电化学方法制备铜钴钠米多层膜

要用旋转圆盘电极，双脉冲电位法从单一的含有铜离子和钴离子的镀液中电沉积Ｃｕ－Ｃｏ纳米多层膜，并用ＴＥＭ．ＡＥＳ和Ｘ－射线衍射研究镀层的形貌和组成。结果表明：多层膜结构为纯铜和含有少量铜的铜钴合金层交替组成。铜在钴层中的含量，随着液中的铜含量的增大和转速的提高而提高。     

双离子AB交联型聚醚类固体电解质及其电流变液的性能

将α，ω－双甲基丙烯酰氧基封端的聚乙二醇与高氯酸锂络合，分别用溶液聚合和反相悬浮聚合合成了双离子ＡＢ交联型聚醚类高分子固体电解质（ＡＢＣＰＥ２）及其组成的无水电流变（ＥＲ）液．研究了ＡＢＣＰＥ２本身的离子导电性和含ＡＢＣＰＥ２的ＥＲ液的活性和电性能，并用扫描电镜表征了ＥＲ液中的粒子．获得了离子导电率高达８．０×１０－５Ｓ／ｃｍ（２５℃）的高分子固体电解质和活性较高的无水ＥＲ液．     

电镀液中铜、铁、铅和锌等杂质元素的原子吸收光谱测定

电镀液中常见的有害杂质:铜、铁、铅和锌等的允许含量随镀液种类和杂质元素不同而异。例如,镀镍液中的铜、铁、铅和锌的允许范围在几个至几十个毫克/升内,而镀铬液中的铁的允许范围却在1—几克/升内。1964年Whittington报告用原子吸收加入法测镀镍液中的铜、铁、铅和锌。我们也用过此法。此法比较麻烦。虽然Parker报告把电镀液稀释后直接用原子吸收法测锌、铜、铬,但未报导具体条件。本文除测定镀镍液和镀钻液中低含量铁仍用加入法外,铜、铅、锌及镍、钴镀液中高于50毫克/升铁都用稀释法。实验表明:     

不同化学镀液中p—Si上激光诱导局部沉积铜

在化学镀铜溶液中，ｐ－Ｓｉ片在波长为５１４．５ｎｍ的激光束的照射下，得到了选择性的铜镀层。采用ＡＥＳ、ＳＥＭ、ＲＢＳ和电学技术对比了在３种含不同还原剂的镀液中得到的镀层的形貌、组成、界面扩散及电学性质，探讨了液相激光诱导化学沉积铜的机理。     

芳族硝基化合物电还原中Cu-Ni合金的电极活性

本文采用共沉积法制备了以铜为基体的不同Ｃｕ／Ｎｉ比的Ｃｕ－Ｎｉ合金镀层,并用稳态极化法研究了这些镀层在使用硝基苯（ＮＢ）和１,５－二硝基蒽醌（１．５－ＤＮＡ）制备对氨基苯酚（ＰＡＰ）及１,５－二氨基－４,８－二羟基蒽醌（１,５－ＤＡ－４,８－ＤＨＡ）等电化学还原过程中的阴极活性．研究表明,在ＰＡＰ和１,５－ＤＡ－４,８－ＤＨＡ电合成体系中,不同Ｃｕ／Ｎｉ比的合金阴极具有不同的交换电流密度（ｉｏ）和表观活化能（ＥＡ）,其中以０．０５ｍｏｌ／ＬＣｕＳＯ４·５Ｈ２Ｏ＋０．６ｍｏｌ／ＬＮｉＳＯ４·６Ｈ２Ｏ＋０．２５ｍｏｌ／ＬＮａ３Ｃｉｔ·２Ｈ２Ｏ组成的镀液,并在控制电流密度为０．６Ａ·ｄｍ－２、ｐＨ值为６、体系温度为５０℃等工艺条件下镀制的Ｃｕ－Ｎｉ合金试片（ＣＮ－３０）,具有最大的ｉｏ和最小的ＥＡ值,与常规所用的Ｃｕ、Ｃｕ／Ｈｇ、蒙乃尔合金等阴极相比,ＣＮ－３０试片的电极性能最佳     

电解制备铒钴中间合金的电化学研究

采用循环伏安法和恒电位电解后的电位－时间曲线等方法，研究了ＫＣｌ－ＥｒＣｌ３熔体中Ｅｒ＾３＋在钴电极上的电极过程。结果表明，Ｅｒ＾３＋在钴电极上还原，首先上成铒钴合金，然后才析出纯金属铒，研究了以钴作自耗阴极制取铒钴合金的工艺条件，得到含铒高达９２ｗｔ％的铒钴中间合金，其组成是Ｅｒ３Ｃｏ和Ｅｒ，铒的回收率＞９０％，电流效率８０％。     

