基于超微电极的原位电化学拉曼光谱

原位电化学拉曼光谱是一种重要的光谱电化学技术.基于超微电极的原位电化学拉曼光谱将拉曼光谱反映的结构信息与电极表面的电化学过程从实验上严格对应和关联,为深刻理解电化学反应机理提供依据.本文综述了采用超微电极作为工作电极的原位电化学拉曼光谱的研究方法和应用进展,总结了应用超微电极作为工作电极开展电化学拉曼光谱实验的方法和具有表面增强拉曼活性的超微电极制备方法,展示了如何利用在超微电极表面获得的拉曼光谱与界面电化学过程的严格关联研究单个锌颗粒电化学氧化过程、吡啶分子在Au电极表面的电化学吸附过程,以及如何利用该技术能以高的信噪比和灵敏度同时测量光电流与分子反应这一特性研究对巯基苯胺选择性光氧化反应.采用超微电极作为工作电极的原位电化学拉曼光谱技术极大拓展了拉曼光谱技术的研究范围,有望成为探索(光)电化学反应的有力工具.     

应用镍超微电极的电化学表面增强拉曼光谱技术研究

镍(Ni)电极在电化学中应用广泛.原位表征Ni电极表面的吸附物种有益于帮助理解电极反应历程、指导发展高效电催化剂.应用超微电极作为工作电极的电化学表面增强拉曼光谱技术结合了超微电极表面的传质特性和分子水平的高灵敏度表征,是研究Ni电化学的有力手段.本文所述的研究工作通过在金(Au)超微电极表面电吸附具有SERS活性的A...     

超微电极的新进展

超微电极是当前电化学前沿领域和研究热点之一。本文主要介绍了超微电极的基本原理、种类和特点 ,并结合国际上超微电极的最新研究现状 ,介绍了超微修饰电极的特点及其在电分析化学中的应用 ;超微电极在扫描探针显微学、固态电化学、生物细胞体内检测和分析化学等方面中的应用。     

超微电极实验:基本原理、制备方法和伏安性能

超微电极的电极尺寸小，双电层电容小，IR降小，传质速率快，响应快，信噪比高，兼具时间和空间分辨率，不仅可以研究快速电极反应动力学性质，而且可以作为电化学扫描显微镜探针，实现基底反应活性的成像，在电化学各个领域均有重要应用，成为一种重要的电化学实验方法。本文将扼要介绍超微电极的基本原理、简易的制备方法及伏安性能的表征实验，以期对开展超微电极实验研究的电化学工作者有所裨益。     

亚微米级叉指型超微带电极阵列的加工和电化学表征

超微电极具有常规电极无法比拟的优良的电化学特性.超微电极包括单超微电极和超微电极阵列,单超微电极响应电流较小,一般仪器难以检测;而超微电极阵列除具有单超微电极的特点外,还能增加测量时的响应电流,有利于仪器检测.其中的叉指型超微带电极阵列(IDA)具有产生-收集效应,可提高检测的灵敏度,实现低浓度测量[1～4].将微电子技术和微细加工技术应用于化学和生物传感技术已引起关注,利用微细加工技术可以实现传感器的微型化、集成化和智能化;减少测量使用的样品量;使传感器的敏感元件具有确定的形状和尺寸,提高测量结果的一致性.本文用多…     

超微电极制备技术及材料研究进展

综述了超微电极电化学以及超微电极的制备方法和材料研究进展。重点介绍了自组装技术、模板法和新的刻蚀手段等技术在超微电极制备中的应用,从电极材料和包覆材料两方面对材料的研究进展情况予以说明,并对未来超微电极的发展趋势进行了展望。     

单体动态电化学

由于个体的差异性和异质性作用,整体平均测量掩盖了个体的本征性质和电化学性能之间的关联.单体碰撞电化学作为一种强大而方便的电化学方法,已被用于研究超微电极上自由扩散的单个个体随机碰撞过程中的电化学行为.然而,个体的动态行为与其电化学反应过程息息相关.因此,对于单体动态电化学行为的研究可实时获取单体在电极界面上的动态电化学...     

