电化学分析的发展及应用

评述了从2001年1月-2002年12月间我国电化学分析发展的概况。内容分极谱与伏安法，微电极、超微电极和修饰电极，离子选择性电极与传感器，示波分析法，电泳及色谱电化学，光谱电化学、电致发光，扫描电化学显微镜及石英晶体微天平，化学计量学方法，电位分析及其它和仪器装置及实验技术等。引用文献591篇。     

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

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     

聚脱氧腺苷酸/还原石墨烯纳米复合膜电化学传感器检测核黄素

以含32个碱基的聚脱氧腺苷酸(A32)作为黏合剂,将水合肼还原的石墨烯(RGO)固定在金(Au)电极表面,制备A32/RGO纳米复合膜电化学传感器.利用循环伏安法和交流阻抗法对传感器制备过程进行表征,并用循环伏安法和微分脉冲伏安法研究了该传感器的电化学行为.研究结果表明,与裸Au电极和A32修饰的Au电极相比,RGO/A32/Au电极对核黄素有较高的电化学活性,其还原峰电流与核黄素的浓度在0.025~2.75μmol/L范围内呈线性关系,检出限(S/N=3)为15 nmol/L.该传感器具有灵敏度高、抗干扰能力强及稳定性好等优点,可用于人尿中核黄素的分析测定.     

隐丹参酮的电化学性质及其与DNA相互作用的研究

利用循环伏安法(CV)、线性扫描伏安法(LSV)、方波伏安法(OSWV)等电化学技术研究了隐丹参酮在玻碳电极(GCE)上的电化学氧化过程,并用计时电量法和恒电位库仑电解法等对其在电极表面的吸附行为及氧化还原机理进行了探讨.此外利用自组装DNA修饰玻碳电极研究了隐丹参酮与DNA之间的相互作用.     

电化学分析

本文是《分析试验室》定期评述中“电化学分析”第二篇和“离子选择电极”第三篇评述文章,它第一次将上述两课题合并为“电化学分析”课题。它对1987～1990年间(其中离子选择电极为1989～1990年)国内电化学分析的进展作了全面评述。内容包括:基础理论研究、极谱与伏安分析、溶出分析、化学修饰电极、液-液界面电化学、色谱电化学与流动注射分析检测、光谱电化学、离子选择电极、库伦分析及其他分析方法     

金刚石薄膜电化学

金刚石由于其特殊的物理与化学性质,早在几百年前就吸引了人们对它的关注.化学气相沉积(chemical vapor deposition,CVD)法制备的高掺杂硼复合多晶金刚石薄膜,为金刚石薄膜在电化学中的应用开辟了新的领域.作为新型碳素电极材料,高掺杂硼复合多晶金刚石薄膜具有许多目前使用的电极材料所不可比拟的优异特性如:宽电化学势窗,低残留电流,极好的电化学稳定性以及表面不易被污染等.本文综述了高掺杂硼复合多晶金刚石薄膜电极在电化学中的几个重要应用,包括电分析、电合成及电化学法处理废水等.     

化学修饰电极的研究 Ⅵ.聚乙烯二茂铁膜电极的表面表征和组成

本文研究了用等离子体法在玻璃炭上制备聚乙烯二茂铁(PPVF)膜电极的伏安行为及其XPS分析.结果表明PPVF膜电极的伏安行为和组成均与其制备条件有关.PPVF膜电极的二茂铁与二茂正铁之间的氧化还原反应是在电极上快速进行电荷转移的电化学过程.PPVF膜电极的伏安特性受膜中电活性物量、膜的厚度和组成的影响.伏安法和XPS法都可以用来表征PPVF膜制备条件的变化.     

Nano-NiO/Nafion膜修饰电极的电化学行为研究

纳米材料修饰电极是将纳米科学与化学修饰电极有机结合起来的一个新的研究领域.将纳米材料的独特性能应用到电分析化学中,成为电化学分析领域一个研究热点.抗坏血酸的分析方法有光度法、滴定法和电化学分析法~([1,2])等.在裸电极上,抗坏血酸的电化学氧化存在较高的过电位,因此,电化学分析中一般采用化学修饰电极.     

