Corosion Potential Imagingat the InterfaceofCoating／MetalbyaNewElectrochemicalTechnique

在绝大多数环境下，聚合物／金属界面的腐蚀破坏的本质是电化学过程，因此，不少电化学技术，包括直流稳态技术和交流阻抗技术等被广泛用于研究金属／聚合物界面的腐蚀破坏机制，评测有机涂层的耐蚀性能．然而，由于聚合物／金属界面腐蚀破坏的“闭塞”条件和聚合物膜层的高绝缘性，传统的电化学方法均不能直接获得聚合物／金属界面二维空间的腐蚀电位分布，难以直接研究聚合物／金属界面的腐蚀破坏过程及相关的影响因素．聚合物／金属界面腐蚀电位的测量有助于研究聚合物／金属等复合材料界面腐蚀破坏机理，评测有机聚合物涂覆层的耐蚀性能．本文提出一种微计算机控制的阵列电极技术，用于原位测量金属／聚合物界面电位分布．首次建立了８×８阵列电极和微机控制的阵列电极测量系统，可直接测量聚合物／金属界面腐蚀电位的二维分布．由此可深入研究有关腐蚀物种在聚合物相内传输过程，聚合物涂层的不均一性及缺陷分布，以及聚合物／金属界面腐蚀的发生、发展机制．应用阵列电极技术首次在原位获得聚合物涂层的缺陷分布及不均一性，并考查了聚合物涂层缺陷对诱导聚合物／金属界面腐蚀破坏的关系．阵列电极技术还首次提供了在聚合物／金属界面腐蚀破坏发展过程中阴、阳极同时存在，共同发展的直接的     

导电聚合物的纳米结构及其在生物医学领域的应用

由于表面效应、小尺寸效应和量子效应,使纳米结构的导电聚合物材料与传统聚合物材料相比,显示出更优越的性能。基于神经组织对电场和电刺激敏感性,使得导电聚合物纳米材料在生物医学应用方面很有前景。本文综述了纳米结构的导电聚合物的合成方法,及其在生物医学领域的应用。合成方法主要关注于硬模板法、软模板法和无模板自组装法,以及这些方法中导电聚合物纳米结构的形成机理。总结了具有纳米结构的导电聚合物,如纳米颗粒、纳米纤维和纳米管等作为神经电极涂层材料和生物传感器等方面的应用。     

化学修饰电极的研究Ⅱ.聚乙烯二茂铁膜修饰电极的新极谱循环图

化学修饰电极是近年来电化学领域中新发展起来的活跃研究方向。在电极表面的化学修饰方法中,聚合物涂层法是近二、三年才兴起的研究课题,其中把电活性氧化还原体固着于电极表面制成聚合物薄膜电极尤其引人注意。我们用等离子体聚合法成功地制出了聚乙烯二茂铁化学修饰电极。化学修饰电极的表面可用各种能谱方法表征,但电化学方法,特别是循环伏安法,是更为灵敏有效的方法。各类新极谱法是近年来新发展的半算符电分析法。用新极谱法研究化学修饰电极未     

聚合物在离子选择电极上的应用

本文概述了聚合物膜离子选择电极的发展、制备、应用等方面的研究情况。分别对固态膜类和液膜类聚合物膜离子选择电极的优缺点和发展前景进行了分析,并讨论了聚合物在膜电极中的作用,以及聚合物的结构对膜电极性能的影响。     

功能性聚合物薄膜修饰电极

化学修饰电极是当前在电化学、电分析化学方面十分活跃的研究领域。功能性聚合物薄膜由于其特殊的化学结构赋予其许多独特的功能,诸如选择性、分子识别、pH敏感、光化学敏感等;功能性聚合物修饰电极可以赋予电极许多特殊功能,拓展电极的应用范畴,故而备受关注。本文分别从分子印迹聚合物传感器和生物酶传感器制备的角度,综述在电极表面构筑功能性聚合物薄膜的材料以及方法,重点论述电泳沉积技术在电极修饰中的新应用。这些功能性聚合物薄膜在电极表面的构筑方法可以广泛的拓展到其它传感器的制备中,并指导特殊的传感器的制备,具有重要的研究和应用价值。     

