Distance-independent charge-transfer resistance at gold electrodes modified by thiol monolayers and metal nanoparticles

The electrochemical properties of An electrodes sequentially modified by self-assembled monolayers (SAM) of carboxyl-terminated alkane thiols, ultrathin poly-L-lysine (PLL) film, and diluted monolayers of Au nanoparticles are investigated by electrochemical impedance spectroscopy (EIS). The phenomenological charge-transfer resistance (R-ct) for the hexacyanoferrate redox couple at the equilibrium potential exhibited an exponential increase with increasing methylene units (x) in the SAM. The increase of R-ct between x = 1 and 10 was described by a well-defined decay parameter beta = 1.16 +/- 0.04 per methylene unit. This behavior suggests that the kinetics of electron transfer is controlled by coherent electron tunneling across the carboxyl-terminated SAM. Adsorption of the PLL brings about an average 2.5 times decrease in R-ct independent of x. The ultrathin PLL film (thickness less than 1 nm) induces an increase of the surface concentration of the redox couple without affecting the beta value observed for the SAM-terminated electrodes. Diluted monolayers of An nanoparticles with an average 19.2 +/- 2.1 nm diameter generate significant changes in the dynamics of electron transfer. In contrast to the behavior in the absence of nanoparticles, a distance-independent R-ct was observed for x > 5. Detailed analysis of the electrochemical responses as a function of the particle number density revealed that the rate-determining step is the charging of the nanoparticles by the redox species. It is concluded that the electronic communication between the nanoparticles and the electrode Surface over distances as large as 13 angstrom originates from electron transport through the trapped redox probe. The several orders of magnitude changes of the apparent R-ct upon nanoparticle adsorption further suggest that electron transport through the film does not occur via a classical hopping mechanism. A mechanism based on nonthermalized electron transport via the density of the redox probe at the Fermi energy (hot electron transport) is proposed to account for the experimental observations.