Dynamic Aspects of the Formation of Molecular Assemblies at Single Crystal Electrode | Solution Interfaces

单晶电极分子组装体形成的动态方面|

• 批准号: 12450344
• 负责人: OKAJIMA Takeyoshi
• 金额: $ 7.04万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450344/
• 关键词: single crystal electrode; self assembled monolayer; dynamics; infrared spectroscopy

We have succeeded to obtain molecular information about the mercury electrode | electrolyte solution interface using in situ infrared reflection absorption spectroscopic technique with an amalgamated gold electrode. It was indicated that perchlorate anions, which has been recognized to be weakly bounded to the mercury surface, can adsorb at potentials more positive than the pzc of the electrode. The structural change of water molecules in the double layer was also investigated. In addition, the adsorption behavior of carbonate anions at single crystal gold electrode surfaces was studied both in electrochemical and spectroscopic techniques.Adsorption of a series of symmetric alkyl viologens on single crystal gold, mercury and highly oriented pyrolytic graphite (HOPG) electrodes was studied. Molecular orientations of adsorbed viologens were found to be strongly dependent on both the electrode materials and the atomic surface structures. The characteristic electrochemical responses observed at each electrode were explained in terms of the order structures of adsorbed viologens.Anion recognition of SAMs of nickel azamacrocyclic compounds on the gold electrode was studied. Electrochemical investigations revealed that these compounds can sense various non-electroactive anions. A sensing mechanism based on potential-dependent coordination of anions to the nickel(III) was proposed. A SAM of 4-aminothiophenol undergoes oxidative dimerization reaction to form an electroactive species. The reaction process was monitored for the first time by time-resolved infrared spectroscopy.]

我们成功地获得了有关汞电极的分子信息|电解质溶液界面使用汞齐金电极的原位红外反射吸收光谱技术。结果表明，高氯酸根阴离子，这已被认为是弱结合的汞表面，可以吸附在电位比pzc的电极更积极。研究了水分子在双电层中的结构变化。此外，还利用电化学和光谱技术研究了碳酸根阴离子在单晶金电极表面的吸附行为，研究了一系列对称烷基紫精在单晶金、汞和高取向热解石墨（HOPG）电极上的吸附行为。吸附的紫精的分子取向被发现是强烈依赖于电极材料和原子表面结构。用紫罗碱的有序结构解释了在每个电极上观察到的特征电化学响应，并研究了镍氮杂大环化合物自组装膜在金电极上的阴离子识别。电化学研究表明，这些化合物可以检测各种非电活性阴离子。提出了一种基于负离子与镍（III）电位依赖性配位的传感机理。4-氨基苯硫酚的SAM经历氧化二聚反应以形成电活性物种。首次通过时间分辨红外光谱法监测反应过程。