超重力场中水溶液的电化学反应特性

以Fe3+/Fe2+电对体系和铁氰酸根离子为研究对象, 分别采用循环伏安法、线性扫描伏安法和计时电流法等考察了在超重力条件下Fe3+/Fe2+电对体系和铁氰化钾离子的电化学行为, 为认识和发展超重力场中电化学反应过程的研究提供了一定的理论及实验依据.     

暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程

对硝基苯硫酚是表面增强拉曼光谱研究中最常用的探针分子之一,对硝基苯硫酚在电极表面电化学还原反应的研究有助于对芳香族硝基化合物还原机理的认识. 本文应用暂态电化学-表面增强拉曼光谱技术,研究了对硝基苯硫酚在循环伏安和计时电流法过程中的表面增强拉曼光谱. 结果表明,实验实现了完全与电化学检测时间分辨率同步的表面增强拉曼光谱检测,以最快5毫秒的时间分辨率研究了对硝基苯硫酚分子在金电极表面的还原过程. 结果分析推测其此反应过程极快,在5毫秒的时间分辨率下仍难以捕获其中间物种. 本研究为人们更深层次研究和认识硝基苯类化合物电化学还原过程提供了参考和方向.     

Electrochemical Oxidation of Ammonia on Ir Anode in Potential Fixed Electrochemical Sensor

Ir catalyst possesses a good electrocatalytic activity and selectivity for the oxidation of NH3 and/or NH4OH at Ir anode in the potential fixed electrochemical sensor with the neutral solution. Owing to the same electrochemical behavior of NH3 and NH4OH in a NaClO4 solution, NH4OH can be used instead of NH3 for the experimental convenience. It was found that the potential of the oxidation peak of NH4OH at the Ir/GC electrode in NaClO4 solutions is at about 0.85 V, and the current density of the oxidation peak of NH4OH is linearly proportional to the concentration of NHaOH. The electrocatalytic oxidation of NH4OH is diffusion-controlled. Especially, Ir has no electrocatalytic activity for the CO oxidation, illustrating that CO does not interfere in the measurement of NH4OH and the potential fixed electrochemical NH3 sensor with the neutral solution, and the anodic Ir catalyst possesses a good selectivity. Therefore, Ir may have practical application in the potential fixed electrochemical NH3 sensor with the neutral solution.     

Recent Advances in Real-Time Analysis of Electrochemical Reactions by Electrochemical Mass Spectrometry†

Electrochemical mass spectrometry (EC-MS) is a powerful tool to capture and analyze the intermediates and products during electrochemical reactions. This hyphenated technique combines electrochemistry with mass spectrometry using specific apparatuses, which helps researchers study mechanisms of redox reactions by in situ detecting chemical composition changes. Recently, various EC-MS methods have been applied in a series of electrochemical reactions to reveal the mechanisms, mainly in the areas of electrochemical sensors, organic electrochemistry, and electrocatalysis. In this review, we intend to summarize the recent advances in real-time analysis of different types of electrochemical reactions by EC-MS and offer an outlook on the perspectives in these areas.      

钇在二甲基亚砜溶剂中的电化学行为

研究了ＹＣｌ３－ＬｉＣｌＯ４－ＤＭＳＯ（二甲基亚砜）体系电导率与温度的关系,及钇在Ｐｔ和Ｃｕ电极上的电化学行为。结果表明,Ｙ＾３＋在Ｐｔ和Ｃｕ电极上可一步不可逆还原为Ｙ,在铜电极上于－２．５００Ｖ（ｖｓ ＳＣＥ下恒电位电解,可获得粘附性好、Ｙ含量达９７．９％（质量分数）的均匀沉积膜。利用循环伏安法、计时电流法、计时电位法测定了Ｙ＾３＋离子在２９８Ｋ下,ＹＣｌ３－ＬｉＣｌＯ４－ＤＭＳＯ溶液中的扩散系     

Electrochemical substitution of hydrogen in ferrocene

Interaction of radicals R^. formed in anode decarboxylation of carboxylate anions with the ferricinium cation generated at the same electrode leads to alkylferrocene derivatives. A similar reaction of the ferricinium cation with radicals formed from dibasic acids or their semiesters yields esters of ferrocenyl- containing carboxylic ácids. Monosubstituted ferrocene, particularly those containing electron donor substituents, undergo further substitution to give di- and polysubstituted products. The procedures are described that lead to predominant isolation of either mono- or poly-substituted products.The results of qualitative and quantitative analyses of the polymethylation products show that orienting effects by the substituents are the same for radical substitution in the ferricinium cation and for electrophilic substitution in ferrocene.     

电化学生物传感器在发酵领域中的应用

本文综述了近10年来电化学生物传感器在发酵领域中的研究及应用。首先介绍了电化学生物传感器的基本原理及分类,然后对发酵领域中应用和研究最为广泛的酶电极以及微生物电极传感器进行了分类描述,并重点介绍和归纳了葡萄糖、乳酸、酒精以及甘油生物传感器的研究现状,集中探讨了两类传感器的抗干扰性与选择性等特性。     

Electrochemical Impedance Spectroscopic Analysis on the Electrochemical Deposition of Lead Dioxide in Acidic Medium

Electrochemical deposition of pure lead dioxides and modified lead dioxides incorporated with As(V) on a gold electrode was investigated by cyclic voltammetric, in-situ electrochemical impedance spectroscopic, and reflective UV-vis spectroelectrochemical techniques. The focus was given to analyze electrochemical impedance spectroscopic data obtained under various deposition conditions, i.e.,different deposition potentials.     

Electrochemical Fluoro-Chalcogenation

Electrochemical fluoro-chalcogenation (S, Se) of alkenes and alkynes, and recycle use of in situ generated PhSeF for allylic fluorination are discussed.     

