现场光谱电化学研究的新进展

电化学以两个凝聚相的荷电界面为其主要研究对象．它广泛地应用于能源、材料等重要科学领域，并对生命科学的发展发挥着重要作用［1，2］．为了从分子水平上深化对电化学界面的认识，自七十年代中至八十年代初采用了紫外可见反射、拉曼和红外光谱技术对电化学体系进行现场（in-situ，又称原位）研究，开创了光谱电化学新领域[3,4]．光谱电化学在／＼十年代发展迅速，推动电化学研究由宏观进入微观、由统计平均深入至分子水平【‘一刀．近年来，随着各种光谱仪器性能的提高以及非线性光谱等新技术的发展，现场光谱电化学研究不断拓宽新领域，…     

组合电化学--电化学研究中的新策略

组合电化学是一种新的电化学研究策略，通过设计和构建大量多样性的电极阵列，并对其进行高通量筛选和表征，快速、高效地实现了体系的电化学研究。本文综述了近年来进行的组合电化学研究，重点介绍了组合光学筛选方法、组合电化学合成方法以及电化学平行筛选方法，并探讨了各种方法的优势和存在的问题。     

抗癌药物与DNA作用的电化学研究进展

针对当前电化学研究领域中的热门课题——DNA的电化学研究，阐述了与DNA的电化学研究相关的理论基础，其中包括作用机理和作用模式等，概述了其近几年的研究进展，并在此基础上对抗癌药物与DNA的相互作用的电化学研究工作特别是该研究的潜在应用，即抗癌药物的新型筛选方法——电化学筛选方法进行了介绍。     

质子交换膜燃料电池催化剂的研究方法

质子交换膜燃料电池性能的提高受限于电极上催化剂的电化学活性，而对催化剂的研究有助于人们深入了解其化学状态、电子结构等因素与电化学活性之间的关系。本文详细地介绍了有关质子交换膜燃料电池催化剂等五种研究方法(旋转薄层电极、固态核磁共振、X射线吸收光谱、电化学石英晶体微天平、差分电化学质量光谱)的原理、应用技巧以及在催化剂研究中所揭示的信息和局限性，并对今后的发展进行了展望。     

有机电化学的发展史

本文回顾了有机电化学和有机电化学工业的发展历程，阐述了有机电化学的研究领域，从而展望了有机电化学的发展方向。     

电化学免疫分析法研究进展

电化学免疫分析法是将免疫分析与电化学分析技术相结合的一种免疫分析新方法，近十多年来，电化免疫分析的研究有了迅速的发展。本文对电化学的免疫分析法的标记物、免疫方法、电化学检测技术进行了概括总结，并展望了电化学免疫分析的发展前景。     

《电分析化学与生物传感技术》

电分析化学利用物质的电学和电化学性质进行表征与测量。它不仅能进行组成和形态分析，而且对电极过程的理论研究和生命科学、信息科学、环境科学的发展具有重要的作用。该书从电分析化学研究涉及的电化学基础知识出发，总结了现代电分析化学研究常用方法的基本原理，概括和吸收了国内外近年来在电分析化学与生物传感器领域的新成就和相关文献，阐述了当代电分析化学及其在生命分析化学特别是生物电化学研究中的应用，     

自组装膜技术在电分析化学中的研究与应用

本文对自组膜（ＳＡＭｓ）在电分析化学中的研究和应用进行了比较全面的综述。ＳＡＭｓ是单分子膜化学修饰电极发展的最高形式，本文着重阐述了硫醇／金单分子层自组膜在微电极、生物电化学和生物传感器、液相色谱电化学、电催化、光谱电化学等电分析化学研究领域中的应用，并进行了展望。     

光电化学生物分析研究进展

光电化学生物分析是近年来新出现并发展迅速的一种分析技术,其检测原理是基于在光照下识别元件和目标分子之间的生物识别作用造成光电活性物质产生的电信号的改变,以实现对待测物的定量测定。由于其灵敏选择性检测的优点及其在生物分析中的巨大潜力,该方法吸引了较多的关注,并且在检测性能和生物传感应用等方面也取得了较大进步。本文针对光电化学生物分析中常见的四种应用领域,即直接光电化学检测、光电化学酶检测、光电化学核酸检测以及光电化学免疫分析,综述了近年来国内外在光电化学生物分析研究领域的最新进展,并对其未来发展进行了展望。     

