Crystal structure of Pb<Subscript>6</Subscript>O[(Si<Subscript>6</Subscript>Al<Subscript>2</Subscript>)O<Subscript>20</Subscript>]

The crystal structure of Pb₆O[(Si₆Al₂)O₂₀)] is investigated using X-ray diffraction. The compound has tetragonal symmetry, space group I4/mmm, a = 11.7162(10) Å, c = 8.0435(12) Å, and V = 1104.13(2) ų. The structure is refined to R ₁ = 0.036 for 562 unique reflections with [F ₀] ≥ 4σF. The structure contains two symmetrically independent positions of the Pb²⁺ cations coordinated by five O atoms (Pb²⁺-O^2? = 2.34–2.68 Å). The TO₄ tetrahedra (T = Si, Al) form tubular [(Si₆Al₂)O₂₀] chains extended along the c axis. The O₄ oxygen atom is not bonded to the Si and Al atoms and is octahedrally coordinated by six Pb atoms with the formation of an oxo-centered OPb₆ octahedron. The assumption is made that, in some of lead silicate and aluminosilicate glasses, a number of oxygen atoms are located outside the tetrahedral structure and represent segregation centers of the Pb²⁺ cations due to the formation of oxo-centered complexes.     

Synthesis and crystal structure of the low-temperature modification of Li<Subscript>12</Subscript>Zn<Subscript>4</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>5</Subscript>

The crystal structure of a low-temperature modification of the Li₁₂Zn₄(P₂O₇)₅ compound has been determined by full-profile analysis from the X-ray powder diffraction data. The compound crystallizes in the monoclinic crystal system (a = 5.130(1) Å, b = 13.454(1) Å, c = 8.205(1) Å, β = 90.36(1)°, space group P2₁/n, Z = 4) and has a framework structure in which the zinc and lithium atoms statistically occupy equivalent positions.     

Crystal structure and thermal expansion of ammonium pentaborate NH<Subscript>4</Subscript>B<Subscript>5</Subscript>O<Subscript>8</Subscript>

Anhydrous ammonium pentaborate NH₄B₅O₈ has been synthesized by thermal dehydration of larderellite NH₄[B₅O₇(OH)₂] · H₂O at a temperature of 290°C for 7 h. The crystal structure has been determined from the X-ray powder diffraction data: a = 7.58667(5) Å, b = 12.00354(8) Å, c = 14.71199(8) Å, R _p = 6.23, R _wp = 7.98, R _B = 12.7, R _F = 8.95, and β-KB₅O₈ structure type. The double interpenetrating framework is formed by pentaborate groups, each consisting of a boron-oxygen tetrahedron and four triangles, in which all oxygen atoms are bridging. The thermal behavior of the NH₄B₅O₈ compound has been investigated using thermal X-ray diffraction. As for other pentaborates of this type, the thermal expansion of the NH₄B₅O₈ compound is anisotropic and reaches a maximum along the a axis. The thermal expansion coefficients are as follows: α _a = 39 × 10^?6, α _b = 6 × 10^?6, α _c = 20 × 10^?6, and α _V = 65 × 10^?6 °C^?1.     

Synthesis and crystal structure of a new modification of sodium tetrahydroxyborate NaB(OH)<Subscript>4</Subscript>

A new polymorphic modification of sodium tetrahydroxyborate NaB(OH)₄ is synthesized and its crystal structure is determined. The compound crystallizes in symmetry space group P2₁2₁2₁ with the unit cell parameters a = 5.323(5) Å, b = 9.496(5) Å, and c = 6.596(5) Å. The discrepancy factor for 511 symmetrically nonequivalent reflections is R = 0.0188. Layers that are formed by boron tetrahedra, aligned parallel to the (010) planes, and alternate with layers of sodium cations can be distinguished in the structure.     

