Preparation and electrical conductivity of thin films of Rb4Cu16I7Cl13

A thin film of the copper ion conductor Rb₄Cu₁₆I₇Cl₁₃ was prepared on a glass plate by vacuum evaporation. An appropriate thin film was obtained by controlling the amount of the electrolyte mounted in a boat, the evaporation time etc. and by heating the deposited film at a temperature between 130 and 210° C. The electronic and ionic conductivities of the film measured by d.c. and a.c. techniques were nearly equal to those of a dense tablet of the solid electrolyte.     

An investigation of the solid-state cell Cu/Rb4Cu16I7Cl13/CuxTiS2

The solid electrolyte cell Cu,Z/Z/Cu_xTiS₂,Z, graphite (Z=Rb₄Cu₁₆I₇Cl₁₃) was investigated in a search for a cell with high and stable open circuit voltage (OCV). The cells Cu/Cu_x Tis₂ (x=0 and 0.3–0.5) showed only a small reduction in OCV values over 200 days. The cause of the slight decrease of OCV was discussed from the viewpoint of degradation of the cell-component materials. Polarization curves and constant load discharge curves were obtained to indicate that the cathode polarization was predominant and that Cu_xTiS₂ of 0.3x0.5 performed well, as did TiS₂.     

[Mn（IMI）6]（ClO4）2的合成、晶体结构及感度

利用咪唑的水溶液和高氯酸锰水溶液反应制备高氯酸六咪唑合锰(II),培养出该配合物的单晶.用元素分析、红外光谱、DSC、TG-DTG和X射线单晶衍射等方法对该化合物进行了表征.结果表明,该晶体属于单斜晶系,空间群为P2(1)/n,晶胞参数a=11.721(2) nm, b=7.2191(13) nm, c=16.402(3) nm, β=90.064(3)°,V=1387.9(4) nm~3; Dc=1.585 g/cm~3; Z=2;F(000)=678, μ=0.160 mm, R_1=0.036 7, ωR2_=0.137 2.该化合物的分子式为[Mn(IMI)_6](ClO_4) _2,是由6个咪唑分子直接与二价锰离子配位、与高氯酸根离子结合形成的配合物.热分析结果表明,在10 K/min的升温速率下,该配合物的热分解过程由1个吸热峰和1个放热峰组成,剩余残渣量在9.9%左右.感度测试结果表明,该配合物为不敏感型的含能配合物.     

Cu(NH3)2(FOX-7)2的晶体结构和热行为

用l,1-二氨基-2,2-二硝基乙烯的钾盐[K(FOX-7)·H2O]和硝酸铜在氨水体系中合成了Cu( NH3)2(FOX-7)2,并培养得到了单晶.该晶体为单斜晶系,空间群P21/c,a=0.68818(7)nm,b=O.73083 (8) nm,c=1.319 66(14)nm,β=95.986°,V=0.6600...     

2, 4, 6-三硝基氯苯的表征及晶体结构

从丙酮溶液中培养了2,4,6-三硝基氯苯(TNCB)的单晶,通过元素分析、红外光谱分析和X-射线单晶衍射分析对TNCB进行了结构表征,属于单斜晶系,P2(1)/c空间群,a=1.2501(1) nm, b= 0.6803(1) nm, c=1.1038(1) nm, β= 102.842(9)°, V= 0.91526(15) nm3, Z=2, Dc = 1.797 g/cm3, μ(MoKα)=0.438 /mm, F(000)=496, R1= 0.0395, ωR2= 0.0991.     

FOX-7的晶体结构和热分解特性

以2-甲基-4,6-嘧啶二酮为原料,通过硝化、水解反应,合成出1,1-二氨基-2,2-二硝基乙烯(FOX-7),产率为85.1%,并用元素分析、红外、质谱、核磁进行表征.以乙腈为溶剂培养得到了FOX-7单晶,用X射线单晶衍射仪测定晶体结构.结果表明,晶体属单斜晶系,空间群为P21/n.晶体学参数为:a=0.693 0(14) nm, b=0.663 0(13) nm, c=1.136 0(2) nm,β=90.43(3)°,V=0.521 9(18) nm3, Z=4, Dc=1.885 g·cm-3,μ=0.179 mm-1, F(000)=304.用DSC和TG-DTG技术研究了热分解过程. 结果表明, FOX-7分解由一个吸热和两个放热过程组成, 吸热峰由晶型转变引起, 放热峰由分解所致; TG曲线由两个失重过程组成;较高的分解温度表明FOX-7有较好的热稳定性.     

