快速电化学动力学测量装置

由于电解池时间常数和iR降的限制,传统上绝大部分电化学实验的时间尺度是在秒或毫秒的范围,超微电极的应用使得快速电化学动力学测量成为可能。考虑一个盘电极,双电层电容Cd以及瞬态电流i都与电极面积即半径平方成正比,而溶液内阻R_u则与电极半径成反比,因此,电解池时间常数R_uC_d和iR_u降都随着电极尺寸的缩小而减小。一个半     

一种通用型电化学石英晶体微天平电解池的设计

电化学石英晶体微天平(EQCM)同时结合了电化学检测的高灵敏度和石英晶体微天平(QCM)可实时检测电极表面质量变化及阻尼的特点,在电化学研究中具有非常好的应用前景,已得到越来越广泛的应用.本文设计了一种通用型的EQCM电解池,用恒电流电沉积铜的方法测定了QCM Pt电极的质量灵敏因子Cf,分析了Cf实验测定值与理论值偏差的原因,并讨论了在所设计的EQCM电解池中QCM Pt电极的使用范围,为进一步开展EQCM的应用研究提供可靠的基础.     

薄层电解池流动注射法测定铜

薄层电解池做高压液相色谱鉴定器的报道较多。但不用分离装置的简单薄层电解池流动注射法国内似尚未见正式报道,国外报道也很少。Alexandra等曾以管状金电极流动注射安培法测定氯。我们分别以大面积银、铜、玻璃碳、铜面镀金为工作电极装配电解池,试验发现以玻璃碳为最佳。本文报道薄层电解池的结构及用薄层电解池流动注射法测定铜的试验条件及结果。     

钛/活细胞界面原位EIS研究

设计了原位电解池用于生物材料/活细胞界面电化学交流阻抗谱(EIS)的测量, 原位观测了钛/MG63细胞界面EIS行为及其随时间的变化. 原位电解池中引入Ag/AgCl作为参比电极, 解决了EIS测量过程中高频部分信号失真的问题. 钛/MG63细胞界面EIS研究初步结果表明: 活细胞在钛电极表面附着, 可改变界面双电层结构和电极的表面状态, 进而影响界面的电化学性质. 实验发现, 由于钛电极表面氧化层的阻抗信号处于中低频段, 而细胞膜层自身的电化学阻抗响应位于高频范围, 由此, 可分别分析不同的电极过程, 解析其相互关系, 研究活细胞在生物材料表面的作用机理.     

一种新型的长光程薄层光谱电化学池

1 前言光谱电化学是近年来发展起来的一门新兴学科,是把光谱方法和电化学方法结合起来,可进行现场分析的技术.作者曾用夹心式薄层电解池研究过超常价态Ag(Ⅲ)、Cu(Ⅲ),大分子冠醚配合物电还原反应的机理.对于一般的薄层电解池,由于从薄层正面透光,主要有三点不足:(1)由薄层溶液厚度决定的短光程,使得溶液粒子的检测灵敏度较低;(2)光透电极既需要透光     

超薄层红外光透电解池的设计和应用

采用真空镀膜技术制得了超薄型红外光透极电极，设计了适用于水溶液体系和多种固体电极体系的红外光透薄层电解池，通过亚铁氰化钾水溶液／金电极体系和亚硫酰氯／碳电极体系的现场红外光谱电化学测试证明：该电解池具有结构简单，光谱响应灵敏，适用范围较宽等优点。     

电化学检测器在液相色谱中的应用——Ⅱ.仪器和应用

电化学检测池的结构与装置 LCEC系统可以简化成图1。一般由四部分组成:样品注入、溶剂传输、色谱分离和电化学检测。本文将主要介绍LCEC仪器中的电分析化学原理。由于电分析检测方法种类繁多,电解池装置(包括电极材料、形状及电解池结构等)的设计也有相当的数量。我们将试图对LCEC系统中电极材料的选择和电解池结构的设计等的一般性原则作出总结。     

薄层光谱电化学

光谱电化学是60年代初发展起来的交叉学科方法。光谱电化学是把光谱技术和电化学方法结合起来,在一个电解池内同时进行测量的一种方法。通常,以电化学为激发信号,而体系对电激发信号的响应则以光谱技术进行监测,两者密切结合发挥了各自的优点,如用电化学方法容易控制调节物质的状态,能定量产生试剂等,而用光谱方法则有利于识别物质。这样,多种信息可同时就地获得,对于研究电极过程机理,电极表面特性,鉴定参与反应的中间体,瞬间状态和产物性质,测量式电极电位(E°＇)和电子转移数     

普鲁士兰修饰电极的现场X射线衍射研究

利用Ｘ射线衍射仪－电化学装置－两台微机联机组成的Ｘ射线衍射差谱全自动电化学测量系统，并结合特制的电解池，现场测定了普鲁士兰修饰电极薄膜在电化学变过程中的Ｘ射线衍射差谱。结果证实在变色过程为了平衡体系电荷而进入和脱出修饰薄摸的Ｋ＾＋导致了薄膜晶体结构的转变。理论计算的Ｘ射线衍射差谱与实测结果基本一致。     

电化学沉积制备纳米结构铜电极及其葡萄糖检测性能

利用电化学沉积法制备了高电活性的纳米结构铜电极材料, 采用扫描电子显微镜和电化学方法分别对电极表面形貌和电化学性能进行了表征, 研究了实验参数对葡萄糖电氧化活性的影响. 结果表明, 改变沉积条件可以调控沉积铜的形貌及电催化活性. 在最佳条件下制备的铜纳米结构电极对葡萄糖检测的灵敏度为1310 μA·L/mmol, 检出限为5.0×10^-7 mol/L(S/N=3).     