Crystal structure of new compound (Rb,K)<Subscript>2</Subscript>Cu<Subscript>3</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

A new compound of (Rb,K)₂Cu₃(P₂O₇)₂ is obtained by high-temperature reactions from a mixture of RbNO₃, KNO₃, Cu(NO₃)₂, and (NH₄)₄P₂O₇. The crystal structure was solved by direct methods and refined to R ₁ = 0.056 for 5022 independent reflections. The compound belongs to a rhombic crystal system, P2₁2₁2₁, Z = 8, a = 9.9410(7) Å, b = 13.4754(6) Å, c = 18.6353 (3) Å, and R = 0.056. The basis of the structure is a complex copper-phosphate skeleton of the composition of [Cu₃(P₂O₇)₂]^2–, which can be regarded as consisting of two types of heteropolyhedral layers parallel to the (001) plane. The layers are alternated with each other, forming a frame, in the cavities of which the positions of alkali cations are located, statistically populated with K⁺ and Rb⁺ ions. Based on the refined populations of the positions of alkali cations, an exact chemical formula of the compound can be written as Rb_1.28K_0.72Cu₃(P₂O₇)₂. The compound is the most complex among those known to this day of the composition of A₂ ^IB₃ ^II(P₂O₇)₂ (A = Li, Na, K, Rb, or Cs; B = Ni, Cu, or Zn).     

Synthesis and structural refinement of fully dehydrated fully Zn<Superscript>2+</Superscript>-exchanged zeolite Y (FAU), |Zn<Subscript>35.5</Subscript>|[Si<Subscript>121</Subscript>Al<Subscript>71</Subscript>O<Subscript>384</Subscript>]-FAU

The single-crystal structure of |Zn_35.5|[Si₁₂₁Al₇₁O₃₈₄]-FAU per unit cell, a = 24.794(1), dehydrated at 673 K and 1 × 10^?6 Torr, has been determined by single-crystal X-ray diffraction techniques in the space group \( Fd\bar{3}m \) at 294(1) K. The structure was refined using all intensities to the final error indices (using the 930 reflections for which F _o > 4σ(F _o)) R ₁ = 0.0448 (based on F) and wR ₂ = 0.1545 (based on F ²). About 35.5 Zn²⁺ ions per unit cell are found at an unusually large number of crystallographic distinct positions, six. The 0.5 Zn²⁺ ion per unit cell is located at the center of double 6-ring (D6R, site I; Zn(I)-O(3) = 2.642(3) Å and O(3)-Zn(I)-O(3) = 81.23(12) and 98.77(12)°). Two different site-I′ positions (in the sodalite cavities opposite D6Rs) are occupied by 14 and 3 Zn²⁺ ions per unit cell, respectively; these Zn²⁺ ions are recessed 0.67 Å and 1.02 Å, respectively, into the sodalite cavities from their 3-oxygens plane (Zn(I′a)-O(3) = 2.094(3) Å, Zn(I′b)-O(3) = 2.23(5) Å, O(3)-Zn(I′a)-O(3) = 110.32(12)°, and O(3)-Zn(I′b)-O(3) = 100.9(30)°). Site-II′ positions (in the sodalite cavities opposite S6Rs) are occupied by 6 Zn²⁺ ions, each of which extends 0.63 Å into the sodalite cavities from their 3-oxygens plane (Zn(II′)-O(2) = 2.164(3) Å and O(2)-Zn(II′)-O(2) = 112.00(12)°). Twelve Zn²⁺ ions are found at two nonequivalent sites II (in the supercage) with occupancies of 7 and 5 ions, respectively; these Zn²⁺ ions are recessed 0.52 Å and 0.96 Å, respectively, into the supercage from their 3-oxygens plane (Zn(IIa)-O(2) = 2.138(12) Å, Zn(IIb)-O(2) = 2.28(4) Å, O(2)-Zn(IIa)-O(2) = 114.2(10)°, and O(2)-Zn(IIb)-O(2) = 103.7(25)°).     

