Rubidium-conducting solid electrolytes in Rb2 ? 2xFe2 ? xVxO4 system

New solid rubidium-conducting electrolytes based on rubidium monoferrite in the system of Rb_{2 − 2x} Fe_2−x V _x O₄ are synthesized and studied. It is found that introduction of V⁵⁺ ions causes a drastic decrease in the electronic conductivity component prevalent in pure RbFeO₂ with a simultaneous increase in the ionic conductivity. The latter becomes predominant at an increase in the concentration of vanadium. The optimum compositions of the studied electrolytes feature a very high cationic rubidium conductivity (∼1.8 × 10⁻² S cm⁻¹ at 200°C, more than 10⁻¹ S cm⁻¹ at 700°C). The results are compared with the data obtained earlier for similar systems based on RbGaO₂ and RbAlO₂.     

Cationic mobility in Li3?2xNbxFe2?x(PO4)3 complex phosphates

Synthesis and ionic conductivity of Li_3−2x Nb _x Fe_2−x (PO₄)₃ complex phosphates were studied by X-ray powder diffraction and impedance spectroscopy. These phosphates are formed only at 900–1000°C. Variations in their thermal expansivity and unit cell parameters induced by aliovalent doping were characterized. The conductivity of these materials increases monotonically in the series Li_0.5Nb_1.25Fe_0.75(PO₄)₃-LiNbFe(PO₄)₃ and Li_1.2Nb_0.9Fe_1.1(PO₄)₃-Li₃Fe₂(PO₄)₃, which is explained by consecutive occupation of the Li(1) and Li(2) positions in their structures. Original Russian Text ? A.R. Shaikhlislamova, I.A. Stenina, A.B. Yaroslavtsev, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 12, pp. 1957–1962.     

Cation mobility in modified Li1 ? xTi2 ? xNbx(PO4)3 lithium titanium NASICON phosphates

Li_{1 − x} Ti_{2 − x} Nb _x (PO₄)₃ NASICON materials are prepared and studied by X-ray diffraction, ⁷Li and ³¹P NMR spectroscopy, and impedance spectroscopy. Vacancy mobility in Li_{1 − x} Ti_{2 − x} Nb _x (PO₄)₃ is lower than interstitial lithium mobility. Nb⁵⁺ cations with low doping levels increase cation mobility in LiTi₂(PO₄)₃. Original Russian Text ? I.Yu. Pinus, I.A. Stenina, A.I. Rebrov, N.A. Zhuravlev, A.B. Yaroslavtsev, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 8, pp. 1240–1244.     

Synthesis and X-ray diffraction study of complex oxides of the Zn2 ? x(ZraSnb)1 ? xFe2xO4 composition

A multicomponent system of complex refractory oxides of the composition Zn_{2 − x} (Zr _a Sn _b )_{1 − x} Fe_2x O₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 4: 1; x = 0−1.0; Δx = 0.05) was studied by X-ray diffraction. The samples were prepared from oxides of appropriate metals by low-temperature plasma synthesis (hydrogen-oxygen flame). Two phases with wide homogeneity ranges were identified: α phase crystallized in the crystal system of inverse cubic spinel and β phase with the structure of tetragonal spinel. The phase boundaries were found. Structural data are presented for about 100 solid solutions.     

Cation mobility in modified Li1 + xTi2 ? xGax(PO4)3 lithium titanium NASICON phosphates

Li_{1 +x} Ti_{2 − x} Ga _x (PO₄)₃(x= 0−0.2) NASICON double phosphates are prepared and studied by high-temperature X-ray diffraction, ⁷Li NMR spectroscopy, impedance spectroscopy, and calorimetry. Doping with Ga³⁺ cations increases cation mobility in LiTi₂(PO₄)₃. Ion conductivity, NMR spectroscopy, and calorimetry data imply the occurrence of a phase transition in LiTi₂(PO₄)₃ and in products of partial gallium-for-titanium substitution. Original Russian Text ? I.Yu. Pinus, I.V. Arkhangel’skii, N.A. Zhuravlev, A.B. Yaroslavtsev, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 8, pp. 1235–1239.     

