Journal of Physical Chemistry B, Vol.105, No.15, 3088-3092, 2001
Effect of the metal on electron transfer across self-assembled monolayers
Electron-transfer kinetic measurements are made on one type of self-assembled monolayer {HS(CH2)(15)COOH with attached [Ru-II(NH3)(5)(4-aminomethylpyridine)]}on gold, platinum, and silver polycrystalline electrodes in one electrolyte at room temperature. Cyclic voltammograms over a wide range of scan rates are analyzed to extract the rate constants as a function of overpotential. Tafel plots are fitted to theoretical curves based on the Marcus DOS theory to obtain the standard rate constants and the reorganization energies. A reorganization energy of 0.8 +/- 0.1 eV is obtained on ah three metals. The standard rate constants for Au, Pt, and Ag are 1.0 +/- 0.3, 1.7 +/- 0.4, and 0.6 +/- 0.2 s(-1). The results confirm the theoretical prediction that the electronic coupling of "d" band states in the metal to remote redox centers is weak.