Effects of co-ion initial concentration ratio on removal of Pb<Superscript>2+</Superscript> from aqueous solution by modified sugarcane bagasse

A modified sugarcane bagasse (SCB) fixed bed column was used to remove Pb²⁺ from aqueous solution. To determine the optimal condition for Pb²⁺ separation, Ca²⁺ was chosen as the model interfering ion, and effects of Ca²⁺ and Pb²⁺ initial concentration ratio (C ₀ ^Ca : C ₀ ^Pb ) on the adsorption of Pb²⁺ were investigated. Results showed that adsorption amount ratio of Ca²⁺ and Pb²⁺ (q _e ^Ca : q _e ^Pb ) had a good linear relationship with C ₀ ^Ca : C ₀ ^Pb . Mass ratio of Pb²⁺ absorbed on the modified SCB was higher than 95% at C ₀ ^Ca : C ₀ ^Pb <1.95, illustrating that Pb²⁺ could be selectively removed from aqueous solution. To verify that, simulated waste water containing co-ions of K⁺, Na⁺, Cd²⁺ and Ca²⁺ was treated, and results showed that the equilibrium amount of Pb²⁺, K⁺, Na⁺, Cd²⁺ and Ca²⁺ adsorbed was 134.14, 0.083, 0.058, 1.28, and 1.28mg g^?1, respectively, demonstrating that the modified SCB could be used to remove Pb²⁺ from aqueous solution in the investigated range.     

Structure of a catalytically active oxo-centered trinuclear cobalt complex triaqua-(μ<Subscript>3</Subscript>-oxo)-hexa(μ<Subscript>2</Subscript>-pivalato-O,O′)-tricobalt(III)

The structure of a catalytically active oxo-centered trinuclear cobalt complex, namely, [triaqua-(μ₃-oxo)-hexa(μ₂-pivalato-O,O′)-tricobalt(III)]¹⁺ · NO ₃ ^? · 3H₂O, has been determined using X-ray diffraction analysis. The compound crystallizes in the hexagonal crystal system, space group of symmetry P6₃/mmc, with the unit cell parameters a = 12.328(1) Å, c = 22.625(1) Å, V = 2978.1(4) ų, Z = 2, and ρ = 1.075 g/cm³. The final discrepancy factor is R1 = 0.0596 for 589 symmetrically nonequivalent reflections with I ? 2σ(I), wR2 = 0.1612, and GooF = 1.035. The high-symmetry complex [C₃₀H₆₀O₁₆Co₃]¹⁺ with symmetry D _6h and a diameter of ～11 Å is an oxo-centered trinuclear cluster consisting of three symmetrically equivalent Co(III) atoms. Among the oxo-centered trinuclear metal complexes known to date, this complex has the highest symmetry and differs by the presence of two chemically equivalent bridges between the metal atoms. Apart from the two positively charged symmetrically equivalent trinuclear complexes, the unit cell contains two symmetrically equivalent NO ₃ ^? ions (statistically disordered over four positions) and six crystal water molecules.     

Modeling Self-Organization Processes in Crystal Forming Systems. Symmetry and Topology Codes of Cluster Self-Assembly of Crystal Structure of Na<Subscript>44</Subscript>Tl<Subscript>7</Subscript> (Na<Subscript>6</Subscript>Tl)

The geometrical and topological analysis of the crystal structure of intermetallide Na₄₄Tl₇ (Na₆Tl, a = 24.154 Å, V = 14091.8 ų, space group F-43m) is carried out. The algorithms of the combinatorial-topological analysis, which ensure the recovery of the symmetrical and topological code (program) of the cluster self-assembly of the crystal structure of an intermetallide, are developed. The topological type of the basic 3D network for two types of cluster precursors corresponds to a simple cubic 3D network P _c with CN = 6 and basic 2D network of type 4⁴. There are eight cluster precursors in the unit cell: four K86 and four K50. The cluster precursor K86 made from 86 atoms is formed from eight icosahedra i-TlNa₁₂ linked by the apices. The center of the cluster precursor K86 is at the position 4a (0, 0, 0) with the point symmetry g = –43m. The 50-atomic cluster precursor K50 consists of six i-TlNa₁₂ icosahedra. The center of the cluster precursor K50 is in the partial position 4b (0, 0, 0) with the point symmetry g = –43m. The symmetrical and topological codes of the self-assembly of 3D structures from nanocluster precursors K86 and K50 are reconstructed in the following form: primary chain → microlayer → microframework.     

