Structures of Atoms and Molecules Adsorbed on the Surface of Single Crystal Electrodes and in situ Measurement of Kinetics of Electrode Reactions

本项目的目的是通过红外反射吸收光谱和其他技术来阐明原子和分子在定义良好的单晶电极上的取向和结构，测量这种电极上氧化还原电极反应的非均相速率常数，并阐明电极/溶液界面的结构对速率常数的影响。我们得到了以下结果。1.我们发现在铂(111)电极上的循环伏安曲线上观察到的特定氢波与阴离子的吸附密切相关。2.阐明了阴离子、碱金属离子和碱土金属离子对界面水结构的影响。3.我们发现(II/III)在铂单晶电极上的氧化还原电极反应速率按如下顺序递减：(111)&gt；(100)&gt；(110)。FT-IR测试还表明，六氰亚铁酸盐分解形成吸附在铂表面的氰化层。基于这些发现，我们提出了一个合理解释的反应机理。4.对电化学薄层池在原位红外反射吸收光谱中的响应时间进行了理论分析。5.通过红外光谱分析，阐明了过氧化氢在镍络合物修饰电极上的氧化反应机理。

The aims of this project were to clarify the orientation and structure of atoms and molecules on well-defined single crystal electrodes by infrared reflection-absorption spectroscopy and other techniques, to measure heterogeneous rate constants of redox-electrode reactions on such electrodes and to elucidate the effect of the structure of electrode/solution interface on the rate constants. We obtained the following results. 1. We found that specific hydrogen wave observed in cyclic voltammograms on Pt (111) electrode is closely related to the anion adsorption. 2. We clarified the effects of anion and alkaline and alkaline-earth metal ions on the structure of water in the interfacial region. 3. We found that the rate of redox-electrode reaction of (II/III) at Pt single crystal electrodes decreases in the order : (111) > (100) > (110). FT-IR measurements also revealed that hexacyanoferrate decomposes to form adsorbed CN layr on platinum surface. Based on these findings, we proposed a reaction mechanism that gives reasonable explanation. 4. Response time of electrochemical thin-layr cells for in situ IR reflectance-absorption spectroscopy was theoretically treated. 5. The reaction mechanism of hydrogen peroxide oxidation at Ni complex modified electrodes was clarified from the infrared spectroscopic evidence.