毛细管电泳安培型电化学检测法

本文评述了近年来安培型电化学检测法在毛细管电泳中的发展概况，归纳了二种检测方式及其装置的结构特点。阐述了金属电极、液膜电极和修饰电极等在电化学检测应用研究中的作用以及此方法在微区分析、活体分析中的重要意义，并展望了其发展前景。     

Recent Advances in in situ multi-spectroelectrochemistry

To consider the past, present and future of in situ spectroelectrochemistry, a review on the recent state of modern spectroelectrochemistry and trends in the development of spectroelectrochemcial techniques is presented for the combined application of different in situ spectroelectrochemcial methods like ESR spectroelectrochemistry, NMR spectroelectrochemistry, Raman spectroelectrochemistry or IR spectroelectrochemistry to electrode systems. Starting with a discussion of the first steps in spectroelectrochemistry in the past, the main part of this review is focused on the advantages of the combined application of spectroelectrochemical techniques in the analysis of electrode reactions. The spectroelectrochemical methods are demonstrated to be successful in electrode reactions both for solid structures like polymers or carbon nanotubes and for molecular structures like fullerenes and oligothiophenes. The final outlook is attributed to future developments in spectroelectrochemistry.     

Spectroelectrochemistry of carbon nanostructures.

This review is focused on charge-transfer reactions at carbon nanotubes and fullerenes. The spectroelectrochemistry of fullerenes deals with the spin states of fullerenes, the role of mono-anions and the reactivity of higher charged states in C60. The optical (Vis-NIR) spectroelectrochemistry of single-walled carbon nanotubes (SWNTs) follows changes in the allowed optical transitions among the Van Hove singularities. The Raman spectroelectrochemistry of SWNT benefits from strong resonance enhancement of the Raman scattering. Here, both semiconducting and metallic SWNTs are analyzed using the radial breathing mode (RBM) and G-modes as well as the second order (D, G') and intermediate frequency modes. Raman spectroelectrochemistry of SWNT allows the addressing of index-identified tubes and even single isolated nanotubes. Optical and Raman spectroelectrochemistry of fullerene peapods, C60@SWNT and C70@SWNT indicates effective shielding of the intratubular fullerene (peas). The most striking effect in the spectroelectrochemistry of peapods is the so-called "anodic Raman enhancement" of intratubular C60. Double-walled carbon nanotubes (DWNTs) give a specific spectroscopic response in Vis-NIR spectroelectrochemistry for the inner and the outer tube. They are better distinguishable by Raman spectroelectrochemistry which allows a precise tracing of the specific doping response of outer/inner tubes.     

聚电解质中电活性物质氧化还原反应机理的现场显微红外光谱电化学研究

用现场显微红外光谱电化学方法研究了几种电活性物质,包括无机盐、有机物、无机聚合物微粒在聚电解质中的氧化还原反应及其机理。     

铜的吸收光谱电化学分析

本文研究了铜的吸收光谱电化学特性和仪器装置以及测量条件对铜的灵敏度影响,结果表明,用双电极电解池和空心阴极光源分别代替单电极电解池和氚灯光源进行铜的吸收光谱电化学测量,灵敏度比West方法提高2.5倍。     

高温红外光谱电化学薄层池的制作与表征

为了拓宽光谱电化学研究范围,开展高温下电化学反应过程,本文研制了一种高温红外光谱电化学薄层池(HTC)。 研制的HTC清洗方便,操作简单,适用于水体系和有机体系。 该HTC可在室温至373 K(根据溶剂沸点,控温精度为±0.5 K)温度范围内使用,具有良好的电化学性能,红外光谱采集谱图清晰信噪比好。 利用铁氰化钾水溶液和对苯醌离子液体溶液的红外光谱电化学行为对HTC进行了表征,得到较满意的结果。     

Nitrogen-doped diamond-like carbon as optically transparent electrode for infrared attenuated total reflection spectroelectrochemistry

