% as large as that for BGO under the same measurement conditions. There may exist a correlation between the scintillation properties and the crystal structural features of Ba₃InB₉O₁₈.     

The monophosphate tungsten bronzes with pentagonal tunnels (MPTBP, P4O8(WO3)2m: A high-resolution electron microscopy study

A series of monophosphate tungsten bronzes of composition P₄O₈(WO₃)_2m with pentagonal tunnels, MPTB_P, have been investigated by high resolution electron microscopy. Most of the micrographs of the integral m members exhibit an asymmetrical contrast which could not be explained qualitatively by the structural models derived from X-ray diffraction studies of some members of the series. Image calculations were thus performed on the m = 4 member (P₄W₈O₃₂), which showed that the unexpected symmetry does not result from a structural anomaly, but could be due to a titled electron beam. The observations revealed that ordered crystals can be obtained up to m = 16. The investigation of the nonintegral m compositions showed two sorts of intergrowths: disordered intergrowths of different m members belonging to the MPTB_P series and ordered intergrowths of the MPTB_P structure with a related phosphate tungsten bronze structure based upon hexagonal tunnels.     

The pyrophosphate NaFeP2O7: A cage structure

The high-temperature form of NaFeP₂O₇ crystallizes in the monoclinic $\text{P2}{}_1\text{c}$ space group with a = 7.3244(13), b = 7.9045(7), c = 9.5745(15), Å, β = 111.858(13)°, and Z = 4. The structure has been refined from 3842 reflections leading to R = 0.040 and R_w = 0.047. The structure of II-NaFeP₂O₇ can be described by alternately stacking layers containing the FeO₆ octahedra and layers formed by the P₂O₇ groups, parallel to (001). Elongated cages are formed where two Na⁺ ions are located. The structure is compared with that of KAlP₂O₇. Both structures are built up from blocks of three polyhedra, [FeP₂O₁₁] or [AlP₂O₁₁], including a small O_octO_tetO_oct angle. These blocks are connected in such a way that several types of tunnels appear in each structure.     

Acid behavior of SiO2?Al2O3 mixed oxides

Surface acidity of a series of silica-alumina mixed oxides have been investigated by IR-spectroscopy and catalytic measurements. Pure alumina was the most active catalyst in the conversion of butan-1-ol, but the E1 part in the reaction increased with increasing SiO₂ content. It was concluded that the number of acidic sites increased with increasing Al₂O₃ content, while the strength of the acidic sites with the silica content.

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- . -I-, E1 SiO₂. , Al₂O₃, - .

     

The luminescence of α- and β-LaNb3O9

The luminescence of undoped and rare-earth-doped LaNb₃O₉ is reported. The two modifications (α and β) show striking differences. Whereas undoped β-LaNb₃O₉ does not luminesce at all (down to 4.2 K), α-LaNb₃O₉ emits efficiently with a quenching temperature of 250 K. Energy transfer from niobate to rare-earth dopants is observed for the α, but not for the β modification. The rare-earth dopant emission consists of sharp lines for the α modification, but is considerably broadened for the β modification. The luminescence properties are discussed in terms of the crystal structure. In addition results for α-NbPO₅ will be given.     

An oxygen deficient fluorite with a tunnel structure: Bi8La10O27

A new lanthanum bismuth oxide, Bi₈La₁₀O₂₇, has been synthesized. It crystallizes in the Immm space group with the following parameters: a = 12.079 (2) Å, b = 16.348 (4) Å, c = 4.0988 (5) Å. Its structure was determined from powder X-ray and neutron diffraction data. It can be described as an oxygen deficient fluorite superstructure (a ≈ 3a_F/√2, b ≈ 3a_F, c ≈ a_F/√2) in which bismuth and lanthanum, as well as oxygen vacancies, are ordered. The structure consists of fully occupied (110) or lanthanum planes (La) which alternate with mixed planes and fully occupied oxygen planes (A) which alternate with two sorts of oxygen deficient (110) or planes (B and C) according to the sequence . The anionic distribution determines tunnels where the bismuth ions are located, forming diamond-shaped based tunnels. The coordination of bismuth and lanthanum is discussed. The high thermal factor of some oxygen atoms suggests that this oxide exhibits ionic conductivity.