Metal Nanoparticle Enhancement of Electron Transfer to Tethered Redox Centers through Self-Assembled Molecular Films

Metal-nanoparticle-mediated electron transfer (ET) across an insulator thin film containing nanoparticles with attached redox centers was studied using electrochemical impedance spectroscopy. Specifically, a gold spherical microelectrode was modified with 16-amino-1-hexa-decanethiol, creating an insulator film. This was followed by the electrostatic adsorption of gold nanoparticles and the covalent attachment of Os²⁺ redox centers. A variation of the Creager-Wooster method was developed to get quantitative information regarding the ET kinetics of the system. The experimental data obtained from a single measurement was fitted with a model that decouples two or more ET processes with different time constants and considers a Gaussian distribution of tunneling distances. Two parallel ET mechanisms were observed: one in which the electrons flow by tunneling between the surface and the redox couples with a low k_ET⁰ = 1.3 s^-1 and a second one in which an enhancement of the electron transfer is produced due to the presence of the gold nanoparticles with a k_ET⁰ = 7 × 10⁴ s^-1. In this study, we demonstrate that the gold nanoparticle electron transfer enhancement is present only in the local environment of the nanoparticle, showing that the nanoscale architecture is crucial to maximize the enhancement effect.