Kinetic Evidence That the Solvent Barrier for Electron Transfer Is Absent in the Electric Double Layer

Classical capacitance studies have revealed that the first layer of water present at an aqueous metal-electrolyte interface has a dielectric constant less than 1/10th of that of bulk water. Modern theory indicates that the barrier for electron transfer will decrease substantially in this layer; yet, this important prediction has not been tested experimentally. Here, we report the interfacial electron transfer kinetics for molecules positioned at variable distances within the electric double layer of a transparent conductive oxide as a function of the Gibbs free energy change. The data indicate that the solvent reorganization is indeed near zero and increases to bulk values only when the molecules are positioned greater than 15 Å from the conductive electrode. Consistent with this conclusion, lateral intermolecular electron transfer, parallel to a semiconducting oxide electrode, was shown to be more rapid when the molecules were within the electric double layer. The results provide much needed feedback for theoretical studies and also indicate a huge kinetic advantage for aqueous electron transfer and redox catalysis that takes place proximate to a solid interface.