Raman spectra and surface structure of CaO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass leached in potassium hydroxide solutions

It is difficult to research on the surface structure of amorphous phase in fly ash during leaching reaction due to crystalline phase and complex structure. In the present work, in order to reveal the effects of leaching reaction on the surface structure of amorphous phase in fly ash, the modelling CaO-Fe₂O₃-Al₂O₃-SiO₂ glass was prepared by the traditional melting methods. The leaching reaction of CaO-Fe₂O₃-Al₂O₃-SiO₂ glass with 7.5 M KOH was investigated by spectroscopy, spectrophotometer and wet chemical method. The results show that the content of Q ¹, Q ², Q ³ and Q ⁴ of glass without corrosion was 4.21, 9.51, 23.03 and 52.55%, respectively, which shows that the network polymerization of glass is compact. The leaching reaction of glass can be described by the following equation: dS/dt = k/(r + S ₀). Leaching in KOH for various times induces the content of Q ⁴ and Q ¹ to be decreased, and Q ² and Q ³ increased, resulted in the depolymerization of network and the surface glass dissolved in alkaline solution to form a gel phase. In stage one of leaching reaction, the rate of iron ion leached from glass surface was slow, which resulted in the small slope of straight-line relationship of leaching curve. In the following stage, the leaching rate of iron ion increased with the prolongation of time.     

Cluster Self-Organization of Intermetallic Systems: Two-Layer Quasi-Spherical Nanocluster Precursors K69 and K26 in the Crystal Structure of Li<Subscript>26</Subscript>Na<Subscript>58</Subscript>Ba<Subscript>38</Subscript> (<Emphasis Type="Italic">cF</Emphasis>488)

The geometric and topological analysis of the crystal structure of intermetallic Li₂₆Na₅₈Ba₃₈ (cF488, a = 27.335 Å, V = 20 424 ų, F-43m) is carried out using computer methods (ToposPro software package). The analysis method is based on determining the chemical composition and structure of an intermetallic cluster precursor and constructing a basic 3D network of the structure in the form of a graph whose nodes correspond to the position of their centers of gravity. Using the method of the complete decomposition of the 3D factor graph of the crystal structure into cluster substructures, we find two types of framework-forming nanoclusters, namely, K69 of the 1@16@52 composition and K26 of the 0@4@22 composition with point symmetry g =–43m. The symmetric and topological code of self-assembly of 3D structures from nanocluster precursors is reconstructed in the following form: primary chain → microlayer → microframework. Clusters Ba5, Na₆(Na₄), and Na₂В are determined as spacers occupying voids in the 3D framework of nanoclusters K69 and K26.     

Crystal Structure and Computational Analysis of a Two-Dimensional Coordination Polymer,BiI<Subscript>3</Subscript>(DppeO<Subscript>2</Subscript>)<Subscript>3/2</Subscript>

Catena-poly[fac-triiodobismuth(III)-tris-(µ-ethane-1,2-diylbis(diphenylphosphane oxide-κ²O,O′))], a 2-D sheet network of BiI₃ was synthesized from BiI₃ and ethane-1,2-diylbis(diphenylphosphane oxide) (DppeO₂) in tetrahydrofuran. The crystal structure revealed a trigonal structure with three-fold symmetry at Bi. Bismuth centers show fac-BiI₃O₃ coordination, with Bi–I?=?2.9416(2) Å and Bi–O?=?2.4583(17) Å. The I–Bi–I and O–Bi–O angles (95.520(7)° and 79.04(6)°, respectively) indicate trigonal distortion in the Bi octahedron. Bridging DppeO₂ ligands centered on inversion centers give rise to a 2-D sheet polymer. The 8.3 Å thick sheets consist of three layers in a sandwich structure. The outer layers are composed of phenyl rings and BiI₃ groups with the iodide atoms pointing outward. The central layer consists of the O=PCH₂CH₂P=O bridging groups. Computational results suggest that semi-conducting behavior arises from Bi(III) centers. A halide to DppeO₂ π* transition is suggested by theoretical results.     