Crystal structures of La1 ? xSr2 + x(GeO4)(V1 ? xMoxO4) (x= 0?0.4) solid solutions

The phase compositions of theLaVO₄-SrMoO₄(1) and Sr₂GeO₄-SrMoO₄ (2) binary systems, which bound the Sr₂GeO₄-LaVO₄-SrMoO₄ (3) ternary system, and the LaSr₂(VO₄)(GeO₄)-Sr₂GeO₄+SrMoO₄ section (4) of system 3 are studied at subsolidus temperatures. Systems 1 and 2 consist of a mixture of the initial compounds, and the La_{1 − x} Sr_{2 + x} (GeO₄)(V_{1 − x} Mo _x O₄) (where 0 ≤ x ≤ 0.4) region of substitutional solid solutions with a palmierite structure is formed in system 3. The unit cell parameters of the solid solutions are determined. The distribution of the lanthanum and strontium cations over two positions of the cationic sublattice is described. Original Russian Text ? V.D. Zhuravlev, V.G. Zubkov, A.P. Tyutyunnik, Yu.A. Velikodnyi, N.D. Koryakin, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 135–137.     

Crystal Structure of [Co?6H2O][Co?4H2O?2Gly]?2SO4

The crystals of [Co6H₂O][Co4H₂O2Gly]2SO₄ were studied by X-ray diffraction analysis (triclinic, P , a = 5.975(5), b = 15.469(5), c = 6.765(5) , =120.71(5), =83.23(5), =98.77(5)°). The structure contains complex cations of two types: [Co6H₂O]²⁺ and [Co4H₂O2Gly]²⁺ and SO ₄ ^2– anions linked by hydrogen bonds and electrostatic forces. Three chemically nonequivalent charged layers can be distinguished in the structure: one layer is formed by cobalt hexaaqua complexes, another by [Co4H₂O2Gly]^2– complexes, and the third layer consists of sulfate anions interlaying the former two. The layers alternate along the b axis and are connected by a 3D system of hydrogen bonds.     

H2O、CO2组分对NOx存储-还原性能的影响

NOx存储-还原技术是控制汽车稀燃NOx排放的重要手段之一,在汽车尾气中H2O、CO2组分含量均相对较高,有必要弄清这些组分对NOx存储-还原特性的影响。论文以MnOx改性Pt/Ba/Al2O3催化剂为研究对象,评价在不同气氛下的NOx存储能力和催化还原性能。结果表明：CO2、H2O组分均抑制催化剂的NOx存储性能,H2O的抑制作用主要表现在低温区,CO2抑制NOx存储的现象在高温区更为显著。CO2对NOx存储速率的抑制作用较H2O更为明显,且其NOx存储速率随着温度的升高表现的差异性更为明显。对于NOx催化还原过程,CO2、H2O或CO2 H2O添加均导致N2选择性降低,其N2选择性按CO2 > H2O > CO2 H2O的顺序降低。     

Structure and luminescence of [Tb0.5(C6NO2H5)3(H2O)2]2n·(H3O)4n(ZnCl5)n(ZnCl4)2n

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb_0.5(C₆NO₂H₅)₃(H₂O)₂]_2n ·(H₃O)_4n (ZnCl₅) _n (ZnCl₄)_2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.     

新型三维超分子化合物{[Co(H2bptc)(ptcp)(H2O)2]·H2O}n的水热合成和晶体结构

A novel cobalt(Ⅱ) complex with biphenyl-3,3′,4,4′-tetracarboxylic acid (H₄bptc) and 2-phenyl-1,3,7,8-tetraazacyclopenta[l]-phenanthrene (ptcp), {[Co(H₂bptc)(ptcp)(H₂O)₂]·H₂O}_n(1), has been synthesized by hydro-thermal method and was characterized by elemental analysis, single crystal X-ray diffraction and thermal gravimetry (TG). It crystallizes in monoclinic, space group Pn with a=0.719 44(14) nm, b=1.259 4(3) nm, c=1.681 9(3) nm, β=93.30(3)°, V=1.521 5(5) nm³, Z=2, C₃₅H₂₆CoN₄O₁₁, M_r=737.53, D_c=1.610 g·cm^-3, μ(Mo Kα)=0.639 mm^-1, F(000)=758, S=1.024, R₁=0.076 7 and wR₂=0.120 6. The structural analyses reveal that the title complex is a 1D zigzag chain strcture along the c axis, which is stacked to furnish a three-dimensional supramolecular net structure via hydrogen bonding interactions. CCDC: 793796.     