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.     

恒电流电解-BCO分光光度法测定纯铜中铜含量不确定度的评定

对采用恒电流电解-BC0分光光度法测定纯铜中铜含量的不确定度进行了评定.对测量重复性、电解重量法、光度法等影响测量结果的不确定度分量进行了分析和量化.当纯铜中铜的质量分数为99.93%时,扩展不确定度为0.01%,k=2.     

Titanium-supported nickel-copper oxide catalysts for oxidation of carbon(II) oxide

Nickel-copper compositions for catalytic oxidation of carbon(II) oxide to carbon(IV) oxide were prepared by impregnation of oxide films on titanium surface, obtained by plasma electrolytic oxidation followed by annealing. Plasma electrolysis oxide coatings with a layer thickness of 5 to 50 μm were generated using different electrolytes. The compositions were studied by X-ray powder diffraction, X-ray spectral analysis, and electron microscopy, and moisture absorption of the initial plasma electrolytic structures was estimated. A linear correlation was found between the overall concentration of nickel and copper (4 to 25 mol %) in the surface layer of ∼2–5-μm compositions and their catalytic activity. The overall concentration of nickel and copper was found to increase in parallel with the moisture absorption of plasma electrolytic oxidation coatings. Nickel-copper compositions based on plasma electrolytic oxidation coatings generated in a silicate electrolyte displayed the best catalytic, mechanical, and adhesion properties.     

Determimation of Cu and Fe in Hobium by Electrolytic Dissolution and Atomic Absorption Spectroscopy

Abstract

The method of electrolytic dissolution in organic solvents (saturated with NH₁Cl) followed by atomic absorption spectroscopy was applied to the determination of Fe and Cu impurities in niobium metal. It was found that a previously reported decrease in sensitivity could be attributed to precipitation of NH₄Cl on the walls of the feeding chamber of the spectrometer and could be avoided by diluting the solution before measurement.     

Electrolytic synthesis of nipecotic acid ethyl ester

An electrolytic method was suggested for the synthesis of nipecotic acid ethyl ester in a diaphragm electrolytic cell on a copper cathode in aqueous alcoholic alkali solution.     

高温红外光谱电化学薄层池的制作与表征

为了拓宽光谱电化学研究范围,开展高温下电化学反应过程,本文研制了一种高温红外光谱电化学薄层池(HTC)。 研制的HTC清洗方便,操作简单,适用于水体系和有机体系。 该HTC可在室温至373 K(根据溶剂沸点,控温精度为±0.5 K)温度范围内使用,具有良好的电化学性能,红外光谱采集谱图清晰信噪比好。 利用铁氰化钾水溶液和对苯醌离子液体溶液的红外光谱电化学行为对HTC进行了表征,得到较满意的结果。     

Electrochemical Deposition and Spectroelectrochemical Response of Bromophenol Blue Films on Gold

Bromophenol blue (BPB) was electropolymerized onto a Au substrate. The effects of voltammetric cycle number, BPB concentration, and pH on film thickness, density, optical absorption, and electrochemical susceptibility were evaluated, and favorable deposition conditions were identified. Quantitative measurement of the film mass via quartz crystal microbalance enabled determination of the molar volume and revealed a strong dependence of film density with deposition pH. Finally, electrochemical control of the optical properties of BPB films was demonstrated via in situ spectroelectrochemistry. We believe this is the first demonstration of electropolymerization of pure BPB on Au, and thus the first demonstration of poly(BPB) as an electrochemically switchable optical coating.     

Autoxidation and metal surface catalysed oxidation of uranium (III) in acid solutions

The oxidation of uranium (III) in acid solutions has been studied by spectrophotometric measurement in an inert gas atmosphere. Uranium (III) obtained by reduction of uranyl salt with zinc amalgam was oxidized more rapidly than that prepared by dissolution of uranium amalgam or electrolytic reduction of uranyl ion. The oxidation is strongly catalysed by copper or lead ion contained as a trace impurity in zinc. The autoxidation and the metal surface catalysed oxidation of uranium (III) are discussed.     

Nafion－甲基紫精修饰电极测定超氧化物歧化酶的活性研究

本文利用Ｎａｆｉｏｎ－甲基紫精（ＭＶ）修饰电极对溶氧的电催化还原反应间接测定超氧化物歧化酶（ＳＯＤ）活性。用本方法测定ＳＯＤ活性，灵敏度高，抗干扰能力强，线性范围宽，而且操作快速、简便。     

Piezoelectric transmission spectroelectrochemistry with a normal piezoelectric quartz crystal as an optically-transparent electrode

Piezoelectric transmission spectroelectrochemistry (PTSEC), i.e., the combination of electrochemistry and spectroelectrochemistry (SEC) with electrochemical quartz crystal microbalance (EQCM) technique is reported by using a normal piezoelectric quartz crystal (PQC) as an optically-transparent electrode (OTE). A theoretical relationship between the PQC response and the spectroelectrochemical response is derived and used to estimate the apparent molar absorptivity of the absorbing species deposited on the OTE on the PQC surface. The complex of copper with aspartic acid is used to test this new PQC-SEC technique. Results show that the combination of three such diverse techniques provides a very useful methodology for studying electrode processes and electrode surface characteristics in situ.