微流控芯片中超微电极的制作及其在芯片-电化学检测中的应用

设计并制作了集成有超微电极的玻璃微流控芯片.在电化学检测芯片1(EC-1)中,以光刻方法制作13μm宽的Pt超微电极,距分离管道末端30μm,优化电极体系和分离电压,检测了电泳分离的神经递质.在电化学检测芯片2(EC-2)中,制作7μm宽的超微电极,在其上游集成城墙式的膜结构,进一步腐蚀后的膜厚度为10μm,具有良好的导电性和散热性能,成功地将高压电场截至在超微电极之前,具有进一步应用于电化学检测的能力.     

碳纤维超微盘电极的制备及对单囊泡胞吐动力学的高分辨研究

利用改良的电化学腐蚀方法制备了碳纤维超微盘状电极,具有方法简便,电极尺寸可控、可多次使用等优点.扫描电镜和伏安表征实验表明电极密封效果良好、电化学性能优良.在鼠嗜铬神经瘤PC12细胞上,用超微盘电极实现了高时空分辨、高保真度的单囊泡胞吐测定.与常规微电极相比,能更准确地反应囊泡融合这一超快过程(毫秒级)的动力学过程.     

超微电极上半微分电分析法

介绍了超微半球电极上具有简单反应时的半微分循环伏安理论。理论表明,超微电极上半微分电流与电活性物质的浓度成正比,并据此提出了一种利用超微半球电极上半微分曲线进行电化学分析测量的新方法。该法具有灵敏度高、分辨率好等特点。     

Numerical modeling of a four-electrode electrochemical accelerometer based on natural convection: The boussinesq flow model vs. The compressible flow model

Two-dimensional numerical simulations are conducted to study the feasibility of applying the Boussinesq approximation to the steady-state buoyancy-driven flow in a four-electrode electrochemical accelerometer. Two kinds of electrode layouts along the electrochemical cell, the anode-cathode-cathode-anode (ACCA) and the cathode-anode-anode-cathode (CAAC), are examined. The results from the model based on the Boussinesq approximation are compared to those from the compressible flow model. Though the Boussinesq flow model leads to fairly large quantitative deviations, it is capable of qualitatively estimating the output electric current when the output electric current increases linearly as the applied axial acceleration. A qualitative difference between the two models are found in the centerline density profiles in the electrochemical cell, which can be explained by the compressibility-induced acceleration/deceleration. It is found that the Boussinesq approximation is good enough for the estimation of the electric current at a single electrode while can make large deviations of the cathodic current difference, i.e., the output electric current in this study.     

Electrochemical treatment of tumours: a simplified mathematical model

Electrochemical treatment of tumours implies that tumour tissue is treated with a direct current. During electrolysis, electrical energy is converted to chemical energy through electrochemical reactions at the electrodes. The anode is preferably placed in the tumour and the cathode in a blood vessel or in fresh surrounding tissue. The main electrochemical reactions are chlorine and oxygen evolution, at the anode, if platinum is used. Hydrogen evolution takes place at the cathode. The aim of this paper is to show how mathematical modelling can be used as a tool for defining and optimising the operating conditions of electrochemical treatment (ET) of tumours. A simplified mathematical model is presented for direct current treatment of tumours, focusing on tissue surrounding a spherical platinum anode. The tissue is treated as an aqueous solution of sodium chloride and only the major electrochemical reactions are considered. The model is based on transport equations of ionic species in dilute solutions. Kinetic expressions for the electrochemical reactions, at the anode surface, are introduced. Inputs to the model are the applied current density, and sizes of the anode and electrolyte domain. Concentration profiles of the ionic species and potential distribution, as a function of time, are calculated. In addition, current yields of the anode reactions are obtained from the model.     

Cyclic voltammetry at microstructured electrodes

We present the theoretical treatment of cyclic voltammograms at microstructured electrodes. Calculations of voltammograms permit the determination of electrochemical parameters of redox systems in a single cell in parallel with the determinations of the spectroscopic parameters. The structural parameters of the electrode can be determined using the theoretical treatment presented if the electrochemical parameters of the redox system are known. Furthermore, lithographic-galvanic (LIGA) structures can be used as a model for microporous electrodes. Regression analysis was used to compare experimental and calculated cyclic voltammograms as well as to determine the electrochemical and spectroscopic parameters. A modified Randles-Sevčik equation has been derived to described the peak current dependence of cyclic voltammograms at micro-structured electrodes for both reversible and quasi-reversible charge transfer.     