The Crystal and Molecular Structure of Ethyl p-Chloro α-Cyano-β-Methyl-Cis-Cinnamate,C13H12No2Cl

Crystals of ethyl p-chloro α-cyano-β-methyl-cis-cinnamate, C₁₃H₁₂NO₂Cl, are orthorhombic, space group Pbcn, with eight molecules per unit cell, a = 17.31, b = 8.68 and c = 17.20 Å. The structure was solved by direct methods and refined subsequently by Fourier techniques. The benzene ring makes a dihedral angle of 60.0° with the ethylenic group. This suggests significant steric effects of the β-methyl group and of the carbonyl group on the orientation of the benzene ring. The conformation of the ethylene bond and the carbonyl group around the C_α? C bond is roughly cisoid and the angle of twist is 16.5°. Nearest-neighbour >C = C <groups make contact across a two-fold axis at a center-to-center distance of 4.33 Å.     

Hydration of calcium chlorosilicate Ca3SiO4Cl2

The investigations of the hydration of the calcium chlorosilicate have shown that this phase dissolves congruently. However, unlike in the case of calcium orthosilicate, a high content of silica is retained in the solution. The dissolution process proceeds at first rather slowly and after 60 minutes its rate becomes considerably increased. On the calorimetric curve this corresponds to a short induction period. After 2 hours the hydrates are already detectable by X-ray examination. They are for H₂O/dry sample = 10, CSH and CH, and for H₂O/dry sample ratio = 1, CSH, CaCl₂CHH and CH. An addition of the SiO₂ gel or CSH phase considerably accelerates the process, reducing simultaneously the induction period. Under these conditions the hydrates are detectable by X-ray examination after 1 hour. It is probable that the induction period occuring in the hydration of chlorosilicate is due to the nucleation of the CSH phase.     

草酸钴、氯化钴、钴酸锂中铁的测定

对电子化工原料及产品草酸钴、氯化钴、钴酸锂中的铁进行测定,基体中高含量的钴对铁(约0.001%)的测定造成了干扰.用乙酸乙酯萃取其中的铁,采用邻菲罗林光度法测定,测定结果相对标准偏差1.46%～2.69%,加标回收率98.49%～98.82%.方法简便、快速,目前已应用于实际工作中.     

Synthesis,Crystal Structure,and Luminescence Properties of Y4Si2O7N2: Eu2+ Oxynitride Phosphors

Y₄Si₂O₇N₂: Eu²⁺ phosphor has been prepared by a pretreatment method. Reduction in Eu³⁺ ions into Eu²⁺ by the use of hydrogen iodide (HI) is verified by X‐ray absorption near‐edge structure (XANES) and electrode potential analysis. Y₄Si₂O₇N₂: Eu²⁺ phosphor has a broad emission band in the range of 400–500 nm. Furthermore, the effect of Zr doping on the structure and luminescence properties of Y₄Si₂O₇N₂: Eu²⁺ phosphor is researched. It found that the Zr doping leads to an emission blueshift, and improves the luminescence intensity and thermal quenching behavior of Y₄Si₂O₇N₂: Eu²⁺ phosphors. Prospectively, the pretreatment approach could be extended to develop other Eu²⁺‐doped compounds.     

