Three-dimensional atomic imaging of Y and (B12)13 clusters in YB56 by HREM and crystallographic image processing

The three-dimensional atomic image of YB₅₆ was obtained by inverse Fourier transformation of three-dimensional phases and amplitudes in three high-resolution images along [100], [110] and [111] of YB₅₆ crystals. After crystallographic image processing, the image directly showed the three-dimensional potential map of the crystal, which showed (B₁₂)₁₃ clusters and Y atom positions. The present method would be useful for three-dimensional structure analysis in nanoscale regions.     

Microstructures of YBa2Cu3O7/La0.7Ca0.3MnO3 and La0.7Ca0.3MnO3/YBa2Cu3O7 bi-layers grown on (001)LaAlO3

Epitaxial YBa₂Cu₃O₇/La_0.7Ca_0.3MnO₃ (YBCO/LCMO) bi-layers and La_0.7Ca_0.3MnO₃/YBa₂Cu₃O₇ (LCMO/YBCO) bi-layers were grown on (001)LaAlO₃ by pulsed laser deposition, and their microstructures were compared by transmission electron microscopy investigation. In the YBCO(100 nm)/LCMO(150 nm) bi-layers, the LCMO layer consists of columnar grains of ~ 17 nm in diameter and contains mixed orientation domains of [100]_c, [010]_c and [001]_c. The YBCO layer is totally c-axis oriented and the YBCO lattices are tilted − 2.5° to + 2.5° as they grew on the rough surfaces of LCMO columnar grains. For the LCMO(140 nm)/YBCO(140 nm) bi-layers, the LCMO/YBCO interface is sharp and flat. The initial 12-nm thickness of the YBCO layer is composed of c-axis oriented domains, and the upper part of YBCO layer is [100] oriented. The LCMO layer was predominantly [001]_c oriented while [100]_c-oriented domains were occasionally observed.     

Synthesis and crystal structure of Cu2NiO(B2O5) and Cu2MgO(B2O5)

A transport reaction synthesis technique has been used to prepare single crystals of two pyroborate compounds having the formulas Cu₂NiO(B₂O₅) and Cu₂MgO(B₂O₅). The two compounds are isostructural and crystallize in the monoclinic space group P2₁/c. Cu₂NiO(B₂O₅): a=3.2003(10), b=14.775(3), c=9.097(3), β=93.28(4), V=429.4(2) Å³, Z=4; and Cu₂MgO(B₂O₅): a=3.2401(6), b=14.790(2), c=9.147(2), β=94.88(2), V=436.7(2) Å³, Z=4. The structures of Cu₂NiO(B₂O₅) and Cu₂MgO(B₂O₅) were, respectively, refined from 804 and 1000 independent reflections to the final residuals R1=0.0366, wR2=0.0911 and R1=0.0231, wR2=0.0644. Both compounds exhibit a chevron-like structure built up of ribbons, made of edge-connected copper and nickel-oxygen polyhedra, running along the (1 0 0) direction. These ribbons are connected from one another via oxygen atoms and the cohesion of the three-dimensional network is ensured by [B₂O₅] entities. Cu in part occupies the position for Ni or Mg, so that the compounds actually are solid solution compounds. Ni or Mg atoms are octahedrally coordinated by oxygen, while the two pure Cu sites show [4] and [4+1] coordination, for Cu(1) and Cu(2), respectively. The ELNES B-K edge spectra for the two compounds support that the borate group present is [B₂O₅].     

Structural characterization, thermal, spectroscopic and magnetic studies of the (C3H12N2)0.75[Mn1.50Fe1.50(AsO4)F6] and (C3H12N2)0.75[Co1.50Fe1.50(AsO4)F6] compounds

