Infrared Spectroscopic imaging of reactions at solid-liquid interfaces

固液界面反应的红外光谱成像

• 批准号: 18350038
• 负责人: OSAWA Masatoshi
• 金额: $ 9.26万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18350038/
• 关键词: Infrared Spectroscopy; Imaging; Solid-Liquid Interface; Surface-Enhanced Spectroscopy; Electrochemical Oscillations; Electrocatalysis; Reaction Intermediates; Formic Acid; 固液界面; Chemical wave; 表面増強赤外分光法; ホルムアロデヒド

This project aimed to image chemical reactions that propagate two dimensionally over solid surfaces in solution by using infrared spectroscopy. Different from conventional optical microscope, two dimensional distributions of chemical species involved in the reactions can be imaged by plotting the intensity or frequency of a molecular vibration characteristic to each species. To realize the IR imaging, a 64 x 64 multi-channel MCT detector (Focal Plane Analyzer, FPA) was used. The target we have interested in is fast reactions of adsorbed monolayers and an experimental difficulty of the present approach is the very low IR absorption. To overcome this problem, surface-enhanced infrared absorption spectroscopy (SEIRAS) developed in this laboratory was couple. After great efforts, we have succeeded in imaging the spatial distribution of CO adsorbed on Pt electrodes (including patterned electrodes) and demonstrated the usefulness of this approach. However, we have not yet succeeded in monitoring spatially and temporally oscillating patterns that are expected to be formed under galvanostatic or potentiostatic electro-oxidation of formic acid due to the low signal-to-noise ratio of the image and the slow data transfer rate from the FT-IR spectrometer to the controlling computer (the data size of one image is a few GB). This problem will be removed in future by modifying the electronics of the spectrometer.In parallel, we investigated the mechanisms of several catalytic reactions at the electrochemical interface, such as hydrogen evolution reaction on Pt and Ag, electro-oxidation of small organic molecules (CO, methanol, formaldehyde, formic acid, and dimethyl eter). The most notable achievement in this series of study is that electrooxidation of small organic molecules occurs through formate species adsorbed on the surface. The mechanism of each reaction was examined in detail by IR spectroscopy.

该项目旨在通过使用红外光谱对溶液中固体表面上二维传播的化学反应进行成像。与传统的光学显微镜不同，通过绘制每个物种的分子振动特征的强度或频率，可以成像参与反应的化学物种的二维分布。为了实现IR成像，使用64 X 64多通道MCT检测器（焦平面分析仪，FPA）。我们感兴趣的目标是吸附单分子膜的快速反应，目前的方法的实验困难是非常低的红外吸收。为了克服这个问题，本实验室开发的表面增强红外吸收光谱（SEIRAS）耦合。经过大量的努力，我们已经成功地成像的空间分布的CO吸附在铂电极（包括图案化电极），并证明了这种方法的实用性。然而，我们还没有成功地监测的空间和时间振荡模式，预计将形成恒电流或恒电位下的甲酸的电氧化，由于低信噪比的图像和缓慢的数据传输速率从FT-IR光谱仪的控制计算机（一个图像的数据大小是几GB）。同时，我们研究了电化学界面上的几种催化反应的机理，如Pt和Ag上的析氢反应，有机小分子（CO、甲醇、甲醛、甲酸和二甲基醚）的电氧化反应。这一系列研究中最显著的成果是有机小分子的电氧化是通过吸附在表面上的甲酸盐物种发生的。通过红外光谱对反应机理进行了详细的研究。

项目成果

「研究成果報告書概要(和文)」より

摘自《研究结果报告摘要（日文）》

• 发表时间: 2005
• 作者: Kawauchi;et. al.;Nishimura et al.;Dezawa et al.;Yoshizawa et al.;星野 幹雄;星野 幹雄
• 通讯作者: 星野 幹雄

Formic acid electrooxidation on Pd in acidic solutions studied by surface-enhanced infrared absorption spectroscopy

• DOI: 10.1039/b805955a
• 发表时间: 2008-01-01
• 期刊: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
• 影响因子: 3.3
• 作者: Miyake, Hiroto;Okada, Tatsuhiro;Osawa, Masatoshi
• 通讯作者: Osawa, Masatoshi

Structure of water at the electrified platinum-water interface:: A study by surface-enhanced infrared absorption spectroscopy

• DOI: 10.1021/jp710386g
• 发表时间: 2008-03-20
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Osawa, Masatoshi;Tsushima, Minoru;Yamakata, Akira
• 通讯作者: Yamakata, Akira

Electrochemical behaviors of dimethyl ether on platinum single crystal Electrodes. Part I : Pt (111)

二甲醚在铂单晶电极上的电化学行为。

• 发表时间: 2008
• 期刊: Journal of Electroanalytical Chemistry 619
• 作者: 奥村渉;渋谷洋行;森寺信勝;菅原正雄;K. Nakata;K. Nakata;A. Yamakata;L. Lu
• 通讯作者: L. Lu

Mechanistic study of formic acid oxidation on Pt electrodes in Acidic Solution by real-time surface-enhanced infrared spectroscopy

实时表面增强红外光谱研究酸性溶液中铂电极上甲酸氧化的机理

• 发表时间: 2006
• 期刊: Journal of Physical Chemistry B 110
• 作者: Y. Tong;L. Lu;Y. Zhang;Y. Gao;G. Yin;M. Osawa;S. Ye;H.-F. Wang;K. Kunimatsu;Keiji Kunimatsu;Y. -X. Chen;G. Samjeske
• 通讯作者: G. Samjeske