《电化学方法原理和应用》

由北京大学邵元华、中国科学院长春应用化学研究所朱果逸、董献堆、张柏林翻译的A.J.Bard和L.R.Fau lkner的《电化学方法原理和应用》(第二版)已于2005年5月由化学工业出版社出版。该书第一版于1980年出版以来,得到全世界电化学及电分析化学界广泛好评,被许多大学选作高年级和研究生的教科书。第二版在第一版基础上作了重要的增补,主要包括近年来快速发展的新领域:超微电极的应用、完整表面上的电化学现象、修饰电极、现代电子转移理论、扫描探针方法、液相色谱电化学联用方法(LCEC)、阻抗谱学、现代形式的脉冲伏安法和各种谱学电化学技…     

Amperometric enzyme electrodes in analytical chemistry

Summary An overview is given of works on the construction and application of amperometric enzyme electrodes for the determination of metabolites in biological solutions. The following electrodes are dealt with: monoenzyme and polyenzyme electrodes involving amperometric detection of hydrogen peroxide, bienzyme electrodes with oxidase-peroxidase, electrodes based on organic metals and chemically modified electrodes, dehydrogenase electrodes, amperometric hydrolase electrodes and highly sensitive electrodes involving chemical amplification. Biocatalytic stripping and macrokinetic behaviour of the electrodes are discussed.

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Amperometrische Enzymelektroden in der analytischen Chemie

     

The electrochemistry of gold–platinum alloys

The electrochemical properties of gold, platinum and gold–platinum alloy electrodes under different heat treatment conditions have been studied in 0.5 M H₂SO₄ and 0.5 M NaOH. The electro-oxidation of 0.1 M ethylene glycol in 0.5 M NaOH at these electrodes has also been studied. It was found that all the gold–platinum electrodes are more active for ethylene glycol electro-oxidation than both pure gold and platinum, and that the gold–platinum electrodes in the solid solution condition are more active than the two-phase electrodes. Poisoning of all the electrodes occurs during electrolysis of ethylene glycol at a fixed potential. Potential pulsing is successful in removing the poisoning species formed at the pure gold and pure platinum electrodes. High apparent current densities are found during the first few cycles at the Au–Pt alloy electrodes. These high current densities are also associated with more severe poisoning – than at both pure gold and platinum – and longer cleaning cycles are needed to remove the poisons at these electrodes.     

Hydrogel-based flexible micro-reference electrodes for use in alkaline and neutral pH solutions

Two types of nonbreakable, flexible micro-reference electrodes filled with gel-electrolytes were prepared for use in solutions with alkaline and neutral pH. The electrodes are intended for electrochemical measurements, in which chloride-free conditions are important. Due to the flexible, bendable construction of the electrodes, electrochemical experiments at locations difficult to access with common reference electrodes are enabled. Hg|HgO-type electrodes were prepared from amalgamated Au wires, followed by oxidation of the amalgam, which is mounted in a PTFE tube filled with 0.1M NaOH solution immobilized in a PAA-g-PEO gel. The potential of this type of electrode was found to be 0.162?±?0.002 V (SHE) at room temperature. Cu|CuSO₄ electrodes, consisting of a Cu wire immersed in a saturated CuSO₄ solution jellied with gelatin, showed a stable open-circuit potential of 0.312?±?0.001 V (SHE). Further characterization of the electrodes was performed in terms of electrochemical impedance spectroscopy and micro-polarization measurements. As an alternative to the flexible electrodes, rigid electrodes in glass enclosure were fabricated in analogy to the flexible-type electrodes.     

Comparison of Trap‐state Distribution and Carrier Transport in Nanotubular and Nanoparticulate TiO2 Electrodes for Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSCs) with nanotubular TiO₂ electrodes of varying thicknesses are compared to DSCs based on conventional nanoparticulate electrodes. Despite the higher degree of order in one‐dimensional nanotubular electrodes, electron transport times and diffusion coefficients, determined under short‐circuit conditions, are comparable to those of nanoparticulate electrodes. The quasi‐Fermi level, however, is much lower in the nanotubes, suggesting a lower concentration of conduction band electrons. This provides evidence for a much higher diffusion coefficient for conduction band electrons in nanotubes than in nanoparticulate films. The electron lifetime and the diffusion length are significantly longer in nanotubular TiO₂ electrodes than in nanoparticulate films. Nanotubular electrodes have a trap distribution that differs significantly from nanoparticulate electrodes; they possess relatively deeper traps and have a characteristic energy of the exponential distribution that is more than two times that of nanoparticulate electrodes.     

Amineptine Plastic Membrane Electrode Based on its Ion Associate with Tetraphenylborate and Phosphomolybdic Acid

New amineptine hydrochloride (Am-Cl) ion-selective electrodes (conventional type) based on amineptinium-tetraphenylborate (I) and amineptinium-phosphomolybdate (II) were prepared. The electrodes exhibited mean slopes of calibration graphs of 57.9?mV and 53.8?mV per decade of (Am-Cl) concentration at 25?°C for electrodes (I) and (II), respectively. The electrodes can be used within the concentration range 3.16×10^?5?10^?2?M (Am-Cl) at a pH range of 2.0–3.9 for both electrodes. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficients of the electrodes, which were 0.00172?V?°C^?1 and 0.00091 V?°C^?1 for (I) and (II) electrodes, respectively. The electrodes showed a very good selectivity for (Am-Cl) with respect to a number of inorganic cations and sugars. The standard addition method is successfully applied to determine (Am-Cl) in pure solutions and in amineptine-containing tablets.     

