Ferrocene-terminated alkanethiol self-assembled monolayers: An electrochemical and in situ surface-enhanced infra-red absorption spectroscopy study

Rudnev, Alexander; Zhumaev, Ulmas; Utsunomiya, Toru; Fan, Chunjie; Yokota, Yasuyuki; Fukui, Ken-ichi; Wandlowski, Thomas (2013). Ferrocene-terminated alkanethiol self-assembled monolayers: An electrochemical and in situ surface-enhanced infra-red absorption spectroscopy study. Electrochimica acta, 107, pp. 33-44. Elsevier Science 10.1016/j.electacta.2013.05.134

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The effect of anions on the redox behavior and structure of 11-ferrocenyl-1-undecanethiol (FcC11) monolayers (SAM) on Au(1 1 1) single crystal and Au(1 1 1-25 nm) thin film electrodes was investigated in 0.1 M solutions of HPF6, HClO4, HBF4, HNO3, and H2SO4 by cyclic voltammetry (CV) and in situ surface-enhanced infrared reflection-absorption spectroscopy (SEIRAS). We demonstrate that the FcC11 redox peaks shift toward positive potentials and broaden with increasing hydrophilicity of the anions. In situ surface-enhanced IR-spectroscopy (SEIRAS) provided direct access for the incorporation of anions into the oxidized adlayer. The coadsorption of anions is accompanied by the penetration of water molecules. The latter effect is particularly pronounced in aqueous HNO3 and H2SO4 electrolytes. The adlayer permeability increases with increasing hydrophilicity of the anions. We also found that even the neutral (reduced) FcC11 SAM is permeable for water molecules. Based on the property of interfacial water to reorient upon charge inversion, we propose a spectroscopic approach for estimating the potential of zero total charge of the FcC11-modified Au(1 1 1) electrodes in aqueous electrolytes.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Rudnev, Alexander; Zhumaev, Ulmas and Wandlowski, Thomas

Subjects:

500 Science > 540 Chemistry

ISSN:

0013-4686

Publisher:

Elsevier Science

Language:

English

Submitter:

Alexander Rudnev

Date Deposited:

17 Jan 2014 09:37

Last Modified:

02 Sep 2015 11:23

Publisher DOI:

10.1016/j.electacta.2013.05.134

Uncontrolled Keywords:

Self-assembled monolayer, Ferrocene, Alkanethiol, Infrared spectroscopy, SEIRAS, Cyclic voltammetry

BORIS DOI:

10.7892/boris.39818

URI:

https://boris.unibe.ch/id/eprint/39818

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