High-temperature transformations of Cu-rich hydrotalcites

CuM(II)Al ternary hydrotalcites (M(II) = Ni, Co and Mg) with a (Cu+M(II))/Al atomic ratio of 3.0 and Cu/M(II) atomic ratio of 5.0 were synthesized by coprecipitation under low supersaturation. Powder X-ray diffraction of the as-synthesized samples showed a pattern characteristic of hydrotalcite-like (HT-like) structure (JCPDS: 41-1428). Thermal analyses of these samples showed four stages of weight loss/heat change when recorded in nitrogen. Analysis of the evolved gases characterized the nature of these transformations. The thermoanalytical effects differed significantly especially for the high-temperature transformations, when the treatment was performed in oxygen. In situ powder X-ray diffraction of the samples was carried out to elucidate the phase evolution of these compounds. Surprisingly formation of CuO was noted at temperatures around 200°C well below the destruction of the layered network. The nature of the resulting phases varied with both the nature of the co-bivalent metal ion and the heating atmosphere. FT-IR spectroscopy confirmed the retention of carbonate ions at higher temperatures (above 700°C), although the concentration of carbonate anion (most likely unidentate) varied with the calcination temperature. The crystallinity of CuO increased significantly above 600°C, probably through dissociation of copper oxycarbonate. Significant differences in the thermal transformation temperatures (for the third and the fourth transformations) of these samples containing different co-bivalent metal ions were not observed. This suggests that an association of the co-bivalent metal ions and/or trivalent metal ion in this phase is unlikely. A plausible thermal evolution scheme of these hydrotalcites is proposed.     

NMR Study of the Stoichiometry, Stability, and Ligand Interchange of Silver Ion-Hexathia-18-crown-6 Complex in Binary Dimethyl Sulfoxide Solvent Mixtures at 300 K

Proton NMR was used to study the complexation reaction between silver ion and hexathia-18-crown-6 in a number of binary mixed solvents of dimethyl sulfoxide with acetonitrile and methanol. Formation constants for the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. The influence of solvent composition on the stability of the resulting complex is discussed. The exchange kinetics of Ag⁺-hexathia-18-crown-6 in 70-30 wt.% dimethyl sulfoxide-acetonitrile and 75-25 wt.% dimethyl sulfoxide-methanol were studied by proton NMR line-shape analysis. In both solvent mixtures, the exchange of thiacrown ether between the free and complexed sites was found to proceed via a dissociative pathway. The exchange rates and the activation parameters E _a, H , S, and G for the ligand exchange were determined and the influence of solvent properties on these parameters discussed.     

X-Ray Powder Diffraction Studies of Polyhydrates of Cross-Linked Tetraisoamylammonium Polyacrylates

X-ray powder diffraction studies were performed of the polyhydrates, formed at positive temperature in swelled grains of carboxylic cation-exchange resins in the form of tetraisoamylammonium (cross-linked tetraisoamylammonium polyacrylates, differing in the degree of cross-linking: 1, 2 and 3%). It was shown that the polyhydrates exist as the crystalline phase under specific conditions, determined earlier by DTA technique. Diffraction patterns of the samples, recorded at the temperature +3 ± 1 °C, indicate that the polyhydrates crystallize in hexagonal symmetry, the unit cell parameters are close to a=12.25 Å, c=12.72 Å and do not depend significantly upon the degree of cross-linking. The suppositions were made concerning the size of hydrate crystallites, formed in the swelled grains of the studied resins.This revised version was published online in July 2005 with a corrected issue number.     

液相色谱-串联质谱法检测雄蜂蛹粉中50种抗生素残留

建立了液相色谱-串联质谱检测雄蜂蛹粉中50种抗生素残留（大环内酯类、喹诺酮类、磺胺类、四环素类、硝基咪唑类、林可霉素和氯霉素）的方法。样品经高氯酸溶液和醋酸铅溶液提取沉淀蛋白质，清液用磷酸氢二钾溶液调节pH值至8，经固相萃取净化后进行仪器分析。采用多反应监测正离子或负离子模式检测，可以一次完成对雄蜂蛹粉中50种目标化合物的定性和定量测定。50种抗生素的加标回收率为70.2%~118.3%，相对标准偏差（RSD）为1.8%~13.6%。该方法操作简便，灵敏度高，适用于雄蜂蛹粉中多种兽药残留的分析确证。     

偶合反应化学发光法测定痕量银的研究

本将Ａｇ（Ⅰ）催化Ｓ２Ｏ＾２－８氧化Ｍｎ（Ⅱ）生成ＭｎＯ＾－４的催化反应与ＬｕｍｉｎｏｌＭｎＯ＾－４－ＯＨ＾－的化学发光反应相偶合，建立起一种新的灵敏测定痕量银的化学发光分析法，在所研究的优化条件下，该法测定银的选择性较好，检测限达到３．２×１０＾－１２ｇ／ｍＬＡｇ线性浓度范围为１．０×１０＾－１１－１．０×１０＾－５ｇ／ｍＬＡｇ，用于水样分析，结果较为满意。     