Characterization of the GM1 pentasaccharide-Vibrio cholera toxin interaction using a carbohydrate-based electrochemical system

Antibody- or DNA-based electrochemical systems have been developed widely for several decades, while carbohydrate-based electrochemical systems have been rarely reported. Herein, we used an electrochemical detection system to understand the molecular relationships in carbohydrate-protein interactions that can provide useful information about biological processes in living organisms. This system was also helpful for the development of potent biomedical agents. Electrochemical detection was achieved through the observation of electrochemical response changes of ferrocyanide solution that resulted from the interaction of carbohydrate and protein using a modified GM1 pentasaccharide containing an anchoring thiol group that was directly immobilized on a gold electrode. As the concentration of the GM1 pentasaccharide increased, the current decreased gradually and saturated after 2 nM. We also found that the drop in current depended on the size of the carbohydrate (larger size of the carbohydrate denoted a higher slope of the current reduction), indicating that the current could be modulated by the molecular size of the carbohydrate as well as its concentration. This system was able to detect very low concentrations of carbohydrate (down to 20 fM), which highlighted the advantage of the electrochemical system. Interestingly, we found that a potential shift at the maximum current occurred upon interaction with cholera toxin proteins. By comparing results for different sizes of GM1 analogues, we surmise that the potential shift is closely associated with the specificity for the carbohydrate-protein interaction. Collectively, a carbohydrate-based electrochemical system can be leveraged for the facile and rapid analysis of carbohydrate-protein interactions.     

Characterizations of nickel mesh and nickel foam current collectors for supercapacitor application

Nickel (Ni) current collectors having a three-dimensional and porous structure are considered attractive contestants for high-efficiency supercapacitors. Therefore, Ni current collectors have a unique architecture and outstanding electrochemical properties. This study reports the effect of electrochemical characterizations on the electrochemical behavior and physical properties of Ni mesh and Ni foam. Cyclic voltammetry (CV) and galvanostatic charge discharge (GCD) are used to examine the electrochemical properties and life span of the Ni mesh and Ni foam as a current collector in a supercapacitor application. Structural and microstructural characterizations are performed to verify the formation of an oxide layer after 1000 cycles of CV analysis. Results show that Ni foam can increase the yield electrochemical performance of the supercapacitor. Ni foam present better efficiency (35 F g⁻¹) compared to the Ni mesh (12 F g⁻¹) at 10 mV s⁻¹ scan rate by using 2 mg imaginary mass of active material. This result shows that Ni foam has good electrochemical performance and reversibility, higher pseudocapacitance, weaker polarization, and enhance rotating performance as to Ni mesh. The porous structure of Ni foam is in control for improving of the electrochemical properties, therefore, the electrochemical region was increased and shortened ion diffusion. Structural analysis shows that Ni mesh and Ni foam are oxidized after the electrochemical analysis and transformed to nickel oxide hydroxide (NiOOH). Higher specific surface area between the electrode and electrolyte leads to excellent electrochemical and pseudocapacitive performance of the Ni foam compared to the Ni mesh, even if the materials of current collectors are the same. Hence, the physical structure of the current collectors have a critical part in improving the energy density of the supercapacitor.     

How to avoid interfering electrochemical reactions in ESI‐MS analysis

The presence of electrochemical reactions occurring in an electrospray processes at the point where the current enters the liquid is discussed since the early 1990's. This current transfer to the liquid results in oxidation or reduction of either electrolyte species in the liquid sprayed or of the electrode material in contact with the liquid. As a result, new chemical species are generated. These products of the electrochemical reaction might be detected as altered species in mass spectra; they might be volatile and not recognized at all or accumulate on the electrode surface and cause cross contamination later on. In other cases, it might happen that the products of the electrochemical reactions are the only detectable species formed from an otherwise nondetectable analyte. An electrospray setup in which electrochemical reactions do not interfere with the analyte under investigation excludes the electrochemical reaction as source of sample contamination and sample altering and may serve as reference setup for experiments focused on the electrochemical reaction itself. We present a simple and inexpensive current coupling approach and specify operation conditions for which any impact of the electrochemical reaction on the sample under investigation is inherently excluded. On the basis of a practical example, we show the impact of the electrochemical reaction on sample composition and demonstrate the benefit of using the proposed current coupling method. Because of the obvious benefit of this method and its simple realization, it has the potential to be employed as standard feeding approach, especially for electrosprays operated at small flow rates.     