This contribution describes the development of nitrogen-doped diamond-like carbon (N-DLC) thin films for multi-reflection mid-infrared (MIR) attenuated total reflectance (IR-ATR) spectroelectrochemistry. N-DLC coatings were deposited using pulsed laser deposition (PLD) involving the ablation of a high purity graphite target. The DLC matrix was further modified by ablating the target in the presence of nitrogen gas. This technique offers the advantage of depositing thin films at room temperature, thereby enabling coating of temperature-sensitive substrates including e.g., MIR waveguides. The resulting films were analyzed with X-ray photoelectron spectroscopy (XPS), and determined to be composed of carbon, nitrogen, and adventitious oxygen. Raman spectroscopic studies indicate that the addition of nitrogen induces further clustering and ordering of the sp(2)-hybridized carbon phase. The electrochemical activity of PLD fabricated N-DLC films was verified using the Ru(NH(3))(3+/2+) redox couple, and was determined to be comparable with that of other carbon-based electrodes. In situ spectroelectrochemical studies involving N-DLC coated zinc selenide (ZnSe) MIR waveguides provided evidence concerning the oxidation of N-DLC at anodic potentials in 1 M HClO(4) solutions. Finally, the electropolymerization of polyaniline (PAni) was performed at N-DLC-modified waveguide surfaces, which enabled spectroscopic monitoring of the electropolymerization, as well as in situ studying the structural conversion of PAni at different potentials.     

Spectroelectrochemistry of EuCl3 in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl,LiCl−RbCl,and 3 LiCl−2 CsCl; at 873 K

Key electrochemical properties affecting pyroprocessing of nuclear fuel were examined in four eutectic melts using Eu^3+/2+ as a representative probe. We report the electrochemical and spectroelectrochemical behavior of EuCl₃ in four molten salt eutectics (3 LiCl?NaCl, 3 LiCl?2 KCl, LiCl?RbCl and 3 LiCl?2 CsCl) at 873 K. Cyclic voltammetry was used to determine the reduction potential for Eu^3+/2+ and the applied potentials for spectroelectrochemistry. Single step chronoabsorptometry and thin‐layer spectroelectrochemistry were used to obtain the number of electrons transferred, reduction potentials and diffusion coefficients for Eu³⁺ in each eutectic melt. The reduction potentials determined by thin‐layer spectroelectrochemistry were essentially the same as those obtained using cyclic voltammetry. The diffusion coefficient for Eu³⁺ was the largest in the 3 LiCl?NaCl melt, showed a negative shift in the 3 LiCl?2 KCl melt, and was the smallest in the LiCl?RbCl and 3 LiCl?2 CsCl eutectic melts. The basic one‐electron reversible electron transfer for Eu^3+/2+ was not affected by melt composition.     

一系列单硅烷-寡聚噻吩共聚高分子膜中电荷载流子及其迁移率的研究

研究了一系列由单硅烷和寡聚噻吩组成的共聚高分子膜在较宽掺杂电位范围内的光谱电化学变化规律. 用PSnT表示这一系列共聚高分子, 其中n表示高分子链上寡聚噻吩单元中噻吩环的个数, n分别为5, 7, 8, 10和14. 结果表明在一定的掺杂电位范围内这些PSnT膜可以可逆地电致变色. PSnT膜的光谱电化学和循环伏安研究均表明在电化学掺杂过程中PSnT膜中的寡聚噻吩单元可被两步氧化. 第一步氧化生成极子, 极子可二聚形成p-dimers, 两者之间存在着平衡. 而第二步氧化生成双极子. 双极子不能稳定存在于PS5T和PS7T膜中, 但可稳定存在于其它具有更长寡聚噻吩单元的PSnT膜中. 结合PSnT膜在不同电位下的表观迁移率数据讨论了膜中各种载流子对表观迁移率的影响. 表明当掺杂电位低于两步氧化过程的平均电位Emean时, 膜中表观迁移率的增加主要是由于p-dimers的形成及数量增加所引起的. 随着寡聚噻吩共轭长度(n)的增加, p-dimers更易形成, 因此PSnT膜中载流子的表观迁移率在更低的掺杂电位下开始增加并具有更大的增幅.     

Angular Dependence of Raman Spectra for Electroactive Polymer Films on a Platinum Electrode

Russian Journal of Electrochemistry - The redox transformations in a conducting polymer film on a platinum electrode were studied by Raman spectroelectrochemistry at fixed potentials depending on...     

Spectroelectrochemistry study on the electrochemical reduction of ethidium bromide.

The electrochemical reduction mechanism of ethidium bromide was first studied by spectroelectrochemistry. This reduction was proved to be a two-step process by cyclic voltammetry, differential pulse voltammetry and spectroelectrochemistry, in which each step was proved to be a one-electron transfer process by a spectropotentiostatic fluorescence technique. Hydroethidine was confirmed to be the final product by comparing the spectrum of the product of the electrochemical reduction to that of the product of the chemical reduction of ethidium bromide, and a carbon-centered radical was concluded to be a reasonable intermediate product during the electrochemical reduction of ethidium bromide.