Time-resolved vibrational spectroscopic study of electrode dynamics

本项目旨在利用快速时间分辨红外光谱技术研究电极动力学和动力学。使用表面增强红外吸收光谱（SEIRAS）实现了皮秒范围内的超快时间分辨研究。主要成果如下：1。时间常数为0.1- 1ms的双层充电阻碍了超快电极动力学的研究。通过将所谓的温度跳变方法与皮秒时间分辨SEIRAS相结合，首次避免了这一问题。激光脉冲对界面的快速加热导致水的重新定向导致电势的突然变化。seira的技术发展在硅和锗棱镜上制备非常稳定的seira活性金属薄膜电极的简单而经济的技术已经发展起来。这些技术对上述皮秒时间分辨红外研究的成功做出了重大贡献。电化学振荡的更多分析电化学界面上发生了各种各样的振荡。我们用时间分辨SEIRAS研究了甲酸氧化Pt过程中的电位和电流振荡，并提出了一个新的概念来解释这些振荡，而不需要任何假设。在分子尺度上详细研究了低温燃料电池的基础——铂电极上C_1分子的析氢、氧还原和阳极氧化。我们首次清楚地证明了所有的C_1分子都是通过甲酸氧化CO_2的，这完全修正了一般的共识。采用SEIRAS研究了在Au电极上自组装的腺嘌呤衍生物与硫胺衍生物之间的氢键配对，并以此作为分子识别系统的模型系统。我们还成功地利用三钌配合物制造了新型的地对空导弹。用SEIRAS检测了它们的结构和功能。少

This project aimed at to study electrode kinetics and dynamics by using fast time-resolved infrared spectroscopy. The use of surface-enhanced infrared absorption spectroscopy (SEIRAS) enabled ultrafast time-resolved study in the picosecond range. The main achievements are as follows.1.Ultrafast time-resolved IR spectrscopyDouble-layer charging with a 0.1-1 ms time constant has hampered the study of ultrafast electrode dynamics. This problem was circumvented for the first time by coupling the so-called temperature jump method with picosecond time-resolved SEIRAS. The rapid heating of the interface by a laser pulse results in the sudden change in potential through reorientaion of water.2.Technical developments in SEIRASSimple and cost-effective techniques to prepare very stable SEIRA-active thin metal film electrodes on Si and Ge prisms have been developed. These techniques significantly contributed to the success of the picosecond time-resolved IR studies mentioned above.3.Molecular sca … More le analysis of electrochemical oscillationsA variety of oscillations occur at the electrochemical interface. We investigated potential and current oscillations during formic acid oxidation on Pt by time-resolved SEIRAS and proposed a new concept that explains the oscillations without any assumptions.4.ElectrocatalysisHydrogen evolution, oxygen reduction, and anodic oxidation of C_1 molecules on Pt electrodes that constitute the basis of low temperature fuel cells were examined in detail at the molecular scale. We clearly showed for the first time that all C_1 molecules are oxidized CO_2 via formate, which totally revised the general consensus.5.Structures and functions of self-assembled monolayers (SAMs)Hydrogen bond pairing between an adenine derivative self-assembled on an Au electrode and a thimidine derivative were examined by SEIRAS as a model system of molecular recognition system. We also succeeded in fabricating new types of SAMs using triruthenium complexes. Their structures and functions were examined by SEIRAS. Less