The kinetics for interfacial electron transfer (ET) from a transparent conductive oxide (tin-doped indium oxide, ITO, Sn:InO) to molecular acceptors 4-[N,N-di(p-tolyl)amino]benzylphosphonic acid, TPA, and [Ru(bpy)(4,4'-(POH)-bpy)], RuP, positioned at variable distances within and beyond the electric double layer (EDL), were quantified in benzonitrile and methanol by nanosecond absorption spectroscopy as a function of the thermodynamic driving force, -ΔG°. Relevant ET parameters such as the rate constant, k, reorganization energy, λ, and electronic coupling, H, were extracted from the kinetic data. Overall, k increased as the distance between the molecular acceptor and the conductor decreased. For redox active molecules within the Helmholtz planes of the EDL, k was nearly independent of -ΔG°, consistent with a negligibly small λ value. Rips-Jortner analysis revealed a non-adiabatic electron transfer mechanism consistent with H < 1 cm. The data indicate that the barrier for electron transfer is greatly diminished at the conductor-electrolyte interface.
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