Reusability and selective adsorption of Pb<Superscript>2+</Superscript> on chitosan/P(2-acrylamido-2-methyl-1-propanesulfonic acid-<Emphasis Type="Italic">co</Emphasis>-acrylic acid) hydrogel

Reusability and selective adsorption toward Pb²⁺ with the coexistence of Cd²⁺, Co²⁺, Cu²⁺ and Ni²⁺ ions on chitosan/P(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylic acid) [CS/P(AMPS-co-AA)] hydrogel, a multi-functionalized adsorbent containing –NH₂, –OH, –COOH and –SO₃H groups was studied. The CS/P(AMPS-co-AA) was prepared in aqueous solution by a simple one-step procedure using glow discharge electrolysis plasma technique. The reusability of adsorbent in HNO₃, EDTA-2Na and EDTA-4Na was investigated in detail. The competitive adsorption of the metal ions at the initial stage was compared between their equal mass concentration and equal molar concentration. In addition, the adsorption mechanism of the adsorbent for adsorption of Pb²⁺ was also analyzed by XPS. The results showed that the optimum pH of adsorption was 4.8, and time of adsorption equilibrium was about 180 min. Adsorption kinetics fitted well in the pseudo second-order model. The equilibrium adsorption capacities of Pb²⁺, Cd²⁺, Co²⁺, Cu²⁺, and Ni²⁺ at pH 4.8 were obtained as 673.3, 358.3, 176.7, 235.0 and 171.7 mg g^?1, in their given order. The adsorbent displayed an excellent reusability using 0.015 mol L^?1 EDTA-4Na solution as the eluent, and the desorption ratio could not correctly reflect the true characteristics of adsorption/desorption process. Moreover, the adsorbent showed good adsorption selectivity for Pb²⁺. The molar adsorption capacity at the initial stage with equal molar concentration was more reliable than the mass adsorption capacity during the study of selective adsorption. According to the XPS results, the adsorption of Pb²⁺ ions by the CS/P(AMPS-co-AA) absorbent could be attributed to the coordination between N atom and Pb²⁺ and ion-exchange between Na⁺ and Pb²⁺.     

Structural characterization and superconducting properties of MgB<Subscript>2</Subscript> prepared by SHS-method

Self-propagating high-temperature synthesis (SHS) of bulk MgB₂ superconductor from Mg-2B powder blend is reported. This reaction proceeds violently at 100 A under a protective atmosphere. Since the heat of reaction of Mg and B was not enough for chain reaction, then (Ti + C) mixed powders were used as the ignition agent to assist the reaction (Mg + 2B). In this case, the combustion front moved without any difficulty. The diffraction lines of the product can be indexed to a hexagonal MgB₂ phase, with lattice constants a = 3.0845 Å, and c = 3.5259 Å. For comparison, the direct synthesis of (Mg + 2B) mixture was carried out at (800°C–1000°C). It can be found, that high-temperature sintering (1000°C) will induce the formation of impurities. The MgB₂ grains are fine, well compacted and more homogenous. The structure of materials was studied using XRD, FESEM and EDX. M-H curvatures were measured under the magnetic fields between ?80 kOe and 80 kOe. J _c was calculated from width of magnetization hysteresis loops based on the extended Bean Model.     

Transport properties of solid electrolytes based on <Emphasis Type="Italic">Me</Emphasis>Sm<Subscript>2</Subscript>S<Subscript>4</Subscript>

The solid-solution regions in the MeSm₂S₄-MeS and MeSm₂S₄-Sm₂S₃ (Me = Ca, Ba) systems are revealed. The average ion, cation, and anion transport number of the synthesized solid electrolytes xSm₂S₃[Ca(Ba)S] · (100 ? x)Ca(Ba)Sm₂S₄ (x = 1?10 mol %) are determined by the electromotive force (emf) method with the use of concentration cells with and without transfer. In the phases under investigation, the ion transfer in the temperature range 673–723 K is provided by sulfide ions (\(t_{S^2 } \) = 1.00±0.02). The diffusion coefficients of S^2? ions in the solid electrolytes are determined by potentiostatic chronoamperometry. A vacancy mechanism of defect formation is proposed. It is demonstrated that the transport characteristics of the solid electrolytes based on the CaSm₂S₄ compound are worse than those of the solid electrolytes based on the BaSm₂S₄ compound.     