T（3－BrP）PS_4卟啉用于高效液相色谱法测定微量钴、锌、铜

新显色剂５，１０，１５，２０－四（３－溴－４－磺酸苯基）卟啉，即Ｔ（３－ＢｒＰ）ＰＳ_４，与Ｃｏ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）离子生成螯合物，可在岛津ＣＬＣＯＤＳ柱上用离子对反相高效液相色谱法（ＨＰＬＣ）分离。流动相为２７＋７３的乙腈＋水，内含２０ｍｍｏｌ／Ｌ的乙酸＋乙酸钠缓冲液（ｐＨ６．０）和１０ｍｍｏｌ／Ｌ的四乙基碘化铵（ＴＥＡ·Ｉ）。检测波长为４２０ｎｍ。应用于茶叶、桔皮和紫米中微量钴、锌，铜离子的测定中，结果满意。     

Co-WC电极

从钴镀液中添加ＷＣ微粒复合电沉积制备Ｃｏ－ＷＣ镀层,ＷＣ微粒的加入,加快了阴极电化学反应．Ｃｏ－ＷＣ复合电极在碱性溶液中具有优越的电催化析氢性能,并经受了长期间断电解的试验,电极性能稳定     

钙稀土氟碳酸盐矿物中三种B_8S_6型新规则混层结构的高分辨电镜研究

用选区电子衍射（ＳＡＥＤ）和高分辨电子显微术（ＨＲＥＭ）研究钙稀土氟碳酸盐矿物及其衍生多晶体结构，发现三种不同的氟碳铈矿（Ｂ）与直氟碳钙铈矿（Ｓ）具８：６新规则混层结构（Ｂ_６Ｓ_６－Ⅰ、Ｂ_８Ｓ_６－Ⅱ和Ｓ_８Ｓ_６－Ⅲ），确定了各自的晶体结构类型、晶胞参数、堆垛模式及晶体化学式等。高分辨像的观察分析，揭示出三种Ｂ_８Ｓ_６规则混层结构中的Ｃｅ－Ｆ离子层以及两个Ｃｅ－Ｆ离子层之间的ＣＯ_３离子组具有不同的排列方式，观察和讨论了上述规则混层结构中的无序夹层及堆垛层错等非均匀结构现象     

Fe—RE磁性多层膜的结构稳定性研究

用真空双源蒸镀法在ＮａＣｌ和Ｓｉ单晶衬底上沉积了ＲＥ－Ｆｅ（ＲＥ：Ｄｙ、Ｙ）成分调制多层膜，借助透射电子显微镜（ＴＥＭ）热台及真空退火方式研究了多层膜受热过程中的结构变化规律。受热温度≤２００℃时，多层膜各单层的非晶结构不发生显著变化，且成分调制结构不被破坏，因此，可以认为非昌单支在多层膜在２００℃以下的结构是稳定的。     

Cu-Co bi-metal catalyst prepared by perovskite CuO/LaCoO3 used for higher alcohol synthesis from syngas

Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO3 particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified C02C species.     

Cu-Co bi-metal catalyst prepared by perovskite CuO/LaCoO3 used for higher alcohol synthesis from syngas

Cu-Co bi-metal catalysts derived from CuO/LaCoO₃ perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO₃ to Cu-Co₂C/La₂O₂CO₃ under H₂ pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO₃ particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified Co₂C species.     

Amperometric detection of amino acids with a passivated copper electrode

The amperometric behaviour of a copper electrode towards amino acids is studied by means of a rotating disc electrode. A theoretical model describing the anodic background current in a buffer solution and the increase of the current caused by amino acids is checked experimentally. The influences of the amino acid concentration, the rotation speed of the electrode and the composition of the buffer solution are studied. It is proved that chemical dissolution of a passivating film on the electrode surface, which is enhanced by the complexation reaction between the amino acid and copper(II) ions, is the principle of the phenomena observed. The applicability to flow systems is demonstrated.     

Variability of selectivity coefficients of solid-state ion-selective electrodes

The generalized model for the selectivity mechanism of solid-state ion-selective electrodes has been experimentally verified. The experimental parameters investigated were the concentration of interfering ion, temperature and stirring. Among the systems studied were electrodes sensitive to chloride (bromide, iodide), bromide (chloride, iodide), iodide (chloride, bromide), silver (copper, lead), copper (silver, lead) and lead (silver, copper), the species given in brackets being considered as the interferents. The model has been confirmed except for cases where the concentration of ions formed at the electrode surface by metathesis is too small to be the factor that dictates the electrode potential.     

