铜在3%NaCl溶液中腐蚀行为的光电化学研究

Cu以其优异的导电性、导热性和易加工性广泛用于工农业生产中．自然Cu的腐蚀和防腐成为人们很关注的问题．人们已经注意到，Cl-对Cu的腐蚀有影响，并进行过一些研究．但目前使用光电化学方法研究这一问题的文章尚不多见，特别是利用测量开路光电压及其瞬态波形这一现场的、无损的、灵敏的监测方法研究户对Cu电极腐蚀全过程的文章尚未见到．本文正是利用如上方法及XPS，AES方法，研究了Cl-对Cu电极腐蚀的全过程，取得了一些有意义的结果．1实验方法Cu电极用99．99％（质量分数）的Cu制成，面积约为39mm2；电极底部由Cu导线焊接引出，…     

Potentiometric behaviour of the copper electrode in aqueous copper(II) perchlorate solutions containing sodium chloride

It is demonstrated that the copper metal electrode corrodes in the presence of copper(II) ions in solution. A model based on mass balance can properly describe the experimental results. In the presence of copper(II) ions the copper electrode responds to copper(I), indicating that the electrode potential corresponds to a mixed potential.     

利用碘离子增感效应和金电极导数阳极溶出法研究铜丶铅和镉的同时测定

A method of simultaneous determination of copper (II), lead (II) and cadmium (II) in sulphuric acid-iocide ion medium was established by derivative anodic stripping voltammetry (DASV) on the gold electrode. The peak theights of lead and cadmium were increased by enhancement effect of iodide ion and the peaks of bismuth and copper were well formed and completely resolved on gold electrode in the presence of iodide ion, therefore peak of copper is not affected by bismuth. The sensitivities for copper, lead and cadmium were very high and their peak potentials in the stripping voltammogram were +0.25, -0.2 and -0.27 volt, respectively. The dependence of peak height of these elemets on their concentrations was linear. The detection limits for copper, lead and cadmium were 0.2 0.2 and 0.05 ppb, respectively. We have further studied the electrode process by means of triangle cyclic voltammetry and proved that he electrode reaction of copper is reversible, and that the reversibility of electrode reactions of lead and cadmium is not good.     

Dynamics of copper electrodeposition onto fibrous carbon electrodes

Distribution of copper electrodeposited from a sulfuric acid solution onto fibrous carbon electrodes, copper deposition rate, and current efficiency by the metal were studied in relation to the electrolysis duration, electrical conductivity of the electrode, geometric current density, and solution flow rate. The variation of the electrode thickness on which copper ions discharge at the limiting diffusion current at various solution flow rates and the electrode thickness on which the whole amount of oxygen dissolved in the electrolyte is reduced were calculated in relation to the solution flow rate and geometric current density. The main factors governing the distribution of copper across the electrode thickness and the electrolysis parameters from the beginning of the process till ??clogging?? of a part of the electrode by the metal were determined.     

Effect of chloride ions on the behaviour of the orion copper(II) ion-selective electrode

The normal shiny surface of a copper(II) ion-selective electrode tarnishes when exposed to chloride ions. Polishing with fine emery cloth easily removes this dull surface layer and fully restores the proper potential response characteristics of the electrode. No such loss of character is evident with a non-chloride based reference electrode except in the presence of added chloride ions. The electrode also seems less affected in premixed solutions of copper(II) and chloride. the chloride ions then being largely bound as copper(II) chloro-complexes.     

Using nanoparticle aggregation to give an ultrasensitive amperometric metal ion sensor

Herein we show an electrochemical sensor for the detection of copper ions that has a limit of detection below 1 pM. This extraordinarily low limit of detection is achieved in two ways. The first is to use SAM modified electrodes to give low background current where electron transfer to the underlying polycrystalline electrode is achieved through gold nanoparticles attached to the terminus of the SAM. The gold nanoparticles are modified with cysteine to allow copper accumulation. The second way the low detection limits are achieved is by the addition of cysteine-modified nanoparticles to the sample solution, as well as the SAM modified electrode. The complexation of copper with the nanoparticles in solution causes them to aggregate with these aggregates accumulating on the electrode. Thus a higher percentage of copper in the solution is collected at the electrode giving the enhanced detection limits.     

