An extended open framework based on disordered [Nb6Cl9O3(CN)6] cluster units: Synthesis and crystal structure of Cs3Mn[Nb6Cl9O3(CN)6]0.6H2O

The synthesis and crystal structure of Cs₃Mn[Nb₆Cl₉O₃(CN)₆]0.6H₂O are described in this work. It crystallizes in the cubic system (space group Fm-3m; a=15.708(5) Å) and is characterized by a static orientational disorder of the [Nb₆Cl₉O₃(CN)₆]⁵⁻ cluster units. It results in a framework structurally related to that encountered in the well known Prussian Blue family prepared for different hexacyanometallates. The charge of the framework is compensated by cesium cations that are located in the tetrahedral cavities of the c.f.c. lattice of units along with water molecules. We will evidence the features that act in the crystallization of solid state compounds built up from ordered or disordered units as well as the influence of orientational disorder on interatomic distances obtained from single-crystal X-ray diffraction investigations.     

Isolation and single crystal study of [Nb2(μ-OMe)2(OiPr)8]. Can alcohol interchange provide the homoleptic niobium isopropoxide?

Niobium isopropoxide, Nb(OⁱPr)₅, is an attractive precursor of simple and complex niobium oxides in sol-gel technology. This compound cannot, unfortunately, be obtained by alcohol interchange starting from linear chain homologues such as Nb(OMe)₅ or Nb(OEt)₅. The equilibrium in the latter reaction favours formation of mixed-ligand complexes, [Nb₂(OR)₂(OⁱPr)₈], R = Me, Et. In particular, [Nb₂(OMe)₂(OPrⁱ)₈] (1) has been isolated in high yield from repeated treatment of Nb₂(OMe)₁₀ with excess of isopropanol. The X-ray single crystal study reveals a dinuclear structure containing a pair of edge-sharing octahedra with methoxide ligands in the bridging position. Infrared (IR) and mass spectroscopy (MS) studies confirmed the incomplete ligand substitution. The ¹H-NMR spectra suggest equilibrium between different molecular forms in solution. Solvothermal interaction of 1 with La chips in toluene/isopropanol media results in formation of a mixture of LaNb₂(OⁱPr)₁₃ and La₂Nb₄(μ₄−O)₄(OH)₂(μ−OⁱPr)₈(OⁱPr)₈ (2). Electronic Supplementary Material The online version of this article (doi: ) contains supplementary material, which is available to authorised users.     

碱性水溶液中4Na2SO4·2H2O2·NaCl的分解动力学

以低浓度(30(wt)%)的双氧水制备了硫酸钠-过氧化氢-氯化钠加合物,各组分的含量均接近于理论值,其纯度为99.3%;在323K和333K下,研究了4Na2SO4*2H2O2*NaCl于碱性水溶液中的分解动力学.结果表明,在不同条件下,其分解均为一级反应;随着温度和pH的增加,其分解速率加快.置信水平为95%时k和C0的联合置信域均为椭圆形且面积较小,求得的参数精确度较高;优化出的模型能较准确地描述4Na2SO4*2H2O2*NaCl于碱性水溶液中的分解过程.     

聚乙烯醇重氮衍生物-聚甲基丙烯酸高分子复合物固定酶的制备和性质的研究

本文用聚乙烯醇缩对苯甲醛氯化重氮物和聚甲基丙烯酸复合物作为载体,制备了固定化纤维素酶和葡萄糖氧化酶。此固定化酶有较高的活性,贮存、反应稳定性和热稳定性比固定化前都有较大提高。     

二水合二氯化-氯四水二(2,2''-联吡啶-N,N''-二氧化物)合钕(Ⅲ)的合成、表征与结构

在无水乙醇中合成出2,2′-联吡啶-N,N′-二氧化物与氯化钕形成的配合物单晶Nd(bipyO₂)₂Cl₃·6H₂O.通过元素分析、红外光谱、差热、热重分析等对该晶体进行了组成及性质鉴定.X射线结构分析表明、该配合物晶体属单斜晶系,空间群为C_2/C.晶胞参数a=17.456Å,b=7.491Å,c=21.078Å,α=γ=90°,β=100.66°,V=2708.9ų.Nd³⁺离子与两个bipyO₂,四个H₂O分子和一个Cl^-离子形成配位数为九的配阳离子,其中Nd-O(bipyO₂)平均键长为2.511A,Nd-O(H₂O)平均键长为2.500Å,Nd-Cl键长为2.899Å。     

Analysis of degradation mechanism of plasticized PVC under artificial aging conditions

A plasticized poly(vinyl chloride) (PVC) has the advantage of low cost, long-term stability and flame resistance among other commodity plastic, and has been in service as a product in railway field. However, the transition of the plasticizer concentration through the degrading condition and its relationship with the mechanical properties, the molecular motion, the appearance of surface and other properties was not clear. These relationships were studied by means of Rheovibron, pulse NMR, GC/MS, GPC, SEM and other methods. The bulk properties show similar change between weathering and thermal aging. In addition, the molecular chain was little influenced, however, the plasticizer concentration shows obviously different transition through each phase of aging conditions. According to the results of the observation of surface and section, different appearances between weathering and thermal aging were indicated and these appearances closely relate to the bulk properties. In conclusion, through the weathering condition, a stepwise flow out of inorganic components and plasticizer was presumable to be a main mechanism of the degradation. On the other hand, through the thermal aging condition, the rearrangement and aggregation of the molecular chain by the annealing effect were conceivable as the main mechanism of the degradation.     

Synthesis of Ethyl Methyl Carbonate by Homogeneous Catalysis 均相催化合成碳酸甲乙酯

 利用碳酸二甲酯和碳酸二乙酯进行酯交换反应制备了碳酸甲乙酯,并考察了Ti(OBu)4,Ti(OPh)4,Bu2SnO和BuSnCl3在这一反应中的催化性能. 结果表明,这些催化剂对该反应都有较好的催化性能. 其中,Bu2SnO的催化性能最好,在103 ℃下反应3 h时,碳酸甲乙酯的收率可达45.6%. 提出了Bu2SnO催化剂对碳酸二甲酯与碳酯二乙酯酯交换反应的可能机理.     

低价钛引起的酰氯与脂肪酮的还原偶联反应

在低价钛(TiCl4-Zn)试剂作用下, 酰氯与两分子脂肪酮发生分子间交叉还原偶联反应生成烯烃3。     

阴极限制型Li／SOCl2电池过放电产物的热分析

Li/SOCl_2电池体系以其高比能量和优异的放电性能引起了电源界的重视。有关该体系的不安全行为曾有一些研究。本文用DSC、EDAX、XPS等方法分析了电池的反应产物和热敏性,和模拟组分对比,以图找出引起电池热失控爆炸的原因。     

选矿流程样品中铌和钍的X射线荧光光谱法测定

采用Ｘ射线荧光光谱法，以铑靶的康普顿散射线强度为内标，测定了铁矿石选矿流程样品中的铌和钍。方法简便、快速、准确，完全能够满足选矿工艺研究和日常生产对样品中铌和钍分析的要求。