Microstructure studies of perfluorocarboxylated ionomer membranes

The ionic microstructure of perfluorocarboxylated ionomer membranes has been studied with Cu, Fe and Eu as a function of ion concentration and water content. Techniques used were EPR, Mössbauer spectroscopy and magnetization measurements. In the copper membranes we distinguish isolated Cu²⁺ ions, acetate dimers and copper ions in small particles of a carboxylate compound. The dimers and this compound are destroyed when sufficient water is present in the membrane. Ferric ions cannot be introduced directly into the membrane from solution but ferrous membranes can be aged or oxidized to give small groups of hydrated Fe³⁺ coexisting with isolated hydrated Fe²⁺. The mean square displacement of the Mössbauer probe ions increases less rapidly with temperature than in Nation® due to the lower water content and stronger cation-anion association in the carboxylated membrane. Precipitation of the exchanged ions in the membrane was achieved by soaking in KOH solutions.     

Effect of metal ions on the response of a cyanide-selective electrode

An extended model and its experimental verification are presented for the response of a cyanide-selective electrode in the presence of metal ions. The model takes into account the effect of metal-hydroxide complexes ar high pH values. The electrode responds to the total cyanide concentration even in the presence of an excess of zinc and cadmium ions. When copper(I) is present, the cyanide complexes must be decomposed before the total cyanide concentration can be measured. The results show the importance of considering both metal-cyanide and the metal-hydroxide complexation.     

Two-column ion-exchange method for the determination of copper-complexing capacity and conditional stability constants of copper complexes for ligands in natural waters

Sample solutions titrated with Cu(2+) ions are passed sequentially through two ion-exchange columns in an automated flow system. The first column is packed with Chelex-100 resin and retains Cu(2+) ions that are free or derived from copper complexes that dissociate in the column. The second column is packed with AG MP-1 anion-exchange resin and retains negatively charged Cu(II) complexes. The retained copper species are then eluted from the columns and determined on-line with a flame atomic-absorption spectrophotometer. It is necessary to correct for a small fraction of free Cu(2+) ions that pass through the first column and are retained by the second column. The Cu(II)-complexing capacity of sample solutions is determined from plots of the concentration ratio of free Cu(2+) ions to Cu(II) complexes vs. the concentration of free Cu(2+) ions. Conditional stability constants of the copper complexes are also estimated from these plots. The complexing capacity of sample solutions is also determined rapidly by measuring the concentration of complexed Cu(II) after spiking the sample with an excess of Cu(2+) ions. The sample solutions tested were 4.0muM NTA, 4.0-mg/l. humic acid, and a river water.     

Precipitation of monodispersed basic iron(III) sulfate (sodium jarosite) particles

Uniform sodium jarosite particles were obtained by forced hydrolysis of ferric salt solutions to which copper sulfate, sodium sulfate, and sodium nitrate were added. It was found that at the same concentrations of ferric and sulfate ions the particle size and yield decreased with the lowering of the concentration of sodium ions, but the morphology remained the same. At a sufficiently small content of sodium in the reacting solution, no precipitation of sodium jarosite particles was observed. Finally, chemical and XRD analyses showed that small amounts of copper ions are incorporated in the crystal lattice which, with the change in the Na⁺/H₃O⁺ ratio, slightly affected the structure of this mineral, but not its other properties. Received: 12 July 2000 Accepted: 18 August 2000     

Catalytic properties of Cu-Co catalysts supported on HNO3-pretreated CNTs for higher-alcohol synthesis

HNO 3 -pretreated CNTs were employed as supports, and a special ultrasound-assisted impregnation method was designed to prepare supported Cu-Co catalysts for higher-alcohol synthesis from syngas. The catalysts used in this work were characterized by N 2 adsorption-desorption, TEM, XRD, H 2 -TPR, CO-TPD techniques. It was found that the pre-treatment procedure of CNTs remarkably promoted the catalytic properties of the Cu-Co/CNTs catalysts. For the Cu-Co catalyst supported on CNTs pre-treated by 68 wt% HNO 3 , some active components were introduced into the CNTs channels, their dispersions and the amount of strongly adsorbed CO-species were improved. The CO conversion and alcohol yield on the HNO 3 -pretreated Cu-Co/CNTs catalyst were increased by ～21% and ～69%, respectively, compared with those on the normal Cu-Co/CNTs catalyst.     

Application of the zone melting technique to metal chelate systems-V Zone chromatographic separation of metal chelates on columns of some inert solid solvents

Binary mixtures of acetylacetone and 8-hydroxyquinoline chelates of copper(II), nickel(II), cobalt(II) and cobalt(III) were processed by zone-chromatography on columns of some naphthylalkyl ethers as inert solid solvents. The metal chelates were separated to give chromatograms on the columns according to the ratio of their distribution coefficients. Distribution coefficients of metal ions varied with the type of chelating agent used and the solid solvent, and were found to be strongly affected by operating conditions, especially zone length, zone travelling speed and initial concentration of the metal chelate.