Solution-Combustion Synthesis of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> as a Cathode Material for Lithium-Ion Batteries

A cathode material for lithium-ion batteries–LiNi_1/3Co_1/3Mn_1/3O₂–was prepared by solution combustion synthesis and characterized by XRD, SEM, and galvanostatic charge/discharge cycling. The sample calcined at 950°C for 10 h showed best charge/discharge performance. An initial discharge capacity (C) of 150.5 mA h g^–1 retained 95.7% of its value after 75 charge/discharge cycles at I_c = 14 mA g^–1 (0.2C rate), I_d = 70 mA g^–1 (0.5C rate).     

Density and microhardness of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The density d at a temperature of 25°C is measured by the hydrostatic weighing method, the Vickers microhardness H _V is determined, and the fluctuation free volume fraction f _g is calculated for glasses in the SrO-B₂O₃-SiO₂ system with a constant strontium oxide content in the range from 35 to 45 mol %. It is demonstrated that the quantities H _V and f _g decrease and the density d increases with an increase in the SrO content.     

Synthesis of Titanates with a Ramsdellite-Type Tunnel Structure Crystallizing in the Li<Subscript>2</Subscript>O-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> System in Different Gaseous Media

The ramsdellite-type phases crystallizing in the Li₂O-Fe₂O₃-TiO₂ system in the course of synthesis in gaseous media at different oxygen partial pressures are studied. Solid solutions based on the ramsdellite structure with the composition Li₂Ti_3?xFe _x O_{7 ? δ} (0 ≤ x ≤ 0.7) are prepared in an oxidizing medium (P_O2 = 1 atm) for the first time. Analysis of the results obtained by electron paramagnetic resonance and Mossbauer spectroscopy revealed that, in these solid solutions, all iron ions are in the oxidation state Fe⁺³.     

Synthesis and Thermoelectric Properties of Ceramics Based on Bi<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Co<Subscript>1.7</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Oxide

Layered ceramics based on bismuth–calcium cobaltite with varied cobalt oxide contents is synthesized by the solid-phase method, the ceramics phase composition is determined, and the microstructure, thermal expansion, electroconductivity, and thermal electromotive force are investigated. The formation of just one compound, ternary oxide composed of Bi₂Ca₂Co_1.7O _y , is established within the quasi-binary Bi₂Ca₂O₅–CoO _z system. The effect of the cobalt oxide content on the Bi₂Ca₂Co _x O _y ceramics’ microstructure and physicochemical properties is analyzed. The single-phased ceramic sample Bi₂Ca₂Co_1.7O _y demonstrated the highest power factor value among all the investigated samples—26.0 μW/(m K²) at a temperature of 300 K. This sample showed the lowest value of the thermal linear expansion coefficient of 9.72 × 10^–6 K^–1.     

Parameters of luminescence and the local structure of Eu<Superscript>3+</Superscript> centers in fluorogermanate glasses

The influence of the chemical nature of the local environment of Eu³⁺ ions on the parameters of luminescence of these centers in glasses of the (BaGeO₃)_{1 ? x ? y} (Al₂O₃) _x (0.45CaF₂ · 0.55MgF₂) _y (x = 0.25, y = 0; x = 0.17, y = 0.17; x = 0.15, y = 0.22; x = 0.07, y = 37.00; x = 0, y = 0.45) system is investigated. The oxidation state of europium atoms and the degree of homogeneity of their local environment in the glasses are determined using ¹⁵¹Eu Mössbauer spectroscopy.