导电聚合物酶电极的研究概况

简述导电聚合物酶电极的制备及其在生物传感器领域的应用，主要包括导电聚合物固定酶的方法、反应机理、以及导电聚合物酶电极的最近进展等。     

Nafion聚合物涂层碳纤维微电极微分脉冲伏安法测定咖啡因的研究

咖啡因属生物碱,是中枢神经兴奋药物之一~[1]。目前,咖啡因的常用测定方法有紫外分光光度法~[2]和高效液相色谱法~[3]等.电化学测定方法已有报道~[4～6],但尚未见到利用Nafion聚合物涂层碳纤维微电极的伏安测定方法.本文提出了一种简单易行的碳纤维微电极及其Nafion聚合物涂层的制造方法.得到了利用该电极微分脉冲伏安法测定咖啡因的最佳体系为     

导电聚合物酶极的研究概况

简述导电聚合物酶电极的制备及其在生物传感器领域的应用，主要包括导电聚合物固定酶的方法，反应机理，以及导电聚合物酶电极的最近进展等。     

聚合物薄膜化学修饰电极

本文评述了聚合物薄膜修饰电极的研究进展,引文24篇。文中讨论了聚合物薄膜修饰电极的特征、电极过程、各种类型以及其应用。     

金属氧化物涂层钛阳极的研究*

金属氧化物涂层钛阳极是指在以钛为阳极的基体表面涂上金属氧化物的电极,简称DSA。本文综述了钛基金属氧化物涂层电极的研究进展,包括钛基钌系涂层电极、钛基锡系涂层电极、钛基铅系涂层电极,以及其它氧化物涂层电极。评述了多元化钛基涂层的性能、各种涂层制备方法的优势与不足,阐明了掺杂稀土以及添加中间层对钛阳极的影响,同时展望了钛基金属氧化物涂层电极的发展方向。     

Dispersed mercury microelectrodes using non-conducting polymer coatings

The preparation and use of polymeric dispersed mercury electrodes were investigated. Both micro- and macroelectrodes were considered and it was found that the polymer-coated electrodes have greater chemical and mechanical stability than conventional mercury thin-film electrodes. It was also found that the polymeric microelectrodes display several advantages in performance over the macroelectrode counterpart.     

Multiple square wave voltammetry of nanomolar and subnanomolar concentrations of europium (III) at polymer-coated electrodes

The ion-exchange voltammetric determination of europium(III) at polymer-coated electrodes is examined. The comparison between the ion-exchange cyclic voltammetric behaviour at glassy carbon electrodes, modified with the poly(estersulfonate) Kodak AQ55 and Nafion, indicates a better suitability of the latter. The use of multiple square wave voltammetry (MSWV) results in a dramatic improvement of the signal-to-noise ratios of the voltammograms recorded at the modified electrodes. Eu (III) determinations by MSWV at Nafion-coated electrodes are characterised by detection limits 2–3 orders of magnitude lower than those obtained with differential pulse voltammetry and the rare earth cation can be analysed at nano- and subnanomolar levels, depending on the experimental conditions adopted.     

导电聚吡咯膜电极上的电催化作用的研究(Ⅰ)——抗坏血酸的电催化氧化

研究导电聚吡咯(PP)膜电极在酸性水溶液中对抗坏血酸(AH₂)的电催化氧化反应,电化学循环伏安结果表明AH₂在PP/Pt电极上的氧化电位比在Pt电极上的氧化电位负移200～300mV。实验分析了反应的Tafel曲线并讨论了可能的反应机理。实验还用XPS、ESR研究手段,探讨了AH₂与PP之间的相互作用,认为整个电催化过程可能是电子传递催化作用和化学催化作用的偶联。     

Effects of resistance and capacitance on the chronoamperometry of polymer-coated electrodes as modeled by a finite elements digital simulation

A finite elements digital simulation of chronoamperometry with polymer-coated electrodes is presented. The model takes account of mass transport by diffusion and migration, and the effects of the uncompensated resistance and capacitance of the system. A graphical method for the analysis of experimental data was introduced and applied to electrodes coated with poly[Ru(II)(bipy)₂(4-vpy)₂]⁺PF⁻₆.     

