Study on laser electrochemical detector

激光电化学探测器的研究

• 批准号: 03804043
• 负责人: WATANABE Iwao
• 金额: $ 1.22万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03804043/
• 关键词: electrochemical analysis; photo-induced electrode reaction; catalytic reaction; laser; microelectrode; マイクロ電極; レ-ザ-; 電気化学検出器; 光電気化学; 分光電気化学

In order to attain a high photon density on an electrode surface, a beam from Ar^+ laser (10 mw at 488 nm) or He-Ne laser (50 mw at 632.8 nm) was focused with an objective and was threw on the micro-electrode. The electrode reaction of [Fe(CN)_6]^<4-> to [Fe(CN)_6]^<3-> was promoted by the laser irradiation through the heating effect, while the reation of Fe^<2+> to Fe^<3+> was suppressed. The promotion and the supression were explained on a basis of change in entropy of the electrode reactions. On the other hand, catalytic current was found in a reaction system where a Fe(III) oxalate was reduced to a Fe(II) oxalate by the laser irradiation in the bulk solution and sequently the Fe(II) oxalate was oxidized at the electrode. The high photon density promoted the reaction cycle between reduction in the solution and the oxidation at the electrode. As the result, the catalytic current was observed. This reaction scheme is available for a new electrochemical analysis.

为了在电极表面获得高光子密度，用物镜聚焦Ar +激光器（488 nm处10 mw）或He-Ne激光器（632.8 nm处50 mw）的光束，并将其投射到微电极上。激光通过加热效应促进了[Fe(CN)_6]^<4->到[Fe(CN)_6]^<3->的电极反应，而抑制了Fe^<2+>到Fe^<3+>的反应。用电极反应熵的变化来解释反应的促进和抑制。另一方面，在本体溶液中通过激光照射将Fe（III）草酸盐还原为Fe（II）草酸盐，随后Fe（II）草酸盐在电极上氧化的反应体系中发现了催化电流。高光子密度促进了溶液中还原和电极氧化之间的反应循环。实验结果显示了催化电流。该反应方案可用于一种新的电化学分析。

项目成果

N.Ogawa: "Electrochemical reduction of nitrate ion at mercury electrodes in the presence of alkaline-earth metal ions." Denki Kagaku. 60. 26-31 (1992)

N.Okawa：“在碱土金属离子存在的情况下，汞电极上硝酸根离子的电化学还原。”

T.Hinoue: "Observation of photopyroelectric signal in X-ray region." Chemistry Letters. 2127-2130 (1992)

T.Hinoue：“X射线区域光热释电信号的观察。”

S. Ikeda: "Structure of metal complexes in solution by the EXAFS and XANES methods, in Structure and Dynamics in Solution, ed. by H. Ohtaki and H. Yamatera" Elsevier Science Publishers, Amsterdam. 39-56 (1992)

S. Ikeda：“通过 EXAFS 和 XANES 方法测定溶液中金属配合物的结构，溶液中的结构和动力学，由 H. Ohtaki 和 H. Yamatera 编辑”Elsevier Science Publishers，阿姆斯特丹。

H.Monjushiro: "Ultraviolet Photoelectron Yield Spectra of Thin Gold Films Measured in Air" Anal.Sciences. 7. 543-547 (1991)

H.Monjushiro：“在空气中测量的金薄膜的紫外光电子产率光谱”Anal.Sciences。

N. Ogawa: "Electrochemical reduction of nitrate at mercury electrode in the presence of alkaline-earth metal ion" Denki Kagaku. 60. 26-31 (1992)

N. Okawa：“碱土金属离子存在下汞电极上硝酸盐的电化学还原”Denki Kagaku。