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

单晶电极表面吸附原子和分子的结构及电极反应动力学的原位测量

• 批准号: 08455393
• 负责人: TOKUDA Koichi
• 金额: $ 4.22万
• 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: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455393/
• 关键词: single crystal electrode; electrode kinetics; ordered interface; hexacyanoferrate; adsorption; infrared spectroscopy; ヘキサシアノ鉄イオン; フェロセン; 電解質イオン; 水

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.

该项目的目的是通过红外反射-吸收光谱和其他技术阐明原子和分子在定义明确的单晶电极上的取向和结构，测量在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Pt（111）电极上循环伏安图中观察到的特定氢波与阴离子吸附密切相关。2.阐明了阴离子、碱金属和碱土金属离子对界面区水结构的影响。3.结果表明，（II/III）在Pt单晶电极上的氧化还原反应速率按（111）>（100）>（110）的顺序减小。FT-IR测试还表明，六氰合铁酸盐在铂表面分解形成CN吸附层。基于这些发现，我们提出了一个反应机理，给出了合理的解释。4.本文从理论上讨论了电化学薄层池用于现场红外反射-吸收光谱的响应时间。5.从红外光谱的角度阐明了过氧化氢在镍络合物修饰电极上的氧化反应机理。

项目成果

K.Yamada: "Microelectrode with Leak of Solution" Denki Kagaku. 66・3(未定). (1998)

K. Yamada：“溶液泄漏的微电极”Denki Kagaku 66・3（待定）。

Fusao Kitamura: "Infrared spectroscopic observation of water at a polycrystalline gold electrode/aqueous halide solution interface" J.Electroanal.Chem.412・1. 183-188 (1996)

Fusao Kitamura：“多晶金电极/卤化物水溶液界面处的水的红外光谱观察”J.Electroanal.Chem.412·1（1996）。

Fusao Kitamura: "In situ infrared spectroscopic study of water at a polycrystalline gold electrode surface" J.Electroanal.Chem.(印刷中).

Fusao Kitamura：“多晶金电极表面水的原位红外光谱研究”J.Electroanal.Chem.（出版中）。

F.Kitamura et al.: "Infrared Spectroscopic Observation of Water at a Polycrystalline Gold Electrode/Aqueous Perchlorate Solution Interface" Electrochim.Acta,. 42(in press.). (1997)

F.Kitamura 等人：“多晶金电极/高氯酸盐水溶液界面处水的红外光谱观察”Electrochim.Acta，。

Fusao Kitamura: "Kinetic and in situ infrared spectroscopic study of Fe(CN)_6^<3->/Fe(CN)_6^<4-> couple on platinum single crystal electrodes" J.Electroanal.Chem.(印刷中).

Fusao Kitamura：“铂单晶电极上 Fe(CN)_6^<3->/Fe(CN)_6^<4-> 电偶的动力学和原位红外光谱研究”J.Electroanal.Chem.（出版中） 。