Effect of attachment of trimethylchlorosilane and polymer adsorption on stability of silicon photoelectrodes in aqueous solutions

Attachment of trimethylchlorosilane to the surface of Si improved its stability in aqueous solutions in the case of p-type conductivity. Adsorption of polymers such as poly(methyl-methacrylate) and poly(ethyleneterephthalate) was useful for improving the stability of n-type Si. Photoelectrochemical properties of polymer-coated electrodes seem to be governed by the thickness of adsorbed polymers and are unaffected by the pH of the electrolyte.     

Preparation of polymer-coated electrodes containing metal ions complexing sites by electropolymerization of 2-mercaptobenzimidazole and 2-mercaptobenzothiazole on glassy carbon

The possibility of producing polymer-coated electrodes containing complexing agents capable of collecting metal ions was investigated. The organic ligands 2-mercaptobenzimidazole and 2-mercaptobenzothiazole were used as monomers for electropolymerization on glassy carbon electrodes. The electroanalytical applicability of the modified electrodes was evaluated for Hg²⁺ ions, by applying a chemical preconcentration step with subsequent measurement by differential pulse voltammetry. The influence of some electropolymerization parameters, such as scan rate, monomer concentration and the number of cyclic scans, on the voltammetric response of mercury(II) was studied. A 5 min preconcentration period allowed the detection of 0.08 mg/L (4.0 × 10⁻⁷ mol L⁻¹) mercury.     

Carbon papers with conductive polymer coatings for use in solid-state supercapacitors

Conductive polymer-coated carbon papers have been fabricated through polymerisation of pyrrole-based monomers oxidised with various heteropolyacids. Smooth surfaces are obtained when multiple coatings are applied to the carbon surface and give good contact with the Nafion^® electrolyte. Cyclic voltammetry was used to study the electrodes and a.c. impedance and charge / discharge cycling was used to study membrane electrode assemblies (MEA). MEAs were fabricated using a hot-press technique.     

Physical Interpretation of Mixed Ionic-electronic Conductive Polymer-coated Electrodes by a Simple Universal Impedance Model

A simple equivalent electrical circuit is used to obtain the physical parameters of electrical circuit elements from measured electrochemical impedance spectra. This model consists of four circuit elements with a clear physical meaning for each of the elements. Compared to complex models with multiple constant phase elements or Warburg impedances, our model is suitable for extracting physical values for important electrode parameters with low errors. The feasibility of the model was shown by investigating pure metal or polymer-coated electrodes. Here, gold electrodes were coated either with Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT : PSS), Polypyrrole:poly(styrenesulfonate) (PPy : PSS), or (PEDOT/PPy) : PSS by means of electropolymerization. The model could demonstrate the ionic-electronic differences such as the ion accessibility of the differently coated electrodes. To prove the correctness of the model, the obtained results were compared to the literature.     

导电聚吡咯膜电极的现场电化学-ESR研究

本文报导聚吡咯(PP)膜电极在水溶液中的电化学─ESR行为, 定性地探讨了电位,电量对PP膜中极化学形成与转化过程的影响, 并在PP膜/溶液界面存在电化学反应的情形下, 考察了PP膜中可能的电荷传输机理。     

Extension of the voltammetric theory to inert,permeable thin-film coated rotating disc electrodes: Part II. Behaviour of ferrocene-ferricinium ion and quinone-hydroquinone systems on polymer-coated electrodes

The voltammetric behaviour of ferrocene-ferricinium ion and quinone-hydroquinone systems is investigated on electrochemically thin film polymer coated electrodes. Ferrocene oxidation is studied in 0.1 M NBu₄ ClO₄-nitromethane on rotating disc platinum electrodes coated with poly(2-hydroxymethyl-1,4-phenylene) oxide (I), poly-(2,6-dimethyl-1,4-phenylene) oxide (II), and poly[4-(2-aminoethyl)-1,2-phenylene] oxide (III) films. The quinone-hydroquinone system is investigated in aqueous medium (1 M HClO₄) with (I), (II) and poly-(2-cyano-1,4-phenylene) oxide films. Experimental results are in good agreement with the previously calculated voltammetric curves in steady-state mass transfer conditions. The charge transfer and diffusion parameters on these polymer-coated electrodes are calculated The quinone-hydroquinone system is rendered reversible by coating a platinum electrode with I.