Online NMR spectroscopic study of species distribution in MEA–H2O–CO2 and DEA–H2O–CO2

Quantitative online NMR spectroscopy was used for studying the species distribution in solutions of carbon dioxide in aqueous monoethanolamine (MEA) and diethanolamine (DEA). The mass fraction of the amine in the unloaded solution was 0.2 and 0.3 g/g, respectively, the carbon dioxide loading was up to 1.1 ??molCO₂/molamine$1.1\text{\hspace{0.17em}??}\text{mo}{\text{l}}_{\text{C}{\text{O}}_2}/\text{mo}{\text{l}}_{\text{amine}}$, temperatures were between 293 and 353 K. A special apparatus was designed that allows preparing the mixtures gravimetrically and applying pressures up to 25 bar to keep the carbon dioxide in solution. It was coupled to a 400 MHz NMR spectrometer by heated capillaries. By using both ¹H and ¹³C NMR spectroscopy quantitative information on the concentrations of the following species were obtained: amine, carbamate, bicarbonate, and carbon dioxide. Due to the fast proton transfer between molecular and protonated amine, only the sum of their concentrations can be determined. Furthermore, a byproduct, 2-oxazolidone, was observed and quantified. The experimental data were used for developing a thermodynamic model of the studied electrolyte solutions based on the extended Pitzer G^E-model. In the model development, also vapor–liquid equilibrium data from the literature were included. The model gives reliable results both for the species distribution and the vapor–liquid equilibrium of the studied mixtures.     

[{Zn(3-SBA)(2，2′-bipy)(H2O)2}·H2O]n的合成和晶体结构研究

A novel coordination ploymer [{Zn(3-SBA)(2,2′-bipy)(H₂O)₂}·H₂O]_n was synthesized by the hydrothermal reaction of 3-Na₂SBA, ZnSO₄·7H₂O and 2,2′-bipy. The structure was characterized by elemental analysis, IR and single crystal X-ray diffraction. The title coordination ploymer crystallized in monoclinic with space group P2₁, a=0.803 42(18) nm, b=1.501 8(3) nm, c=0.821 13(19) nm, β=109.350(4)°. The coordination polymer has an infinite chain structure and its luminescent property has also been studied. CCDC: 282746.     

一维链状配位聚合物{[Cu(H2bttc)(H2O)3]·3H2O}n的非等温反应动力学和晶体结构

为研究配位聚合物{[Cu(H₂bttc)(H₂O)₃]·3H₂O}_n(H₂bttc=1，2，4，5-benzenetetracarboxylate)的热分解机理和非等温反应动力学进行了DSC和TG-DTG热分析。由热分析结果和FTIR光谱推测了其热分解机理；将Kissinger法、Ozawa法、积分法和微分法得到的动力学参数进行比较确定了第一个失重过程最可能的动力学模型函数。配位聚合物的X射线单晶结构分析表明它由 [Cu(H₂bttc)(H₂O)₃]_n分子链组成，并有客体水分子通过分子间氢键附着在分子链上。这一结构特点与热分析结果相一致。还有一种氢键将分子链连接起来形成二维框架，这一框架在失去配位水和结晶水后到553 K开始分解。     

Synthesis and structures of nine-coordinate K[SmIII (Edta)(H2O)3] · 2H2O and Ten-Coordinate K2[SmIII(Pdta)(H2O)2]2 · 4.5H2O complexes

The title complexes, K[Sm^III(Edta)(H₂O)₃] · 2H₂O(I)(H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and K₂[Sm^III(Pdta)(H₂O)₂]₂ · 4.5H₂O (II) (H₄Pdta = propylenediamine-N,N,N′,N′-tetraacetic acid), were prepared and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. Complex I has a mononuclear structure, and the Sm³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.84(5), b = 35.58(9), c = 12.15(3) ?, V = 8580(38) ?³, Z = 16, ρ _c = 1.925 g/cm³, μ = 3.010 mm⁻¹, F(000) = 4976, R = 0.0252, and wR = 0.0560 for 3510 observed reflections with I ≥ 2σ(I). Complex II has a binuclear structure and the Sm³⁺ ion is ten-coordinated by a Pdta ligand, two oxygen atoms from a carboxylic group of adjacent Pdta ligand and two water molecules, yielding a distorted bicapped square antiprismatic prism. The complex crystallizes in the triclinic crystal system with space group P $ \bar 1 $ \bar 1 . The crystal data are as follows: a = 8.9523(15), b = 10.7106(15), c = 11.6900(19) ?, α = 80.613(5)°, β = 80.397(5)°, γ = 76.530(4)°, V = 1065.7(3) ?³, Z = 1, ρc = 1.970 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I).     