Tuning Mn4+ Red Photoluminescence in (K,Rb)2Ge4O9:Mn4+ Solid Solutions by Partial Alkali Substitution

We report on intense photoluminescence from materials of the (Rb,K)₂Ge₄O₉:Mn⁴⁺ solid solution as a novel class of red‐emitting oxide phosphors. In these compounds, luminescence originates from a virtually ideal substitution of Mn⁴⁺ for Ge⁴⁺ on octahedral lattice sites which are well‐isolated from each other within the unit cell by intermediate GeO₄ species. Complete isostructural substitution of K for Rb is possible across the join. The associated slight shrinkage of the unit cell has only little effect on the apparent Mn⁴⁺ interionic distance, but enables tuning of the absorption cross section and of the band structure, hence, of the emission lifetime, of the excitation band shape, and of emission quantum yield. Partial substitution was also found to reduce thermal quenching of the Mn⁴⁺‐related emission, apparently due to the lower polarizability of the K⁺ ion. In addition, random substitution of Rb by K enables modulation of the interaction of Mn⁴⁺ with its surrounding field at lower symmetry, leading to increasing emission bandwidth, i.e., 595 cm^?1 in K_1.5Rb_0.5Ge₄O₉:Mn⁴⁺ vs 558 or 578 cm^?1 in Rb₂Ge₄O₉:Mn⁴⁺ or K₂Ge₄O₉:Mn⁴⁺ respectively.     

Comparison of multi-valent manganese oxides (Mn4+, Mn3+, and Mn2+) doping in BiFeO3-BaTiO3 piezoelectric ceramics

Different manganese oxides-doping effects were compared in piezoceramic BiFeO₃-BaTiO₃ system. 0.67Bi_1.05(Fe_0.99Mn^x_0.01)O₃-0.33BaTiO₃ (valence state x = 4+, 3+, and 2+) ceramics were prepared via a solid-state reaction process followed by furnace-cooling (FC) or water-quenching (WQ) process. For the FC ceramics, the direct piezoelectric sensor coefficient (d₃₃) was almost independent of valence state of doped Mn, while d₃₃ depended on the fraction of Fe³⁺/Fe²⁺ in WQ ceramics. The d₃₃ value was highest for the donor Mn⁴⁺-doped ceramic, among the FC ceramics, with 175 pC/N. However, acceptor-doping with Mn²⁺ prevented the transition of Fe ion valence state from 3+ to 2+ in the WQ ceramics, the Mn²⁺-doped WQ ceramic showed the largest d₃₃ of 313 pC/N and converse piezoelectric actuator coefficient, d₃₃^* of 352 pm/V, with high Curie phase transition temperature (482 °C).     

3-氨基吡嗪-2-羧酸镍配合物的合成与结构

以3-氨基吡嗪-2-羧酸(3-Hapzac)为配体合成了一个镍的配合物[Ni(3-apzac)_2(H_2O)_2],并利用元素分析、IR以及X射线单晶衍射等手段对配合物进行了表征。在配合物中,配位的水分子、羧基和与氨基都参与形成了氢键,通过强的氢键相互作用使配合物形成了三维超分子网络结构。     

Two Ferroeletric Mechanisms Confirmed in Ba5Ti2O7Cl4

The anticipated existence of two mechanisms of ferroelectricity in Ba₅Ti₂O₇Cl₄ is now confirmed by studying the variation of spontaneous polarization with temperature by hysteresis loop method, by observing the changes in domain structure, and by using thermoanalytical methods. It is found that at around 80°C the spontaneous polarization begins to fall off rapidly, and this fall continues upto 125°C after which the change in Ps is negligibly small. Also, 79°domains associated with Ti⁴⁺ ion begin to disappear at 80°C while 180° and 90° domains associated with Cl^1- ion persist beyond 200°C. Differential thermal analysis (DTA) and differential scanning calorimetry (DSC) data showed ionic changes at 80°C and 125°C. The dc conductivity measurements showed, however, no phase change in this temperature range. From the observed domain structure variation and Ps variation it is inferred that the ionic changes given by DTA and DSC relate to Ti⁴⁺ ion only. It is deduced that at 80°C there is change in Ti⁴⁺ displacement from [110] direction to [100] direction, while at 125°C the Ti⁴⁺ ion loses its off-center position resulting in the loss of ferroelectric mechanism associated with Ti⁴⁺ ion. Since 90° and 180° domain associated with Cl^1- ion continue to persist beyond 125°C, it is obvious that this ferroelectric mechanism continues to exist even as the other ferroelectric mechanism disappears at 125°C.     

