Chemischer Transport von Mischkristallen im System CuMoO4/ZnMoO4

Chemical Vapour Transport of Solid Solutions in the CuMoO₄/ZnMoO₄ System Two solid solutions exist in the system CuMoO₄/ZnMoO₄: Cu_1‐xZn_xMoO₄ with x=0 to x=0.15 and x=0.20 bis x=1, respectively. Single crystals of Cu_1‐xZn_xMoO₄ were obtained by chemical vapor transport in the temperature gradient 973K→873K using Cl₂, Br₂ or NH₄Cl as transport agents. No difference of the Cu/Zn ratio between source and sink was observed for the transport agents Cl₂ and NH₄Cl. A slight shift to higher Zn amounts was observed for single crystals of Cu_1‐xZn_xMoO₄ grown using Br₂ as transport agent. The experimental results were compared with results of model calculations.     

Untersuchungen an einigen Einkristallen des Systems CuxHg1–xCr2Se4

Study of Some Single Crystals of the Cu_xHg_1–xCr₂Se₄ System Single crystals of the Cu_xHg_1–xCr₂Se₄ for 0 ≤ x ≤ 0.077 were prepared by the chemical transport method. The crystals were analyzed and investigated by X-rays. Some electric and magnetic properties of the single crystals were determined and the results obtained are discussed.     

Koexistenzbeziehungen,Darstellung und Eigenschaften ternärer Phasen im System Cu/Mo/O

Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO₄, Cu₃Mo₂O₉, Cu₄Mo₅O₁₇, Cu₆Mo₅O₁₈, Cu_4–xMo₃O₁₂, and Cu_xMoO₃ are found to be thermodynamical stable. The homogeneity range of Cu_4–xMo₃O₁₂ runs to x = 0.1–0.2. Single crystals of CuMoO₄ and Cu₃Mo₂O₉ were grown by chemical transport reactions with TeCl₄, Cl₂, HCl, and Br₂ as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO₄ and Cu₃Mo₂O₉ was investigated with thermal analysis and decompositon pressure measurements.     

Reactive adsorption of hydrogen sulfide by promoted sorbents Cu‐ZnO/SiO2: active sites by experiment and simulation

In the Cu_x‐Zn_(1‐x)O/SiO₂ sorbents for ultradeep adsorptive removal of H₂S from gaseous fuel reformates for fuel cells at room temperature, Cu promoter sites significantly increase sulfur uptake capacity of the sorbents. We report characterization of the family of Cu_x‐Zn_(1‐x)O/SiO₂ sorbents for reactive adsorption of H₂S using X‐ray diffraction (XRD), Brunauer‐Emmett‐Teller (BET) surface area analysis, electron spin resonance (ESR), ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy (DRS) and calculations by the density functional theory (DFT). Both the supported ZnO phase and Cu promoter sites in the Cu_x‐Zn_(1‐x)O/SiO₂ sorbents are nano‐dispersed, as shown by XRD. The Cu_x‐Zn_(1‐x)O/SiO₂ sorbents contain Cu promoter as the Cu²⁺ site of octahedral geometry, as found by the complementary ESR and UV–vis DRS. Mechanism of the promoter effect of the Cu²⁺ site in the Cu_x‐Zn_(1‐x)O/SiO₂ sorbents in reaction with H₂S is proposed based on DFT calculations. Copyright © 2012 John Wiley & Sons, Ltd.     

Chemischer Transport fester Lösungen. 10 [1] Zum Chemischen Transport von quaternären Cobalt(II)‐Zink‐ und Mangan(II)‐Zinkgermanaten

Chemical Vapor Transport of Solid Solutions 10 [1] The Chemical Vapor Transport of quarternary Cobalt(II)‐Zinc and Manganese(II)‐Zinc Germanates By means of chemical vapor transport methods using HCl or Cl₂ as transport agent the crystalline solid solutions (Zn_xCo_1—x)₂GeO₄ and (Mn_xZn_1—x)₂GeO₄ have been prepared (1050 → 900 °C, 850 → 700 °C, respectively). ZnGeO₃ — although unknown as a pure solid — can be stabilized as a mixed crystal (Mn_xZn_1—x)GeO₃ (x > 0, 5).     