Complexing equilibria and redox potentials in the system Ag(II)/Ag(I)-1,10-phenanthroline in propylene carbonate

Predominance areas of various equilibria were identified and complex formation constants of Ag(I) with 1,10-phenanthroline were determined as well as the solubility product of the complex salt for Ag(phen)₂ClO₄ in propylene carbonate. The solubility product of AgNO₃ in propylene carbonate was estimated. The value of the formal potential of the system Ag(phen) ₂ ²⁺ /Ag(phen) ₂ ⁺ inPC was determined by chronovoltammetry. Differences in the stability of analogous complexes in water andPC are discussed.

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Die Gleichgewichtskonstante der Komplexierung und die Redoxpotentiale im System Ag(II)/Ag(I)-1,10-Phenantrolin in Propylencarbonat

Zusammenfassung Die Gebiete der Dominanz der einzelnen Gleichgewichte, die Bildungskonstanten ₁ und ₂ der Komplexe Ag(I) mit 1,10-Phenantrolin und der Wert des Löslichkeitsproduktes Ag(phen)₂ClO₄ in Propylencarbonat wurden bestimmt. Das Löslichkeitsprodukt von AgNO₃ in Propylencarbonat wurde abgeschätzt. Die Werte des formalen Potentials des Systems Ag(phen) ₂ ²⁺ /Ag(phen) ₂ ⁺ inPC wurden mit Hilfe cyclischer Voltametrie ermittelt. Es wurden weiterhin die Unterschiede in der Stabilität analoger Komplexe in Wasser und in Propylencarbonat diskutiert.

     

纳米银掺杂二氧化硅复合颗粒的制备及表征

0引言金属纳米颗粒因其粒子尺寸小(1￣100nm),比表面积大,表面原子数多,表面能和表面张力随粒径的下降急剧增大而具有量子尺寸效应[1]、小尺寸效应[2]、表面效应[3]及宏观量子隧道效应[4]等,从而出现了不同于常规固体的新奇特性,如:光学性质、磁性质以及电磁学性质[5],使其在催化、信息存储及非线性光学等领域展示了广阔的应用前景[6]。虽然制备金属纳米颗粒的方法有很多[6],但是由于纳米尺寸的金属颗粒具有较高的表面能,容易发生聚集,所以如何保持其稳定性依旧是比较困难的问题。随着纳米科技的发展,人们正尝试用各种方法来解决这个问题:如…     

Ag／Al2O3选择性催化丙烯还原氮氧化物表面反应机理的原位红外光谱研究

 在富氧条件下Ag／Al2O3对以丙烯为还原剂选择性催化还原NOx的反应有很高的催化活性．本实验成功地利用原位红外光谱分析手段,在真实的催化反应条件下,探讨了丙烯选择性还原NOx的反应机理,证实了催化剂表面反应中间体Al－NCO和Ag－NCO虽在真空中稳定,但在实际反应条件下极为活泼．催化剂表面上R－ONO和R－NO2分解成NCO是整个反应的速度控制步骤．这一结论与在真空系统条件下对其反应机理的研究结果一致,证明了在这一反应体系中两种研究方法的相关性．同时本实验还从反应机理上探讨了催化剂的水蒸气中毒现象．水蒸气的存在阻碍了催化剂表面R－ONO和R－NO2的生成,并进一步阻碍了反应的速度控 制步骤,即R－ONO和R－NO2向Al－NCO和Ag－NCO的转化,但这是一种完全可逆的暂时中毒现象．结合相应的催化剂活性评价结果对表面反应机理进行了讨论．     

Zinc-catalyzed Williamson ether synthesis in the absence of base

Zinc powder was found to be a highly efficient catalyst for the synthesis of aromatic ethers using microwave heating in the presence of N,N-dimethylformamide as well as under stirring in an oil-bath using tetrahydrofuran as solvent without any inorganic base. This method can be used for selective mono-, di- or tri-O-alkylations.     

Synthesis and Crystal Structure of Ag2（admtrz）2（CF3CO2）2（admtrz=4—amino—3,5—dimethyl—1,2,4—triazole）

1 INTRODUCTION Transition metal complexes bridged by 1, 2, 4-triazole group can produce interesting structures and specific properties[1]. Many attempts have been made to synthesize a variety of complexes with paramagnetic centers by using such ligands, and their structures and magnetic properties have been characterized[2]. However, the polynuclear Ag(I) complexes bridged by 1, 2, 4-triazole have been poorly studied[3]. Recently, we have prepared a series of silver(I) triazole complex…