一种新型铜配合物Cu_2(C_6H_8O_4)_2(C_3H_7NO)_2的合成和晶体结构

本文以苯并咪唑-5-羧酸、己二酸、硫酸铜为原料,以水/DMF(v/v 1:1)为溶剂,采用水热合成法合成了新型铜配合物Cu_2(C_6H_8O_4)_2(C_3H_7NO)_2单晶,并通过单晶衍射仪测定了晶体结构。该配合物属于为单斜晶系,空间群为P21/n,晶胞参数为:a=9.4764(5)?,b=8.2618(5)?,c=15.0990(8)?,β=106.259(1)o,V=1134.85(11)?3,Z=2。     

咪唑苦味酸盐C3N2H5＋C6N3O7H2^-的合成、晶体结构和量子化学

利用咪唑的醇溶液与苦味酸的醇溶液合成了咪唑的苦味酸盐C_3N_2H_5~+C_6N_3O_7H_2~-,并培养出单晶,通过X射线单晶结构分析法测定了其晶体结构.结果表明,晶体属于正交晶系,空间群为Pbca,晶胞参数为:a=0.895 0 nm,b=1.347 4(3)nm,c=2.016 4 nm,α=β=γ=90°,V=2.431 7(3) nm~3,D_c=1.624 g/cm~3,Z=8,F(000)=1 216.运用Gaussian 03程序,在6-311+G(d)的基组上,用HF和B3LYP两种方法对标题化合物进行了理论研究,并对原子净电荷及原子间布局进行了分析.     

CoCl2-FeCl3-膨胀石墨层间化合物制备

对CoCl2-FeCl3-膨胀石墨层间化合物(EGICs)的制备进行了探讨.结果表明保持其它制备条件不变,仅改变膨胀石墨(EG)与FeCl3的配比即可合成不同阶结构的EGICs;随着n(EG)∶n(FeCl3)增大,EGICs趋向于高阶,在一定配比下可合成纯阶样品;原料配比固定,提高反应体系的Cl2分压有利于制得纯净的EGICs.     

氢键配合物[Mn(H_2O)_2(HNic)_2]晶体的合成及结构表征

用3d金属离子锰与2-羟基-3-吡啶羧酸配体合成出新的水杨酸式螯合具有三维网络结构的Mn(H_2O)_2(HNic)_2配合物。均三苯甲酸苯环上一、三、五位置上的羧基都有脱质子化进行各种不同的结合,利用这点水溶液合成氢键配合物Mn(H_2O)_2(HNic)。我们采用常规分析方法即元素分析谱等,对配合物进行了表征.利用X-射线衍射晶体结构分析,结果显示该配合物属于单斜晶系,空间群为P2(1)/c,每一各晶胞包含两个Mn(H_2O)_2(HNic)_2分子,一个2-羟基-3-吡啶羧酸分子,通过N原子质子化的H原子与临近2-羟基-3-吡啶羧酸分子上的羟基上O原子又形成了一个八元环的氢键结构,该配合物具有复杂的氢键结构。     

Electrochemical behaviour of Mn3+/Mn2+, Co3+/Co2+ and Ce4+/Ce4+ redox mediators in methanesulfonic acid

The redox behaviour of Mn³⁺/Mn²⁺, Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ mediators commonly used in indirect oxidation of organic compounds were evaluated in methane sulfonic acid on a glassy carbon working electrode employing cyclic voltammetry. Manganic methanesulfonate exhibits higher instability in dilute methanesulfonic acid. The solid MnO₂ formed during disproportionation on the glassy carbon electrode further affects the reproducibility. Cobaltic methanesulfonate formation occurs only at oxygen evolution region rendering the overall oxidation process less efficient. Ceric methane sulfonate formation is highly efficient over a wide acid concentration range. Ceric methanesulfonate can also be employed over a wide temperature range to oxidize different aromatic compounds.