Heterogeneous electron transfer kinetics and electrocatalytic behaviour of mixed self-assembled ferrocenes and SWCNT layers

Duduzile Nkosi, Jeseelan Pillay, Kenneth I. Ozoemena, Khalid Nouneh, Munetaka Oyama

Research output: Contribution to journalArticlepeer-review

90 Citations (Scopus)


The electron transfer dynamics and electrocatalytic behaviour of ferrocene-terminated self-assembled monolayers (SAMs), co-adsorbed with single-walled carbon nanotubes (SWCNTs) on a gold electrode, have been interrogated for the first time. Ferrocene monocarboxylic acid (FMCA) or ferrocene dicarboxylic acid (FDCA) was covalently attached to the cysteamine (Cys) monolayer to form Au-Cys-FMCA and Au-Cys-FDCA, respectively. The same covalent attachment strategy was used to form the mixed SWCNTs and ferrocene-terminated layers (i.e. Au-Cys-SWCNT/FMCA and Au-Cys-SWCNT/FDCA). Using cyclic voltammetry and electrochemical impedance spectroscopy, the impact of neighbouring SWCNTs on the electron transfer dynamics of the ferrocene molecular assemblies in an acidic medium (0.5 M H2SO4) and in a solution of an outer-sphere redox probe ([Fe(CN)6] 4-/[Fe(CN)6]3-) was explored. The electron transfer rate constants in both media essentially decreased as Au-Cys-FMCA > Au-Cys-SWCNT/FDCA > Au-Cys-FDCA > Au-Cys-SWCNT/FMCA. This trend has been interpreted in terms of several factors such as the locations of the ferrocene species in a range of environments with a range of potentials, the proximity/interactions of the ferrocenes with one another, and electrostatic interaction or repulsion existing between the negatively-charged redox probe and the modified electrodes. The thiocyanate ion (SCN-) was used as a model analyte to examine the influence of the neighbouring SWCNTs on the electrocatalytic ability of the ferrocene assemblies. The Au-Cys-SWCNT/FDCA showed the best catalytic activity (in terms of onset potential and catalytic peak current height) for the oxidation of SCN-, possibly due to the repulsive interactions between the negatively charged SCN- and high number of surface -COOH species at the SWCNT/FDCA. This study has provided some useful insights as to how CNTs co-assembled with ferrocene-terminated thiols could impact on the electron transfer kinetics as well as the electrocatalytic detection of the self-assembled ferrocene layers.

Original languageEnglish
Pages (from-to)604-613
Number of pages10
JournalPhysical Chemistry Chemical Physics
Issue number3
Publication statusPublished - 2010
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Heterogeneous electron transfer kinetics and electrocatalytic behaviour of mixed self-assembled ferrocenes and SWCNT layers'. Together they form a unique fingerprint.

Cite this