Darstellung,Eigenschaften und Kristallstruktur von RuSn6[(Al1/3–xSi3x/4)O4]2 (0 ≤ x ≤ 1/3) – einem Oxid mit isolierten RuSn6‐Oktaedern

Preparation, Properties, and Crystal Structure of RuSn₆[(Al_1/3–xSi_3x/4)O₄]₂ (0 ≤ x ≤ 1/3) – an Oxide with isolated RuSn₆ Octahedra RuSn₆[(Al_1/3–xSi_3x/4)O₄]₂ is obtained by the solid state reaction of RuO₂, SnO₂, Sn, and Si in an Al₂O₃‐crucible at 1273 to 1373 K. The compound is cubic with the space group Fm 3 m (a = 9.941(1) Å, Z = 4, R₁ = 0.0277, wR₂ = 0.0619), a semiconductor and stable in air. Results of Mößbauer measurements as well as bond length‐bond strength calculations justify the ionic formulation Ru²⁺Sn₆²⁺[(Al_1/3–x³⁺Si_3x/4⁴⁺)O₄^2–]₂. The central motif of the crystal structure are separated RuSn₆‐octahedrea. These are interconnected by oxygen atoms, arranged tetrahedrely above the surfaces of the RuSn₆‐octahedrea and partialy filled with Al and Si, respectively. Because of these features the compound can be considered as a variant of the crystal structure type of pentlandite.     

Mechanochemical Synthesis and Temperature‐Dependent Optical Properties of Thermochromic (Ag1−xCux)2HgI4

Thermochromic materials are generally synthesized via high‐temperature melting reaction or solution‐based synthesis. Herein, all‐inorganic thermochromic compounds of (Ag_1?xCu_x)₂HgI₄ were synthesized by solvent‐free simple and scalable mechanochemical grinding at room temperature. Temperature‐dependent electronic absorption spectroscopy along with DSC analysis confirmed the thermochromic events within these materials, and the phase transition temperature varied with solid solution compositions. The photoluminescence (PL) spectra is red‐shifted with the increase in the Cu content in (Ag_1?xCu_x)₂HgI₄ (x=0–1).     

Phosphaniminato‐Acetato‐Cluster von Kupfer und Zink. Kristallstrukturen von [Cu4(NPEt3)2(O2CCH3)6] und [Zn4(NPEt3)2(O2CCH3)6]

Phosphoraneiminato Acetate Cluster of Copper and Zinc. Crystal Structures of [Cu₄(NPEt₃)₂(O₂CCH₃)₆] and [Zn₄(NPEt₃)₂(O₂CCH₃)₆] The anhydrous acetates of copper(II) and zinc react with the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane at 20 °C forming the mixed phosphoraneiminato acetate clusters [Cu₄(NPEt₃)₂(O₂CCH₃)₆] ( 1 ), which forms emerald crystals, and colourless [Zn₄(NPEt₃)₂ · (O₂CCH₃)₆] ( 2 ). In spite of analogous composition the structures of 1 and 2 are completely different. In the asymmetric unit of 1 three copper atoms of an almost isosceles triangle are linked via two nitrogen atoms of the NPEt₃^– groups to form a trigonal bipyramidal aggregate. One of these three copper atoms is chelated by an acetate group, another one is connected with the fourth copper atom via three μ₂‐O₂C–CH₃ groups. The asymmetric units are associated via a μ₂‐O₂C–CH₃ group and a μ₃‐OC(O)CH₃ group at a time so that infinite chains result. In 2 two zinc atoms are linked via the nitrogen atoms of the two NPEt₃^– groups to form an almost centrosymmetric four‐membered ring. Both nitrogen atoms of the four‐membered ring are connected with another zinc atom each. These zinc atoms again are linked with the zinc atoms of the Zn₂N₂ four‐membered ring via two μ₂‐O₂C–CH₃ groups each and additionally coordinated with a terminal acetate ligand each.     

Solid solutions in the Zn-Co-O system: Physicochemical properties

Physicochemical analysis is used to study phase equilibria and to design a concentration diagram for the Zn-Co-O system. ZnO-, CoO-, and Co₃O₄-based mixed crystals with a fixed Zn/Co ratio have different oxygen nonstoichiometry depending on the synthesis and annealing parameters. Metastable clustering is discovered in Zn_{1 ? x} Co_xO_{1 + δ} wurtzite solid solutions, which exist stably in the range 0 ≤ x ≤ 0.2. Magnetization investigation shows that an antiferromagnetic order exists in homogeneous Zn_{1 ? x} Co_xO_{1 + δ} grains; this order is conserved up to 625 ± 25 K. The substitution of praseodymium, neodymium, samarium, or europium for zinc(II) cations in Zn_0.9Co_0.1O_{1 + δ} does not spoil the compensated antiferromagnetism of the wurtzite unit cell.     

