Time-resolved vibrational spectroscopic study of electrode dynamics

该项目旨在利用快速时间分辨红外光谱研究电极动力学和动力学。表面增强红外吸收光谱（SEIRAS）的使用使得皮秒范围内的超快时间分辨研究成为可能。主要成果如下：1.超快时间分辨红外光谱0.1-1ms时间常数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跃方法与皮秒时间分辨SEIRA相结合，这个问题首次得到了解决。激光脉冲对界面的快速加热导致水的重新定向而导致电位的突然变化。2.SEIRASS的技术发展已经开发出在Si和Ge棱镜上制备非常稳定的SEIRA活性金属薄膜电极的简单且具有成本效益的技术。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。3.电化学振荡的分子尺度分析电化学界面处会发生各种振荡。我们通过时间分辨SEIRAS研究了Pt上甲酸氧化过程中的电位和电流振荡，并提出了一个在没有任何假设的情况下解释振荡的新概念。4.电催化在构成低温燃料电池基础的Pt电极上C_1分子的析氢、氧还原和阳极氧化在分子尺度上进行了详细研究。我们首次清楚地证明了所有的C_1分子都是通过甲酸盐被氧化为CO_2的，这彻底改变了普遍的共识。5.自组装单层膜(SAMs)的结构和功能以SEIRAS作为分子识别系统的模型系统，研究了在Au电极上自组装的腺嘌呤衍生物和胸苷衍生物之间的氢键配对。我们还成功地利用三钌配合物制造了新型 SAM。它们的结构和功能由SEIRAS 进行了检查。较少的

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