The (C₃H₁₂N₂)_0.94[Mn_1.50Fe_1.50^III(AsO₄)F₆] and (C₃H₁₂N₂)_0.75[Co_1.50Fe_1.50^III(AsO₄)F₆] compounds 1 and 2 have been synthesized using mild hydrothermal conditions. These phases are isostructural with (C₃H₁₂N₂)_0.75[Fe_1.5^IIFe_1.5^III(AsO₄)F₆]. The compounds crystallize in the orthorhombic Imam space group. The unit cell parameters calculated by using the patterns matching routine of the FULPROOF program, starting from the cell parameters of the iron(II),(III) phase, are: a = 7.727(1) Å, b = 11.047(1) Å, c = 13.412(1) Å for 1 and a = 7.560(1) Å, b = 11.012(1) Å, c = 13.206(1) Å for 2, being Z = 8 in both compounds. The crystal structure consists of a three-dimensional framework constructed from edge-sharing [M^II(1)₂O₂F₈] (M = Mn, Co) dimeric octahedra linked to [Fe^III(2)O₂F₄] octahedra through the F(1) anions and to the [AsO₄] tetrahedra by the O(1) vertex. This network gives rise two kinds of chains, which are extended in perpendicular directions. Chain 1 is extended along the a-axis and chain 2 runs along the c-axis. These chains are linked by the F(1) and O(1) atoms and establish cavities delimited by eight or six polyhedra along the [1 0 0] and [0 0 1] directions, respectively. The propanediammonium cations are located inside these cavities. The thermal study indicates that the structures collapse with the calcination of the organic dication at 255 and 285 °C for 1 and 2, respectively. The Mössbauer spectra in the paramagnetic state indicate the existence of two crystallographically independent positions for the iron(III) cations and a small proportion of this cation in the positions of the divalent Mn(II) and Co(II) ones. The IR spectrum shows the protonated bands of the H₂N- groups of the propanediamine molecule and the characteristic bands of the [AsO₄]³⁻ arsenate oxoanions. In the diffuse reflectance spectra, it can be observed the bands characteristic of trivalent iron(III) cation and divalent Mn(II) and Co(II) ones in a distorted octahedral symmetry. The calculated Dq and B-Racah parameters for the cobalt(II) phase are 710 and 925 cm⁻¹, respectively. The ESR spectra of compound 1 maintain isotropic with variation in temperature, being g = 1.99. Magnetic measurements for both compounds indicate that the main magnetic interactions are antiferromagnetic in nature. However, at low temperatures small ferromagnetic components are detected, which are probably due to a spin decompensation of the two different metallic cations. The hysteresis loops give values of the remnant magnetization and coercive field of 84.5, 255 emu/mol and 0.01, 0.225 T for phases 1 and 2, respectively.     

Crystal structure of the potassium tantalum oxyfluoride K6Ta6.5O14.5F9.5

The crystal structure of K₆Ta_6.5O_14.5F_9.5 has been determined from 714 automatic diffractometer data, and refined in the space group P6 to an R-factor of 0.061. Its structure can be described as a three-dimensional framework lattice formed by the interpenetration of two distinct sublattices with the formulations [Ta₆X₂₁]_n and [Ta_0.5X₃]_n respectively, in which are inserted the K atoms. The three-dimensional skeleton [Ta₆X₂₁]_n is formed entirely of octahedra TaX₆, while the sublattice [Ta_0.5X₃]_n is an infinite chain of trigonal prisms.     

Growth of YB6 single crystals

Single phase, single crystals of YB₆, GdB₆ and ThB₆, several mm in size, have been prepared by use of an AlGa flux growth technique. Crystals were grown in an A atmosphere at 1550°C using Al₂O₃ crucibles that were heated either resistively or inductively. Use of the multi-elemental flux for crystal growth of these peritectically forming borides, has permitted good phase control not easily obtainable by other growth methods. Stoichiometry of these compounds can be varied by controlling the composition of the charge boride in the flux mixture. Measurement of superconducting transition temperatures, electrical resistance ratio and lattice parameters indicate that nonstoichiometric (B rich) crystals result.     

Crystal structure of complexes of Np(VI) and Pu(VI) perchlorates with triphenylphosphine oxide, [NpO2(OP(C6H5)3)4](ClO4)2 and [PuO2(OP(C6H5)3)4](ClO4)2

Single crystals of [NpO₂(TPPO)₄](ClO₄)₂ and [PuO₂(TPPO)₄](ClO₄)₂ isostructural to the complex [UO₂(TPPO)₄](ClO₄)₂ [TPPO = OP(C₆H₅)₃] studied previously were prepared, and the structures of these compounds were determined. The coordination polyhedron of these compounds is a tetragonal bipyramid. The geometric characteristics of the tetragonal bipyramids in the compounds are practically the same despite the actinide contraction of the central atoms, whereas the unit cell volume decreases in the series U-Np-Pu. The equality of the volumes of the coordination polyhedra of the U, Np, and Pu atoms is attributed to the influence of TPPO containing phenyl radicals with negative effective charge. Original Russian Text ? I.A. Charushnikova, N.N. Krot, Z.A. Starikova, I.N. Polyakova, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 5, pp. 407–411.     

