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Development of the Instrument for UV-visible Electroreflectance Measurement for Analysing Redox Behavior of Adsorbed Monolayrs on Electrode Surfaces

紫外-可见光电反射测量仪的研制，用于分析电极表面吸附单分子层的氧化还原行为

基本信息

批准号：
04555196
负责人：
NIKI Katsumi
金额：
$ 4.54万
依托单位：
Yokohama National University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1994
项目状态：
已结题

项目摘要

The new instument for UV-visible electroreflectance (ER) measurement having the following characteristics was developed.1. The instrument can be applied to measurement systems where the absorption spectrum of the oxidized form is different from that of the reduced form or where the amount of adsorbed species changes depending on the electrode potential.2. The instument has high sensitivity (sensitivity of 0.002% at potential-modulation of 5mV) and high stability. In addition, all electrode materials which reflect light can be used for the instrument.3. The electrode reactions of multi-component systems which take place at similar potential range can be separately detected by changing the monitor wavelength and the frequency of potential modulation.4. By investigating the Stark effect, the orientation of adsorbed molecules on the electrode surfaces can be determined.5. Both the real component and the imaginary component of ER response are separately detected, so that the rate of electrode reactions up to around 10^5s^<-1> can be measured.6. The ER measurement in the wide wavelength region between 200 and 900 nm is possible by using a xenophoto lamp or adeuterium lamp as a light source.The following new experimental results were obtained by using the developed instrument.1. The electron transfer reaction rates of cytochrome c through COOH-terminated alkantiols with various chain lengths were measured. The linear relationship between the logarithm of the electron transfer reaction rate and the electron transfer distance was obtained in thick thiol layrs, while a deviation from the linear relation ship was observed in thinner thiol layrs.2. ER measurements of tetraruthenated cobalt meso-tetrakis (4-pyridyl) porphyrin enable us to elucidate that the redox reaction of the cobalt center of porphyrin occurs. Conventional voltammetric techniques could not measure the signal of the cobalt center selectively.

研制了具有以下特点的紫外-可见电反射率（ER）测量仪器.该仪器可应用于氧化形式的吸收光谱与还原形式的吸收光谱不同或吸附物质的量根据电极电位而变化的测量系统。2.该仪器具有灵敏度高（在5 mV调压下灵敏度为0.002%）和稳定性好等特点。此外，所有反射光的电极材料都可以用于仪器。3.通过改变监测波长和电位调制频率，可以分别检测发生在相近电位范围内的多组分体系的电极反应.通过研究斯塔克效应，可以确定吸附分子在电极表面的取向.电流变响应的真实的分量和虚部分量都被分别检测到，因此电极反应的速率可以测量到10 ^5 s ^左右<-1>。采用氙灯或氘灯作为光源，可以在200 ~ 900 nm的宽波长范围内进行电流变率的测量.测定了细胞色素c通过不同链长的端羧基烷硫醇的电子转移反应速率。在厚硫醇层中，电子转移反应速率的对数与电子转移距离呈线性关系，而在薄硫醇层中，电子转移反应速率的对数与电子转移距离偏离线性关系.四钌化钴meso-四（4-吡啶基）卟啉的ER测量使我们能够阐明卟啉的钴中心发生氧化还原反应。传统的伏安技术不能选择性地测量钴中心的信号。