Diazonium salts: Stable monolayers on gold electrodes for sensing applications

The modification of gold electrodes with 4-carboxyphenyl diazonium salts to form stable layers for sensing applications is reported. Electrochemical reduction of 4-carboxyphenyl diazonium salts on gold electrodes yielded more stable layers than alkanethiol self-assembled monolayers in terms of extremes of electrode potential, sonication and with time. The application of the 4-carboxyphenyl modified electrodes for electrochemical sensing, which typically requires short chain alkanethiols on gold electrodes, is demonstrated via the covalent attachment of oligopeptides for the selective detection of Cu²⁺, Cd²⁺ and Pb²⁺. The diazonium salt/peptide modified gold electrodes not only had greater stability but also performed with lowest detected concentration to alkanethiol/peptide modified electrodes and with far greater sensitivity than the metal ion sensors when diazonium salt/peptide modified similar glassy carbon electrodes were employed.     

Application of Ion-Selective Electrodes as Reference Electrodes

Abstract

Reference electrodes limiting interfering effects of conventional reference electrodes on the measurement involving ion-selective electrodes have been developed. They are constructed of a plastic body with porous plug or sleeve junction. Solid state, low impedance, ion-selective electrodes (cupric, cadmium, fluoride) in the equilibrium of corresponding ion solution are used as the half-cells. The absence of interfering ions in the electrolyte allows the determination of the ion of interest at extremely low levels without interference. The electrodes have good reproducibility and stable intercomparison potentials of ± 0.2 mV. The performance of the electrodes has been tested for the measurement of sub-ppm halide levels. Data on stability, reproducibility, effects of temperature, ionic strengthand pH is presented and compared to that of conventional reference electrodes.     

The development of fluoride-sensitive membrane electrodes : Part I. Membranes containing thorium,lanthanum or calcium fluoride

Fluoride-sensitivc membrane electrodes of the Pungor type are described. In these electrodes, a fluoride precipitate is incorporated in a silicone rubber membrane; fluorides of thorium, lanthanum and other rare earths, and calcium have been examined. The method of preparing the precipitate is important; an excess of metal is vital for correct functioning of the final electrode. The most reliable results were obtained with calcium fluoride electrodes, though their sensitivity was less than that of the best lanthanum fluoride electrodes. With these electrodes, linear responses are obtained in the l0^-2–10^-4M fluoride range.     

Preparation and Supercapacitive Performance of Lead Dioxide Electrodes with Three-Dimensional Porous Structure

The three-dimensional porous structure PbO₂ electrodes (3D-PbO₂ electrodes) were prepared in the lead nitrate solution by potentiostatically electrodeposition method using oxygen bubble as dynamic template, which can be used as the positive materials of the supercapacitors. The morphology and structure of 3D-PbO₂ electrodes were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). The supercapacitive performance of 3D-PbO₂ electrodes were investigated by cyclic voltammetry (CV), galvanostatic charge-discharge tests (GCD) and electrochemical impedance spectroscopy (EIS). The specific capacitance of 3D-PbO₂ electrodes can reach 195.6 F g^–1 at 0.2 A g^–1, which is 2.8 times higher than that of Flat-PbO₂ electrodes (68.8 F g^–1). The charge transfer resistance (R_ct) of 3D-PbO₂ electrodes (8.21 Ohm cm^–2) is lower than that of Flat-PbO₂ electrodes (21.32 Ohm cm^–2). The excellent supercapacitive performance of 3D-PbO₂ electrodes can be attributed to the three-dimensional porous structure, which can enlarge the active surface area of lead dioxide electrodes and promote the electrolyte diffusion and electrons propagation.     

Surface activation of plasma-patterned carbon nanotube based DNA sensing electrodes

We have studied the effect of treatment of multiwalled carbon nanotubes (MWCNTs) for use in DNA-based biosensors with oxygen plasma. Well-patterned MWCNT electrodes were photolithographically fabricated on glass substrates. Pure oxygen was used for etching and functionalization of the MWCNT film in a lab-made plasma chamber. The resulting electrodes exhibited a dramatic change in the morphology of their surface, the chemical composition, and the electrochemical properties in terms of peak current and peak potential separation. The electrodes also showed increased DNA immobilization efficiency and much higher sensitivity in the detection of target DNA as compared to non-treated MWCNT electrodes. Plasma treatment was optimized and electrodes were characterized by atomic force microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, and differential pulse voltammetry.