Structure, infrared and Raman spectroscopic studies of new Sr0.50SbFe(PO4)3 and SrSb0.50Fe1.50(PO4)3 Nasicon phases

Two newly synthesised Sr_0.50SbFe(PO₄)₃ [Sr_0.5.] and SrSb_0.50Fe_1.50(PO₄)₃ [Sr.] phases were obtained by conventional solid-state reaction techniques at 1000 °C in air atmosphere. Their crystallographic structures were determined at room temperature from X-ray powder diffraction (XRPD) data using the Rietveld analysis. Both compounds belong to the Nasicon structural family. [Sr_0.5.] and [Sr.] crystallise in rhombohedral system with \textR[`3] {\text{R}}\overline{3} and \textR[`3] \textc {\text{R}}\overline{3} {\text{c}} space group, respectively. Hexagonal cell parameters for [Sr_0.5.] and [Sr.] are: a = 8.227(1) ?, c = 22.767(2) ? and a = 8.339(1) ?, c = 22.704(2) ?, respectively. Sr²⁺ and vacancies in {[Sr_0.50]_3a[□_0.50]_3b}_M1SbFe(PO₄)₃ are practically ordered within the two positions, 3a and 3b, of M1 sites. Structure refinements show also an ordered distribution of Sb⁵⁺ and Fe³⁺ ions within the Nasicon framework. Within the structure, each Sr_(3a)O₆ octahedron shares two faces with two Fe³⁺O₆ octahedra and each vacancy (□_(3b)O₆) site is located between two Sb⁵⁺O₆ octahedra. In [Sr]_M1Sb_0.50Fe_1.50(PO₄)₃ compound, all M1 sites are occupied by Sr²⁺ and the Sb⁵⁺ and Fe³⁺ ions are randomly distributed within the Nasicon framework. A Raman and infrared spectroscopic study was used to obtain further structural information about the nature of bonding in both selected compositions.     

An open-framework bimetallic chalcogenide structure K3Rb3Zn4Sn3Se13 built on a unique [Zn4Sn3Se16] cluster: synthesis, crystal structure, ion exchange and optical properties

Single crystals of K₃Rb₃Zn₄Sn₃Se₁₃ were synthesized by solvothermal method. The building block in this structure is a [Zn₄Sn₃Se₁₆]¹²⁻ cluster which consists of four ZnSe₄ and three SnSe₄ tetrahedra connected through corner-sharing of Se atoms. The 3D network contains intersecting channels running parallel to the crystallographic [2 1 1], [1-1-1] and [12-1] directions. The disordered K⁺ and Rb⁺ cations reside in these channels. Ion exchange of Cs⁺ with disordered Rb⁺/K⁺ ions in the structure showed a partial replacement of 15.8%. Optical diffuse reflectance experiments were carried out and gave a sharp absorption edge at 2.6 eV.     

Phase equilibria in the liquid ternary system [Y(NO3)3(TBP)3]-[UO2(NO3)2(TBP)2]-C14H30 at different temperatures

The phase diagrams of the ternary system [Y(NO₃)₃(TBP)₃]-[UO₂(NO₃)₂(TBP)₂]-tetradecane in the temperature range 298.15–333.15 K were constructed. These diagrams contain the field of homogeneous solutions and the field of separation into two liquid phases (I, II). Phase I is enriched in [Y(NO₃)₃(TBP)₃] and [UO₂(NO₃)₂(TBP)₂], and phase II is enriched in tetradecane. With increasing temperature, the two-phase fields contract. The critical points of the ternary liquid systems depend on temperature. In the two-phase systems, [UO₂(NO₃)₂(TBP)₂] is preferentially distributed in phase I, although the binary system [UO₂(NO₃)₂(TBP)₂] tetradecane is homogeneous over the entire temperature range. Original Russian Text ? V.A. Keskinov, V.V. Lishchuk, A.K. Pyartman, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 5, pp. 417–419.     

