Fourie Transform Infrared Spectroscopic Studies on Organic Electrode Reactions

有机电极反应的傅里叶变换红外光谱研究

• 批准号: 60470083
• 负责人: YASUKOUCHI Kazuo
• 金额: $ 4.8万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470083/
• 关键词: FTIR; Reflective infrared spectroscopy; Electrode; solution interface; In-situ measurement; Cyanometal complexes; Organic thin films; 電解重合; 炭酸ガス還元; チトクロムC; 電極表面測定

FTIF spectroelectrochemistry of various electrode/solution interfaces has been examined in this research project. Followings are main achievements.1. A measuring assembly has been set up for interfacial FTIR spectroelectrochemistry. Use of high sensitive detector, such as MCT detector, and preparation of suitable spectroelectrochemical cell are very important to obtain well defined signals.2. Redox reactions of some cyanometal complexes have been examined using the prepared set up: Oxidation processes of cyanide and ferrocyanide ions were monitored by the C-N stretching vibration at Pt and Au electrodes; CNO<@D1-@>D1 and ferricyanide ions were detected, respectively. For octacyano tungstate(IV) and molybdate(IV), the wave number for the C-N stretching vibration was almost independent of the oxidation state of the central metal. At a gold electrode cyanocomplexes showed rather complicated signals because of dissociation of the electrode. W(CN)<@D34-(/)8@>D3 adsirbed more strongly than CN<@D1-@>D1 onto a gold electrode. No AuCN formation was observed during oxidation of W(CN)<@D24-(/)8@>D3 while AuCN was formed at the electrode surface at high positive potentials during oxidation of Mo(CN)<@D34-(/)8@>D3. Au(CN)<@D3-(/)2@>D3 oxidized at a Pt electrode to give AuCN and CNO<@D1-@>D1 in the absence of excess amounts of CN<@D1-@>D1 or halides;Au(CN)_2 +H_2 - 2e AuCN + CNO^- + 2H^+.3. Thin films of some organic compounds, such as methylviologen, cytochrome c, electropolymerized organic thin films and so on, at the electrode surface were monitored as a function of electrode potential. However, further improvements of the measuring system have been required to get signals due to species adsorbed on the electrode by monolayer; use of modulation techniques would be helpful.

在本研究计画中，我们探讨了各种电极/溶液界面的FTIF光谱电化学。以下是主要成果。建立了一套界面FTIR光谱电化学测量装置。使用高灵敏度的检测器（如MCT检测器）和制备合适的光谱电化学池对于获得清晰的信号是非常重要的.用所制备的装置研究了氰根和亚铁氰化物的氧化还原反应：用Pt和Au电极上的C-N伸缩振动监测氰根和亚铁氰化物的氧化过程，分别检测CNO<@D1-@>D1和铁氰化物离子。对于八氰基钨酸盐（IV）和八氰基钨酸盐（IV），C-N伸缩振动的波数几乎与中心金属的氧化态无关。在金电极上，由于电极的解离，氰基络合物显示出相当复杂的信号。W（CN）<@D34-（/）8@>D3比CN<@D1-@>D1更强地吸附在金电极上。在W（CN）<@D24-（i）8@>D3的氧化过程中没有观察到AuCN的形成，而在Mo（CN）<@D34-（i）8@>D3的氧化过程中，在高正电位下在电极表面形成AuCN。Au（CN）<@D3-（i）2@>D3在没有过量CN<@D1-@>D1或卤化物的情况下在Pt电极上氧化得到AuCN和CNO<@D1-@>D1;Au（CN）_2 +H_2 - 2 eAuCN + CNO^-+2H ^+。一些有机化合物，如甲基紫精，细胞色素c，电聚合的有机薄膜等，在电极表面的薄膜作为电极电位的函数进行监测。然而，由于单层吸附在电极上的物质，需要进一步改进测量系统以获得信号;使用调制技术将是有帮助的。

项目成果

Isao Taniguchi: Bull.Chem.Soc.Jpn.,to be published.

Isao Taniguchi：Bull.Chem.Soc.Jpn.，待出版。

Isao TANIGUCHI: Proc.3rd.Int.Symp.on Redox mechanism and Interfacial Properties of Molecules of Biological Importance. (1988)

Isao TANIGUCHI：Proc.3rd.Int.Symp.on 氧化还原机制和生物重要性分子的界面特性。

Isao TANIGUCHI: Bull.Chem.Soc.,Jpn.

谷口功：Bull.Chem.Soc.，Jpn。

Isao TANIGUCHI: "Interfacial Electrochemistry of Promoter Modified Electrodes for the Rapid Electron-Transfer of Cytochrome c" Proc. 3rd Int. Symp. on Redox Mechanism and Interfacial Properties of Molecules of Biological Importance. (1988)

Isao TANIGUCHI：“用于细胞色素 c 快速电子转移的促进剂修饰电极的界面电化学”Proc。

Isao TANIGUCHI: "In-situ FTIR Study on the Mechanism of Carbon Dioxide Reduction at a Gold Electrode" Bull. Chem. Soc., Jpn.

Isao TANIGUCHI：“金电极二氧化碳还原机制的原位 FTIR 研究”公牛。