硬脂酸钠在蓖麻油/水界面上自组装动力学的研究

以电沉积铜为探针,循环伏安法研究硬脂酸钠在蓖麻油/水界面上自组装的动力学.在涂有蓖麻油的石墨粉-环氧树脂固态电极上,硬脂酸钠自组装膜形成过程可由电沉积铜阳极峰监测,遵从高斯函数生长动力学,生长速率常数为km=0.0006292(±0.0000294)s-1.硬脂酸钠自组装膜能较好地控制铜粒子的球形生长和生长尺度,形成硬脂酸钠自组装-铜纳米粒子复合膜.铜粒子在石墨粉-环氧树脂固态电极上为半球形生长,而在涂油和自组装电极上为球形生长.与蓖麻油涂层相比,石墨粉-环氧树脂固态电极与沉积铜间存在弱相互作用(ΔG0=3.86kJ/mol),而硬脂酸钠羧基与沉积铜也有较弱的相互作用(ΔG0=-2.412kJ/mol).     

Diffusion-layer model for copper solid-state chalcocite membrane electrode; sensitivity to copper(II) ions

The diffusion-layer model for the chalcocite (Cu(2)S) membrane electrode is discussed. It is equivalent to a simpler model based on exchange reactions at the electrode surface. The chalcocite is sensitive to copper(I) and copper(II) ions and the theoretically predicted response is in good agreement with experimental data. The membrane is a conductor, but this does not significantly affect its function as an ion detector. The limitation of the electrode is the membrane solubility as shown when Cu(II) ions in contrast to copper(I) ions are strongly complexed.     

界面移动法测定离子迁移数实验的优化

在基础物理化学实验界面移动法测定离子迁移数中,针对传统实验方案所用镉电极存在的不足之处,改用铜电极进行了平行对比实验,发现采用铜电极的实验方案在保证实验数据有良好准确度的前提下,既能降低电极材料的毒性,也能降低实验相关设备的配置要求。     

Poly-salicylic acid modified glassy-carbon electrode and its application

A poly-salicylic acid modified glassy-carbon electrode (PSAMGCE) was prepared by electro-polymerisation. The behaviour of copper on this electrode was investigated by anodic stripping voltammetry. The electrode is about 40 times more sensitive than the unmodified glassy-carbon electrode. It was applied to the determination of trace copper(II) in water, and shows a 96-106% recovery and a relative standard deviation of ca. 3%.     

Copper(I) activity of the copper(II) ion-selective electrode

The Orion copper(II) ion-selective electrode responds well to copper(II) ions in aqueous medium. However, in the presence of acetonitrile and copper(I) ions, it can behave as a copper(I) ion-selective electrode with Nernstian behaviour.     

Accumulation voltammetry of copper(II) at carbon-paste electrode containing salicylideneamino-2-thiophenol

Summary Accumulation voltammetry of copper(II) was investigated with a carbon-paste electrode containing salicylideneamino-2-thiophenol(SATP). Copper(II) was accumulated as the copper(II)-SATP complex on the electrode without an applied potential by immersing the electrode in 0.01 mol/l acetate buffer (pH 3.8) containing copper(II). The reduction peak of the copper(II)-SATP complex was observed at –0.12 V (vs. SCE) in 0.01 mol/l acetate buffer (pH 3.8) by scanning the potential in a negative direction. The calibration curve for copper(II) was linear in the range of 2×10^–9–1×10^–7 mol/l. Since the accumulation of copper(II) is based on a chemical reaction between copper(II) and SATP, copper(II) was selectively accumulated on the electrode. The presented method was applied to the determination of copper(II) in standard reference materials prepared by the National Institute for Environmental Studies.     

SERS study of the interaction of thiourea with a copper electrode in sulphuric acid solution

The electrochemical interaction of thiourea with a copper electrode in sulphuric acid solution was investigated using Fourier transform Raman and in situ surface-enhanced Raman scattering (SERS) spectroscopy. SERS spectra of thiourea at a copper electrode were obtained in solutions containing greater than 5 ppm thiourea; the spectra obtained were consistent with adsorption of the molecule on the copper electrode via the sulphur atom. The SERS spectra provide evidence of complex formation involving thiourea and sulphate species at the electrode surface.     