Synthesis and study of the properties of K2Y1 ? x ? yEuxTby(MoO4)(PO4) and K2Y1 ? x ? yEuxTby(MoO4)(PO4)1?δ(VO4)δ solid solutions

Al synthesized samples are isostructural and crystallize in the orthorhombic symmetry system, space group Ibca. Particles of the final product of ∼200 nm in size have been obtained. The introduction of the vanadate anion into the matrix composition leads to the lowering of the symmetry of the Eu³⁺ environment and to the rise of the defect luminescence at 450–550 nm because of the unit cell distortion. The luminescence of defects in terbium-europium-containing samples is determined by the sample surface area, which decreases on annealing. The τ, W ₀ and γ parameters of the luminescence kinetics of the samples have been determined.     

Hydrothermal Synthesis and Structural Characterization of a Tubular Arsenic-Vanadate: [CoII(2,2′-bpy)2]2[AsIII8VIV14O42(H2O)]·H2O

The hydrothermal reaction of VOSO₄, As₂O₃, CoC₂O₄·2H₂O and 2,2-bipy yields a novel arsenic-vanadate [Co^II(2,2-bpy)₂]₂[As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O (1), which is characterized by IR, elemental analysis, TGA, magnetic susceptibility and single crystal X-ray diffraction analysis. X-ray diffraction shows that compound 1 is the first example of tubular arsenic–vanadium cluster containing infinite {[Co(2,2-bpy)₂]₂[As₈V₁₄O₄₂(H₂O)]} chain constructed from [As₈V₁₄O₄₂(H₂O)] clusters interconnected through [Co(2,2-bpy)]²⁺ units. Crystal data: 1, orthorhombic, P 2₁2₁2₁, a=12.1401(2) Å, b=15.8722(1) Å, c=39.9533(5) Å, Z=4.Graphical Abstract: A novel polyoxoarsenicvanadate, [Co^II(2,2-bipy)₂]₂ [As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O, is depicted along with a tubular hybrid solid with a rhombic tube formed within the chain.     

一维链状配位聚合物[Cu3(TFSSB)2·(H2O)4·4H2O]n的合成和晶体结构

The title complex [Cu₃(TFSSB)₂·(H₂O)₄·4H₂O]_n (TFSSB=taurine 3-formylsalicylic schiff base) was synthesized by TFSSB and copper(Ⅱ) acetate monohydrate in ethanol solution and the crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic system, space group P2₁ / n，with cell parameters: a=0.927 9(6) nm, b=1.173 0(2) nm, c=1.471(2) nm, β=106.96(2)°, and V=1.531(2) nm³, Z=2, D_c=1.890 g·cm^-3, μ=2.291 mm^-1, F(000)=882, R₁=0.025 9, wR₂=0.065 9. The Cu1 is five-coordinate, the Cu2 is four-coordinate. CCDC: 253298.     

Catalytic activity of V-substituted Cs2Te0.2H0.6 + xPMo12 ? xVxOn heteropoly compounds in selective oxidation of isobutane

A series of Cs₂Te_0.2H_{0.6 + x} PMo_{12 − x} V _x O _n (x = 0–3) heteropoly compounds has been prepared and tested in the partial oxidation of isobutane. Catalytic tests show that at 350°C very high selectivity to methacrylic acid (60.1%) can be achieved at isobutane conversion of 12.2% over a Cs_2.0Te_0.2H_1.6PMo₁₁VO _n catalyst with only one molybdenum atom per unit cell substituted by vanadium. The presence of Te⁴⁺ in the heteropoly compounds appears to interfere with the dehydrqgenation step and favor the formation of methacrolein and methacrylic acid.     

{[Cd(sulfadiazine)2]n [Cd(sulfadiazine)2·H2O]n}(英)

C om m ent Silver and zinc salts of sulfadiazine are widely used to prevent bacterial infection for both hum ans and anim als during burn treatm ents[1~4]. Because the slow release of the m etal ions highly relevant to the biologicalactivity ofthese polym…     

The enthalpies of formation of Sm1 + xBa2 ? xCu3Oy substitution solid solutions

The enthalpies of reactions of Sm_{1 + x} Ba_{2 − x} Cu₃O _y substitution solid solutions (x = 0, 0.1, 0.2, 0.3, 0.7, and 0.8) with 1.07 N HCl were measured at 298.15 K in a hermetic isothermic-shell swinging calorimeter. The results and the literature data were used to calculate the standard enthalpies of their formation from simple substances and binary oxides (Δ_f H _298.15^o and Δ_ox H _298.15^o). The dependence of the enthalpy of formation on the degree of samarium substitution for barium was obtained.