Organic monolayers for interfacing electrocatalytic molecules to nanostructured electrodes

COLL 403

Elizabeth C. Landis, elandis@chem.wisc.edu, Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, WI 53706 and Robert J. Hamers, rjhamers@facstaff.wisc.edu, Department of Chemistry, University of Wisconsin - Madison, 1101 University Avenue, Madison, WI 53706.
Vertically aligned carbon nanofibers (VACNFs) are a novel form of carbon with high stability and extremely high surface area of edge-plane graphite, suggesting they should be an excellent support for electrocatalysis. We have investigated the electrochemical properties of redox-active molecules grafted onto VACNFs as a model system for tethered electrocatalysis. Electrochemical impedance spectroscopy was used to investigate the impact of an attached molecular layer and tethered ferrocene molecules as a function of frequency and potential. Cyclic voltammetry and potential step methods were used to extract electron-transfer rates, and compare the electron transfer rates of ferrocene attached to VACNF with gold and glassy carbon planar surfaces. Electron transfer rates can be correlated with characteristics of the substrate using valence band spectroscopy to find the density of states. These results provide insight into the role of the substrate and organic monolayers in controlling the rates of molecular electrocatalysis at nanostructured electrodes.