Electronic structure and electrical transport characteristics of C60, 2C60 and 4C60 fullerene molecules

The extended Hückel method and the Green’s function method were used to calculate the electronic structure and electrical transport of Au electrode-C₆₀, 2C₆₀ or 4C₆₀ fullerene-Au electrode systems. Furthermore, their electronic structure and electrical transport characteristics were compared and analyzed. The results show that (i) owing to the contact with the Au electrodes, the C₆₀, 2C₆₀ and 4C₆₀ molecules change in their electronic structures significantly, and their energy gaps between LUMO and HOMO are narrow; (ii) the bonding between C₆₀, 2C₆₀ or 4C₆₀ fullerene and Au electrodes is partially covalent and partially electrovalent; and (iii) the conductance of the three fullerenes conforms to the order of C₆₀ > 2C₆₀ > 4C₆₀. Translated from Journal of Materials Science and Engineering, 2006, 24(1): 53–56 [译自: 材料科学与工程学报]     

Synthesis, molecular structure, and characterization of a new 3D-layered inorganic-organic hybrid material: [d/l-C6H13O2N-H]3[(PO4)W12O36]·4.5H2O

A new 3D-layered inorganic-organic hybrid [d/l-C₆H₁₃O₂N-H]₃[(PO₄)W₁₂O₃₆]·4.5H₂O (1), as racemic material in the solid phase, has been synthesized and fully characterized by elemental microanalysis, single crystal X-ray diffraction, and infrared, Raman, and proton nuclear magnetic resonance spectroscopes. The most unique structural feature of 1 is its three-dimensional inorganic infinite tunnel-like framework that results in weak van der Waals interactions along the a-axis. A weak interlayer interaction between the titled layers provides a desirable condition to explore its potential as a host in a host-guest complex. The racemization has been observed in the crystal structure with the centric space group (P2₁/c). The latter consists of α-[(PO₄)W₁₂O₃₆]³⁻and [d/l-C₆H₁₃O₂N-H]⁺ moieties with water molecules linked together by a complex network of hydrogen bond interactions.     

Room temperature synthesis of nearly monodisperse rodlike rutile TiO2 nanocrystals

A new method was developed to synthesize uniform rodlike rutile TiO₂ nanocrystals by the hydrolysis of tetrabutyl titanate [Ti(OC₄H₉)₄] in hydrochloric acid-alcohol aqueous solutions at room temperature. The hydrolytic sol-gel reaction generated 44 nm (diameter) × 200 nm (length) sized rutile TiO₂ nanocrystals. Transmission electron microscopic images showed that the particles have a uniform shape and narrow size distribution. X-ray diffraction and electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the rodlike TiO₂ nanoparticles prepared at room temperature were crystalline rutile structure grown along the [001] direction. The morphology and photocatalytic activity of the TiO₂ nanocrystals formed at different urea concentrations were showed. The rutile TiO₂ nanocrystals formed in the absence of urea exhibited higher photocatalytic activity than the commercial photocatalyst P25 on the photocatalytic degradation of Rhodamine B.     

Microstructure of Epitaxial La0.7Ca0.3MnO3 Thin Films Deposited by Direct Current Magnetron Sputtering on LaAlO3 Substrate

Transmission electron microscopy (TEM) and high resolution electron microscopy (HREM) have been used to study the microstructural properties of La_0.7Ca_0.3MnO₃ films on (001) LaAlO₃ substrates prepared by direct current magnetron sputtering technique. The as-grown thin films with different thickness are perfectly coherent with the substrates. The film suffers a tetragonal deformation in the area near the interface between the film and the substrate. With increasing thickness, the film is partially relaxed. It was found that La_0.7Ca_0.3MnO₃ films consist of two types of oriented domains described as: (1) (110)_f [001]_f||(001)_s[100]_s and (1¹10)_f [001]_f||(001)_s[100]_s and (2) (110)_f [001]_f||(001)_s[010]_s and (1¹10)_f [001]_f//(001)_s[010]_s. Upon annealing, the film is relaxed by the formation of mis¯t dislocations. Other than mis¯t dislocations, two types of threading dislocations with Burgers vector of <100> and <110> were also identified.     