Röntgenographische und schwingungsspektroskopische Untersuchung der Sulvanitmischkristalle Cu3Nb(SxSe1−x)4, Cu3Nb(SexTe1−x)4, und Cu3Ta(SxSe1−x)4 und Cu3Ta(SexTe1−x)4

X-Ray and Vibrational Studies of Sulvanite Mixed Cystals Cu₃Nb(S_xSe_1?x)₄, Cu₃Nb(Se_xTe_1?x)₄, Cu₃Ta(S_xSe_1?x)₄ and Cu₃Ta(Se_xTe_1?x)₄ Solid solutions Cu₃Nb(S_xSe_1?x)₄, Cu₃Nb(Se_xTe_1?x)₄, Cu₃Ta(S_xSe_1?x)₄ and Cu₃Ta(Se_xTe_1?x)₄ with sulvanite structure have been prepared in the range 0 ≤ x ≤ 1. The lattice constants in all systems obey the Vegard rule. Infrared and Raman spectra have been measured. The spectra of the compounds with mixed anion sublattices show additional peaks, compared to those of the end members, because besides the polyhedra MX₄ and MY₄ also groups MX₃Y, MX₂Y₂, and MXY₃ are present, and all groups are able to oscillate independently. By comparison of the peak intensities and the statistical frequency of the groups according to the composition, the additional valence vibrations could be attributed to the groups.     

(Zn1-xMnx)C2O4·2H2O在空气中的热分解动力学研究

用热分析（TG-DTG/DTA）、X射线衍射（XRD）技术和透射电镜（TEM）研究了固态物质Zn_1-xMn_xC₂O₄•2H₂O在空气中热分解的过程。热分析结果表明，Zn_1-xMn_xC₂O₄•2H₂O在空气中分两步分解，其失重率与理论计算失重率相吻合。 XRD和TEM结果表明，Zn_1-xMn_xC₂O₄•2H₂O分解的最终产物为Zn_1-xMn_xO,其颗粒大小约为10-13 nm。在非等温条件下对Zn_1-xMn_xC₂O₄•2H₂O的热分解动力学进行了分析。用Friedman法和Flynn-Wall-Ozawa(FWO)法求取了分解过程的活化能E，并用多元线性回归给出了可能的机理函数。Zn_1-xMn_xC₂O₄•2H₂O两步热分解的活化能分别为155.7513 kJ/mol 和215.9397 kJ/mol。     

Anodic synthesis and XPS analysis of La_(1-x)Na_xCu_2O_4

The single phase La1-x NaxCu2O4 crystals were synthesized by an electrochemical method from molten KOH/NaOH/KNO3 at 280-300℃ while La2-yNayCuO4 were prepared by precipitation from the same molten salt. The resulting crystals were characterized by using SEM, XRD, EDX and XPS. XPS analysis revealed that the La3d satellite structures of La1-xNaxCu2O4 were quite different from those of La2-yNayCuO4. These differences have been attributed to the changes in crystal structures, bond lengths and covalent character of the metal-ligand bonds.     

Spinelle mit substituierten Nichtmetallteilgittern. IV. Rötgenographische Untersuchung der Systeme CuCr2(S1−xSex)4 und CuCr2(Se1−xTex)4

Spinels with substituted Nonmetal Sublattices. IV. CuCr₂(S_1?xSe_x)₄ and CuCr₂(Se_1?xTe_x)₄ Polycrystalline samples of the spinel system CuCr₂(S_1?xSe_x)₄ have been prepared with 0 ≤ x ≤ 1. We found that in the spinel system CuCr₂(Se_1?xTe_x)₄ no solid solution is existent in the range 0.01 ≤ x ≤ 0.70. When S is substituted by Se and Se by Te the lattice constants increase linearely by 0.52 Å and 0.81 Å respectively. The anion-sublattice shows random distribution of the chalcogen atoms, the chalcogen parameters u are constant in the system CuCr₂(S_1?xSe_x)₄ with a mean value of u = 0.382₉. The calculated anion-cation-distances lead to a covalent tetrahedral radius r_Cu = 1.23 Å. This radius is in agreement with the radius r_Cu = 1.22 Å of Cu spinels with Cu in the valence +1.     