Electrochemical immunoassays

Immunoassays (IA) use the specific antigen antibody complexation for analytical purposes. Radioimmunoassays (RIA), fluorescence immunoassays (FIA) and enzyme immunoassays (EIA) are well established in clinical diagnostics. For the development of hand-held devices which can be used for point of care measurements, electrochemical immunoassays are promising alternatives to existing immunochemical tests. Moreover, for opaque or optically dense matrices electrochemical methods are superior. Potentiometric, capacitive and amperometric transducers have been applied for direct and indirect electrochemical immunoassays. However, due to their fast detection, broad linear range and low detection limit, amperometric transducers are preferred. Competitive and non-competitive amperometric immunoassays have been developed with redox compounds or enzymes as labels. This review will give an overview of the most frequently applied principles in electrochemical immunoassays. The potential of an indirect competitive amperometric immunoassay for the determination of creatinine within nanomolar range and the circumvention of the most serious problem in electrochemical immunoassays, namely regeneration, will be discussed.     

Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry

Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long‐term functionality of electrodes. In‐depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO₂ into CO₃^2?. We report the adaptation of a DEMS system for online CO₂ detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO₃^2? as CO₂ in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon‐supported nickel boride (Ni_xB/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution.     

Electrochemical metamaterials

Journal of Solid State Electrochemistry -     

Electrochemical Capacitors

The current literature sources on the electrochemical capacitors, which are divided into the film (dielectric), electrolytic, and supercapacitors, are reviewed. The supercapacitors are in turn subdivided into the double-layer capacitors, which use the EDL recharge on a highly-developed interfacial surface of electrodes; pseudocapacitors, where the charge is stored in a faradaic pseudocapacitance of sufficiently reversible redox reactions and the EDL capacitance; and hybrid capacitors, which employ a variety of electrodes. A macrokinetic theory of operation of double-layer capacitors is considered. Effect of various factors on the properties of electrodes utilized in supercapacitors is analyzed. A novel type of hybrid capacitor, which has a negative electrode of activated carbon cloth and a PbSO₄/PbO₂ positive electrode, is proposed. A theory of capillary equilibrium in hermetically sealed electrochemical capacitors is considered. Specific features of the application of voltammetric and impedance methods to studying electrochemical processes in supercapacitors are revealed. Characteristics of electrochemical capacitors and batteries are compared.     

Electrochemical nanomachining

Free of tool wear, residual stress, and surface damage, electrochemical nanomachining (ECNM) plays an irreplaceable role in advanced manufacturing, via the production of ultra-large scale integrated circuits, microelectromechanical systems, and various nanodevices. The principles of ECNM are classified as electroforming, electrolysis, electrochemical corrosion, and etching. The working modes of ECNM include direct writing and template forming. ECNM applies to not only the fabrication of three-dimensional nanostructures but also the production of super-smooth surfaces with roughness no higher than 1 nm. Both of these are crucial in modern advanced manufacturing. The key point of ECNM is the spatial confinement of electrochemical reactions. This review will focus on this point and briefly introduce the principles, methodologies, applications, and prospects of ECNM.     

Electrochemical immunoassays

Immunoassays (IA) use the specific antigen antibody complexation for analytical purposes. Radioimmunoassays (RIA), fluorescence immunoassays (FIA) and enzyme immunoassays (EIA) are well established in clinical diagnostics. For the development of hand-held devices which can be used for point of care measurements, electrochemical immunoassays are promising alternatives to existing immunochemical tests. Moreover, for opaque or optically dense matrices electrochemical methods are superior. Potentiometric, capacitive and amperometric transducers have been applied for direct and indirect electrochemical immunoassays. However, due to their fast detection, broad linear range and low detection limit, amperometric transducers are preferred. Competitive and noncompetitive amperometric immunoassays have been developed with redox compounds or enzymes as labels. This review will give an overview of the most frequently applied principles in electrochemical immunoassays. The potential of an indirect competitive amperometric immunoassay for the determination of creatinine within nanomolar range and the circumvention of the most serious problem in electrochemical immunoassays, namely regeneration, will be discussed.     

电化学分析

本文是《分析试验室》定期评述中“电化学分析”第五篇评述文章，它评述了从１９９５年１月至１９９６年１２月期间我国电化学分析的进展，内容分基础与理论和方法与应用研究两部分，后者包括极谱与伏安法，络合吸附与催化波，单扫示波极谱与示差脉冲极谱法，溶出分析法，示波分析法，微电极，超微电极与化学修饰电极，离子选择电极与各类传感器，光谱电化学，扫描隧道显微法和液－液界面电化学分析，色谱电化学及电泳，免疫法，电位     

电化学分析

本文是《分析试验室》定期评述中电化学分析第六篇评述文章。它评述了从１９９７年１月至１９９８年１０月期间我国电化学分析的进展。内容分基础理论与应用研究两大部分。前者包括电化学分析理论研究、电分析化学中的化学计量学方法,后者包括极谱与伏安法,络合吸附波与催化波,线性扫描伏安法,示差脉冲伏安法,吸附溶出分析法,示波分析法,微电极、超微电极与化学修饰电极,离子选择电极与各类传感器,光谱电化学,扫描隧道显微法和液／液界面电化学分析,电化学检测／电泳、色谱技术,电化学免疫法,电位分析法及其它等。共引用文献４８３篇。     

电化学分析实验中的数据处理

编写了一套电化学分析数据处理软件 ,旨在实现数据处理的计算机自动化 ,以减少在数据处理过程中所用的时间及提高结果的精确度。介绍了该软件的基本原理、使用方法和应用实例