惰性配合物在铂族金属分离和测定中的应用

介绍了铂族金属在形成各种配合物时不同的动力学性质，评述惰性配合物在铂族金属分离和测定中的应用。     

Thermal decomposition kinetics and lifetime of the complex of Tb2（BA）6（PHEN）2

The thermal behavior of Tb2(BA)6(PHEN)2 (BA: benzoate, and PHEN: 1,10-phenanthroline) in a static air atmospbere was investigated by TG-DTG, SEM and IR techniques. By the kinetic method of processing thermal analysis data put forward by Malek et al., it is defined that the kinetic model for the first-step thermal decomposition is SB(m, n). The activation energy E for this step reaction is 99.07 kJ/mol, the entropy of activation ΔS^≠ is -84.72 J/mol, the enthalpy of activation ΔH^≠ is 94.26 kJ/mol, the free energy of activation ΔG^≠ is 144.77 kJ/mol and the pre-exponential factor lnA is 20.93.The lifetime equation at mass-loss of 10% was deduced as lnτ = -29.0312 19760.83/T by isothermal thermogravimetric analysis.     

8-羟基喹啉-N-氧化物和5,7-二硝基-8-羟基喹啉-N-氧化物与Au(Ⅲ)、Pd(Ⅱ)的配合物之合成

合成4种标题配合物,用元素分析、红外和紫外光谱、摩尔电导、核磁共振氢谱、荧光光谱及X射线粉末衍射物相分析研究了它们的组成和性质及其结构。按结构将配合物分为两类,一是含氢键的离子缔合物;一是含金属—氧键的螯环型配合物。     

螺旋藻多糖铁配合物制备、抗氧化及淋巴细胞增殖活性分析

以三氯化铁为原料,通过络合反应,对螺旋藻多糖(SP)进行结构修饰,制得有机铁化合物〔螺旋藻多糖铁(Ⅲ)配合物SP-Fe(Ⅲ)〕。采用FTIR、DSC、TGA、XRD和SEM对其结构进行了表征,采用DPPH(1,1-二苯基-2-三硝基苯肼)自由基法、羟自由基法等5种方法和MTT(四唑盐)法分析了SP和SP-Fe(Ⅲ)的抗氧化活性和淋巴细胞增殖活性的影响。制备的SP-Fe(Ⅲ)中Fe(Ⅲ)质量分数为16.42%±1.17%。采用5轴蛛网图对SP-Fe(Ⅲ)的抗氧化活性进行了综合评价。结果表明,SP-Fe(Ⅲ)相比SP具有较高的抗氧化活性。在模拟人工胃液消化后,随着消化时间的延长,在pH=6.8的人工肠液中释放出的Fe(Ⅲ)质量分数达到83.64%;在31.25×10–3 g/L的质量浓度下,与SP相比,SP-Fe(Ⅲ)配合物对淋巴细胞增殖提高了44.35%。     

Quantification of response time in poly(vinyl alcohol)–metal complex thermochromic polymeric systems

Thermochromic poly(vinyl alcohol) (PVA)‐based material was synthesized and an extensive study of its thermochromic behavior with respect to response time was carried out. It was observed that it is possible to manipulate the response time by keeping control over chemical and physical parameters. The response time, which is the most important property of a smart material, has in this case been found to be very much influenced by rate of heat transfer into the material. Different compositions of the thermochromic material and their corresponding response time with respect to rate of heat transfer were studied and correlated. First, a theoretical equation was derived and later on it was experimentally verified to quantify the response time in PVA–metal complex‐based thermochromic systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4832–4834, 2006     

基于电容层析成像和模糊模式识别的油气两相流流型辨识新方法的研究

基于电容层析成像和模糊模式识别技术别提出了一种油气两相流流型辨识的新方法。建立了12电极电容层析成像流型自动识别系统，该系统利用Tikhonov正则化原理并结合SIRT(Simultaneous Reconstruction Techniques)算法进行图像重建。Tikhonov正则化原理用于克服图像重建过程中的不适定问题，SIRT算法用于提高最终重建图像的质量。根据流型的随机和模糊特性，提出了一种根据管截面重建图像进行流型辨识的模糊流型判别方法。研究结果表明，提出的流型辨识新方法是有效的。对于层状流、核心流、环状流、均相流等流型，流型辨识的准确率高于95％，辨识一个流型所用的时间小于0.3秒。对于塞状流，流型辨识的准确率高于90％。     

配合物Zn(Him)2(OAc)2的室温固相合成及表征

乙酸锌与咪唑 (Him)通过室温固相反应一步合成配合物Zn(Him) 2 (OAc) 2 ,反应不需溶剂 ,2 0min即可完成 ,产率达 96% ,并用元素分析、红外光谱、热重分析、X -射线粉末衍射和X -射线单晶衍射对产物进行了表征。     

硅铁复合型絮凝剂的实验研究

研究了硅铁复合型絮凝剂的制备方法和絮凝性能 ,确定了其最佳反应条件 ,所得复合型絮凝剂对江水的除浊性能优于聚合硫酸铁 (PFS)和聚合氯化铝 (PAC)。     

Structural features of inclusion complexes of γ-cyclodextrin with various polymers

The crystalline structures of inclusion complexes of γ-cyclodextrin (γ-CD) with poly(ethylene glycol), poly(ethylene adipate), poly(propylene glycol) and poly(isobutylene) were studied by electron microscopy, in combination with X-ray diffraction works and measurements of thermal properties by DSC and TGA. The crystalline structure of as-prepared complexes was tetragonal and its cell dimensions were a = b = 2.380 nm and c = 1.48 nm. When an as-prepared sample was dried in a vacuum at room temperature, the tetragonal modification was transformed into the monoclinic one with the projected cell dimensions of a = 1.75, b = 1.36 nm and γ = 110°. The transformation occurred by progressive ‘shifting’ of rows of polymer necklaces in the [110] direction along the (110) plane in an original tetragonal lamellar crystal. Complexes lost weight by 10-15% in the process of heating up to 140 °C. The tetragonal crystalline modification was transformed into the hexagonal one, and concurrently, the X-ray diffraction profiles of annealed complexes were broadened. When a sample was dried in a vacuum at room temperature or annealed at high temperatures, followed by exposure to water vapor, the original tetragonal crystalline structure was recovered, restoring the original degree of orientation of crystallites in the sample. When water molecules were removed, the lateral stacking order of γ-CD-polymer complexes was destroyed, but the basic necklace structure in which polymer chains threaded through the cavity of γ-CD rings' structure could be retained.     

A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br₂ cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application.