Observation of Redox-State-Dependent Reversible Local Structural Change of Ferrocenyl-Terminated Molecular Island by Electrochemical Frequency Modulation AFM
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- Ken-ichi Umeda
- Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
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- Ken-ichi Fukui
- Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
書誌事項
- 公開日
- 2010-02-10
- DOI
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- 10.1021/la904797h
- 公開者
- American Chemical Society (ACS)
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説明
Electroactive ferrocenylundecanethiol (FcC(11)H(22)SH) islands embedded in an n-decanethiol (C(10)H(21)SH) self-assembled monolayer (SAM) matrix on Au(111) were studied under potential control in 0.1 M HClO(4) aqueous solution using newly developed electrochemical frequency-modulation atomic force microscopy (EC-FM-AFM). The apparent height of the Fc islands from the surface of the matrix SAM increased by about 0.44 nm accompanied by the oxidation of the terminal Fc groups. This potential-dependent reversible change can be explained by formation of an ionic double layer where ClO(4)(-) ions are strongly bound on the Fc(+) groups. Simultaneous measurements of energy dissipation, which corresponds to the energy to keep the cantilever's vibrational amplitude constant, revealed distinct change in the magnitude by the oxidation state of the Fc groups. These results indicate that localized charge at an electrode/electrolyte solution interface can be identified, and microscopic information on the electric double layer at the interface is available by using EC-FM-AFM.
収録刊行物
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- Langmuir
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Langmuir 26 (11), 9104-9110, 2010-02-10
American Chemical Society (ACS)