Synthesis,crystal structures and properties of the new compounds K7–xAg1+x(XO4)4 (X = Mo,W)

Two new isostructural compounds, namely heptapotassium silver tetrakis(tetraoxomolybdate), K_7–x Ag_1+x (MoO₄)₄ (0 ≤ x ≤ 0.4), and heptapotassium silver tetrakis(tetraoxotungstate), K_7–x Ag_1+x (WO₄)₄ (0 ≤ x ≤ 0.4), have been synthesized and found to crystallize in the polar space group P 6₃mc (Z = 2) with the unit‐cell dimensions a = 12.4188 (2) and c = 7.4338 (2) Å for K_6.68Ag_1.32(MoO₄)₄ (single‐crystal data), and a = 12.4912 (5) and c = 7.4526 (3) Å for K₇Ag(WO₄)₄ (Rietveld analysis data). Both structures represent a new structure type, with characteristic [K1(X O₄)₆] `pinwheels' of K1O₆ octahedra and six X O₄ tetrahedra (X = Mo, W) connected by common opposite faces into columns along the c axes. The octahedral columns are linked to each other through Ag1O₄ tetrahedra along with the K2 and K3/Ag2 polyhedra, forming the polar rods (…Ag1O₄–X 1O₄–empty octahedron–Ag1O₄…). Ag1 is located almost at the centre of the largest face of its coordination tetrahedron and seems to have some mobility. The new structure type is related to the Ba₆Nd₂Al₄O₁₅ and CaBaSiO₄ types, and to other structures of the α‐K₂SO₄–glaserite family. The differential scanning calorimetry (DSC) and second harmonic generation (SHG) results show that both compounds undergo first‐order phase transformations to high‐temperature centrosymmetric phases.     

Structural Aspects of Lithium Transfer in Solid Electrolytes Li2x Zn2-3xTi1+xO4 (0.33≤ x≤ 0.67)

Solid solutions Li_{2x Zn2-3x}Ti_1+xO₄, where x =1/3, 1/2, 3/5, 2/3, were studied by powder X-ray diffractometry and differential thermal analysis. Conductivity measurements have been performed in the gas phase at different temperatures and oxygen pressures. Distribution of cations over the sites of the spinel structure has been determined. Conductivity increases substantially with lithium concentration. The high lithium conductivity of Li₃Zn_0.5Ti₄O₁₀ (x=3/5) and Li₄Ti₅O₁₂ (x=2/3) is the result of two sequential phase transitions associated with different lithium distributions in high-temperature phases with defective NaCl type structures. Possible routes of lithium ion transport are discussed and rationalized based on the conductivity and crystal data.     

Hydrothermal synthesis, structure and property of nano-BaTiO3-based dielectric materials

A series of Ba_1-xSr_xTi_1-yZr_yO₃ (0≤x≤0.5, 0≤y≤0.4) and BA_1?xZn_xTi_1?ySn_yO₃ (0≤x≤0.3, 0≤y≤0.3) solid solutions were synthesized by low-temperature/low-pressure hydrothermal method below 170°C, 0.8 MPa. XRD pattern and cell parameters-composition figures of these prepared powders demonstrated that they are completely miscible solid solutions based on BaTiO₃. Furthermore, TEM showed that they have a shape of uniform, substantially spherical particles with an average particle size of 70 nm in diameter. The sintered ceramics of those powders doped by Sr²⁺ and Zr⁴⁺ or Zn²⁺ and Sn⁴⁺ have dielectric constant twelve times higher than and dielectric loss 1/6 those of pure BaTiO₃ phase at room temperature.     

Application of Nanosized Cu0.5Co0.5Fe2O4 Spinel Ferrite as a Nanocatalyst in the Synthesis of 14‐Aryl‐14H‐dibenzo[a,j]xanthene Derivatives under Solvent‐free Conditions

Copper and cobalt substituted spinel ferrites Cu_1‐xCo_xFe₂O₄ (0≤X≤1) have been synthesized by using hydrothermal method. The resultant spinel ferrites were systematically characterized by different techniques such as X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FT‐IR). It was indicated that all the resultant spinel ferrites obtained by the hydrothermal method had the single‐phase crystalline. The resultant spinel ferrites were employed in the synthesis of 14‐aryl‐14‐H‐dibenzo[a,j]xanthene derivatives. It was found that the nanocatalyst Cu_0.5Co_0.5Fe₂O₄ displays the best performance in the synthesis of 14‐aryl‐14H‐dibenzo[a,j]xanthenes. The catalyst was reused several times without significant loss of its activity for the preparation of desired product. In addition high yields of the products, solvent‐free conditions and reusability of the catalyst are other worthwhile advantages of the present study.     