Copper oxide nanoparticles and ionic liquid modified carbon electrode for the non-enzymatic electrochemical sensing of hydrogen peroxide

The direct electrocatalytic reduction of hydrogen peroxide in alkaline medium at a carbon ionic liquid electrode modified with copper oxide nanoparticles was investigated. The electrode was prepared by mixing graphite particles, ionic liquid (n-octylpyridium hexafluorophosphate) and copper oxide nanoparticles. Unlike the film-modified electrode, the fabrication of this electrode is simple and highly reproducible. The combination of the good conductivity of the ionic liquid and the high catalytic activity of the nanoparticles resulted in an electrode with attractive properties for the determination of hydrogen peroxide. The concentration of NaOH and the loading of copper oxide nanoparticles were optimized. The linear range for the determination of hydrogen peroxide is from 1.0 μM to 2.5 mM, the detection limit is 0.5 μM. High stability, sensitivity, selectivity and reproducibility, fast response, the ease of preparation, and surface renewal made the electrode well suitable for the determination of hydrogen peroxide in real samples.     

The determination of reducing carbohydrates using a cation-exchange column and potentiometric detection with a metallic copper electrode

Summary A metallic copper electrode is employed as a potentiometric detector for reducing carbohydrates after their separation on a cation-exchange column. A post-column reactant solution comprising 1 mM copper (II) and 35 mM ammonia is mixed with the column effluent and the metallic copper electrode provides a steady baseline potential by responding in a Nernstian manner to the level of copper ions present. This in turn is affected by the presence of eluted reducing carbohydrates, leading to an indirect detection method for these species. The method is applied to the detection of maltose, lactose, xylose, glucose, sorbose, fructose and arabinose. The electrode response mechanism is discussed and detection limits in the low nanomole range are reported. The potentiometric detector is shown to be more sensitive than refractive index detection.     

巯基乙酸修饰金电极的电化学行为及对铜离子的测定

通过共价自组装的方法制备了巯基乙酸单分子层修饰金电极.在含有铜离子的磷酸缓冲液中搅拌吸附,铜离子与修饰电极表面的巯基乙酸形成的活性配合物吸附在电极表面.用该电极对不同浓度的铜离子进行检测,发现峰电流随铜离子浓度的增大而增大,在0.05~1μmol/L之间出现良好的线性关系,其最低检测限可达10 nmol/L.     

The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction

This communication examines the effect of the surface morphology of polycrystalline copper on electroreduction of CO(2). We find that a copper nanoparticle covered electrode shows better selectivity towards hydrocarbons compared with the two other studied surfaces, an electropolished copper electrode and an argon sputtered copper electrode. Density functional theory calculations provide insight into the surface morphology effect.     

Copper Electrodeposition Dynamics at a Porous Flow-through Electrode

The dynamics of the copper electrodeposition out of a dilute sulfuric acid solution of copper sulfate (straight-through regime, solution supplied from the rear at a velocity of ～1 cm s^?1) onto preliminarily metallized carbonaceous felt of the VINN-250 brand is studied. The profile, which describes the final deposit distribution, qualitatively conforms to predictions made in terms of a dynamic model for a porous electrode described previously, as does the nonmonotonic variation of the gain in the copper weight and the current efficiency for copper with time in the first half of the deposition process. At later stages of the process, along with the enhancement of the tendency towards the forcing of the copper electrodeposition process towards the front end of the electrode, there appears a new factor, which is not taken into account by the method. This factor is the deposition of a loose rough copper layer outside the porous electrode at its front side.     

Effect of some chelating ligands on the potential response of the chalcocite copper ion-selective electrode

The effects of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoacetic acid, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediaminetetraacetic acid, diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid on the behaviour of the synthetic chalcocite (copper(I) sulphide) copper-selective electrode are described. The effects of those ligands on the electrode response at different pH values is explained on the assumption that copper(I) ions contribute to the potential indicated. Copper(I) ions originate from the membrane phase and participate in exchange and redox reactions. The effects of oxygen and temperature are reported. The electrode response can be predicted on the basis of copper(II) equilibria in solution, only if the conditions are such that there is no interference from copper(I) ions.