Accelerating electrochemistry with metal nanowires

Scalable, solution-phase syntheses of metal nanowires are enabling their increased use in electrochemical processes. This review highlights recent results demonstrating how metal nanowires can exhibit better durability and higher activity than traditional metal nanoparticle electrocatalysts on carbon supports. Metal nanowires can also form interconnected two-dimensional and three-dimensional (3D) networks that eliminate the need for a carbon support, thus eliminating the detrimental effects of carbon corrosion. Porous 3D networks of nanowires can be used as flow-through electrodes with the highest specific surface areas and mass transport coefficients obtained to date, enabling dramatic increases in the productivity of electrochemical reactions. Nanowire networks are also serving as 3D current collectors that improve the capacity of batteries. The tunable surface structure and dimensions of metal nanowires offer researchers a new opportunity to create electrodes that are tailored from the atomic scale to the microscale to improve electrochemical performance.     

A pH-controllable electrochemical molecule switch employing a new electrochemical measurement system as switching transducer

A new design concept of electrochemical pH-controllable molecular switch is presented by utilizing a new electrochemical measurement system as switching transducer. A pH sensor is connected in series between the terminal points of the working and counters electrodes of a potentisostat, and immersed in the solution together with a reference electrode, establishing a novel electrochemical measurement system. In this system, the variation of pH-controllable interface potential at the pH-sensing film/solution interface can be converted to current response when amperometry technique is employed. Based on this unique current–potential relationship, a pH-controllable switch is designed to monitor the protonation and deprotonation reaction of pH-sensing molecule. The current direction interchanges between positive and negative via pH control, illustrating a reversible conformation transition between protonated state and deprotionated state of molecule. The magnitude of current value represents the degree of protonation and deprotonation reaction of molecule. The strategy is successfully demonstrated with a remarkably reversible polyaniline-based pH-controllable switch, which confirms the feasibility of the novel electrochemical measurement system as switching transducer for designing electrochemical pH-controllable switches. This study may open up a potential avenue to construct the electrochemical pH-controllable switches.     

基于电化学噪声研究模拟海洋大气环境下304不锈钢的点蚀行为

基于电化学噪声技术建立了不锈钢海洋大气点蚀监测系统,利用该系统对处于干湿循环环境下不锈钢的点蚀行为进行监测. 使用时域谱图、时域统计、频域谱图和散粒噪声理论等分析方法对采集到的电化学噪声数据进行处理分析,并结合动电位极化法,形貌分析法共同研究不锈钢的点蚀行为. 研究结果表明,304不锈钢在模拟海洋大气环境下的点蚀行为分为钝化、亚稳态点蚀和稳态点蚀三个阶段. 在钝化阶段,电位电流噪声信号出现少量的同步异向波动,腐蚀事件发生频率高,平均电量低;在亚稳态点蚀阶段,电位电流噪声信号出现大量的同步同向波动,腐蚀事件发生频率降低,平均电量上升,通过扫描电镜观察蚀点;在稳态点蚀阶段,电位电流噪声信号不仅存在大量的同步同向波动,还出现了同步异向波动,腐蚀事件发生频率较低,平均电量大幅度上升,通过扫描电镜观察到电极表面出现小而浅的蚀点. 而动电位极化法可以证实304不锈钢点蚀的发生. 两种分析方法所得结果具有较好的一致性,证明该监测系统很好地实现了对模拟海洋大气环境下304不锈钢点蚀行为的连续监测,并能判断点蚀的发生.     

Fabrication and Characterisation of Leak-Tight Glassy Carbon Electrodes,Sealed in Glass Employing Silicon Coating,for Use in Electrochemical Detection

Abstract

Glassy carbon discs have been coated with silicon in a chemical vapour deposition process to obtain leak-tight electrodes, sealed in glass. Electrodes with coatings thicker than 5μm prove to be leak-tight in contrast with uncoated ones. Silicon-coated electrodes show faster decay of charging current, less noise and decreased background current. Leak-tightness and electron microscope information correlate well with the electrochemical data. All results can be ascribed to the absence of a void between glassy carbon and glass at Si-coated electrodes. By silicon coating, signal-to-noise ratios are improved with a factor of about 5, as is demonstrated for catecholamines and metabolites in liquid chromatography with electrochemical detection.