Color Tuning in Garnet Oxides: The Role of Tetrahedral Coordination Geometry for 3 d Metal Ions and Ligand–Metal Charge Transfer (Band‐Gap Manipulation)

We explored garnet‐structured oxide materials containing 3d transition‐metal ions (e.g., Co²⁺, Ni²⁺, Cu²⁺, and Fe³⁺) for the development of new inorganic colored materials. For this purpose, we synthesized new garnets, Ca₃Sb₂Ga₂ZnO₁₂ ( I ) and Ca₃Sb₂Fe₂ZnO₁₂ ( II ), that were isostructural with Ca₃Te₂Zn₃O₁₂. Substitution of Co²⁺, Ni²⁺, and Cu²⁺ at the tetrahedral Zn²⁺ sites in I and II gave rise to brilliantly colored materials (different shades of blue, green, turquoise, and red). The materials were characterized by optical absorption spectroscopy and CIE chromaticity diagrams. The Fe³⁺‐containing oxides showed band‐gap narrowing (owing to strong sp–d exchange interactions between Zn²⁺ and the transition‐metal ion), and this tuned the color of these materials uniquely. We also characterized the color and optical absorption properties of Ca₃Te₂Zn_3−x Co_x O₁₂ (0<x ≤2.0) and Cd₃Te₂Zn_3−x Co_x O₁₂ (0<x ≤1.0), which display brilliant blue and green‐blue colors, respectively. The present work brings out the role of the distorted tetrahedral coordination geometry of transition‐metal ions and ligand–metal charge transfer (which is manifested as narrowing of the band gap) in producing brilliantly colored garnet‐based materials.     

Synthesis and Structure Analysis of Aurivillius Phases Pb1‐xBi4‐+Ti1‐xMnxO15

Synthesis Pb_1‐xBi_4+xTi_4‐xMn_xO₁₅ compounds (0 ≤ × ≤ 1) were carried out by molten salts method using eutectic mixture of Na₂SO₄/K₂SO₄ salts (1:1 molar ratio) as the flux. The samples were characterized by X‐ray powder diffraction and refined by Le Bail method using Rietica program. The refinement results revealed that the compounds with the composition 0 ≤ x ≤ 0.6 formed Aurivillius phase with the space group A2₁am while the other composition (x ≥ 0.8) showed another phase beside A2₁am. The ratio b/a of the lattices constants for all the samples are larger than 1 indicating the direction of the orthorhombic along the b axis of their cells. The lattice parameters and volume of the unit cells decrease as the Mn content increasing from x = 0 to 0.6, for x ≥ 0.8 a second phase were observed. The morphologies of Pb_1‐xBi_4+xTi_4‐xMn_xO₁₅ samples were observed by SEM and show plate‐like aggregate crystals, typical of layered compounds belonging to the Aurivillius phase.     

Preparation of MnxNi0.5-xZn0.5Fe2O4 Nanorods by the Co-precipitation Method

Mn_xNi_0:5-xZn_0:5Fe₂O₄ nanorods were successfully synthesized by the thermal treatment of rod-like precursors that were fabricated by the co-precipitation of Mn²⁺, Ni²⁺, and Fe²⁺ in the lye. The phase, morphology, and particle diameter were examined by the X-ray diffrac-tion and transmission electron microscopy. The magnetic properties of the samples were stud-ied using a vibrating sample magnetometer. The results indicated that pure Ni_0:5Zn_0:5Fe₂O₄ nanorods with a diameter of 35 nm and an aspect ratio of 15 were prepared. It was found that the diameter of the Mn_xNi_0:5-xZn_0:5Fe₂O₄ (0≤x≤0.5) samples increased, the length and the aspect ratio decreased, with an increase in x value. When x=0.5, the diameter and the aspect ratio of the sample reached up to 50 nm and 7～8, respectively. The coercivity of the samples first increased and then decreased with the increase in the x value. The coer-civity of the samples again increased when the x value was higher than 0.4. When x=0.5,the coercivity of the Mn_xNi_0:5-xZn_0:5Fe₂O₄ sample reached the maximal value (134.3 Oe)at the calcination temperature of 600 oC. The saturation magnetization of the samples first increased and then decreased with the increase in the x value. When x=0.2, the satura-tion magnetization of the sample reached the maximal value (68.5 emu/g) at the calcination temperature of 800 oC.