A new borophosphate chain anion in an organo-templated iron(III) borophosphate: Synthesis, crystal structure and magnetic properties of (C4H12N2)3Fe6(H2O)4[B6P12O50(OH)2]·2H2O

The organo-templated iron(III) borophosphate (C₄H₁₂N₂)₃Fe^III₆(H₂O)₄[B₆P₁₂O₅₀(OH)₂]·2H₂O was prepared under mild hydrothermal conditions (443 K). The crystal structure was determined from single-crystal X-ray data at 295 K (orthorhombic, Pbca (No. 61), Z=4, a=17.8023(7) Å, b=16.1037(5) Å, c=19.1232(6) Å, V=5482.3(3) Å³, R1=0.055, wR2=0.104, 6576 observed reflections with I>2σ(I)) and contains a new type of borophosphate anion: a mixed open- and loop-branched zehner single chain, , built from heptamers [B₂P₅O₂₁] interconnected by BO₃(OH) tetrahedra sharing their third oxygen corners with additional (terminal) PO₄ tetrahedra to form open branchings. The mixed open- and loop-branched single chains running along [0 0 1] are interconnected by three crystallographically independent iron coordination octahedra to form a 3D framework structure containing eight-membered ring channels running along [0 1 0] and cages, which are occupied by two crystallographically independent piperazine cations and H₂O molecules. The displacement parameters of C and N atoms in the piperazine cations are dramatically influenced by the strength of the hydrogen bond reflecting the shape of the cavities. The magnetic investigations indicate the existence of antiferromagnetic interactions as the major components. A narrow hysteresis at low temperatures indicates a weak ferromagnetic component, due to a non-cancellation of spins.     

Fe2O3 core-NaCo[Fe(CN)6] shell nanoparticles—Synthesis and characterization

A facile precipitation route was developed for the synthesis of cobalt hexacyanoferrate (CoHCF) as a thin shell around cores of nanoparticles of iron(III) oxide, forming nanoparticles of iron(III) oxide@CoHCF (n-Fe₂O₃@NaCo[Fe(CN)₆]). The morphology and structure of the as-prepared n-Fe₂O₃@NaCo[Fe(CN)₆] were characterized by the techniques of electron microscopies, X-ray diffraction measurements, X-ray photoelectron spectroscopy, infrared spectroscopy and thermogravimetry. Carbon composite electrodes of n-Fe₂O₃@NaCo[Fe(CN)₆] were prepared and the electrochemical behavior of the nanoparticles was evaluated using cyclic voltammetry. The redox couples of n-Fe₂O₃@NaCo[Fe(CN)₆] were investigated and the diffusion coefficients of counter cation in the shell of CoHCF were obtained. The effect of size of particles and the structure of CoHCF was also evaluated. n-Fe₂O₃@NaCo[Fe(CN)₆] represented prominent electrocatalytic activity toward the oxidation of some biologically active compounds.     

Neutron powder diffraction and magnetic study of perovskites Pb(Mn1/2Nb1/2)O3 and Pb(Mn1/4Fe1/4Nb1/2)O3

The structural and magnetic properties of the complex metal oxides Pb(Mn_1/2Nb_1/2)O₃ (PMNO) and Pb(Mn_1/4Fe_1/4Nb_1/2)O₃ (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15 K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5 K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700 K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pmm) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [1 1 1] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB³⁺_1/2Nb_1/2O₃ series with the isomorphous substitution B³⁺, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B³⁺ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is also considered.     

Phase Separation in the Ternary Liquid System [Th(NO3)4(TBP)2]— [UO2(NO3)2(TBP)2]—Decane at Various Temperatures

The phase diagram of the ternary liquid system [Th(NO₃)₄(TBP)₂]— [UO₂(NO₃)₂(TBP)₂]—decane was studied within the 298.15–333.15 K range. The system has the area of homogeneous solutions and area of binary liquid subsystems (with separation); one phase (I) is enriched in [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂·(TBP)₂] and the other phase (II), in decane. The temperature does not substantially affect the area of phase separation. In two-phase systems, [UO₂(NO₃)₂(TBP)₂] is mainly concentrated in phase I, in spite of the fact that the binary system [UO₂(NO₃)₂(TBP)₂]—decane is single-phase in the entire temperature range studied. Concentration of [UO₂(NO₃)₂(TBP)₂] in phase I results in redistribution of [Th(NO₃)₄(TBP)₂] into phase II. The points of the critical composition of the ternary system are compositions with similar content of the solvates [Th(NO₃)₄(TBP)₂] and [UO₂(NO₃)₂(TBP)₂] at all the temperatures studied. __________ Translated from Radiokhimiya, Vol. 47, No. 6, 2005, pp. 520–522. Original Russian Text Copyright ? 2005 by Keskinov, Mishina, Pyartman.