Fast Outer-Sphere Electron Transfer and High Specific Capacitance at Covalently Modified Carbon Electrodes.

Carbon electrodes typically display sluggish electron transfer kinetics due to the adsorption of adventitious molecules that effectively insulate the surface. Here, we describe a method for rendering graphitic carbon electrodes permanently hydrophilic by functionalization with 4-(diazonium)benzenesulfonic acid. In aqueous electrolytes, these hydrophilic carbon electrodes exhibit metal-like specific capacitance (∼40 µF/cm2) as measured by cyclic voltammetry, suggesting a change in the double-layer structure at the carbon surface. Additionally, the modified electrodes show fast charge transfer kinetics to outer-sphere one-electron redox couples such as ferro-/ferricyanide as well as improved electron transfer kinetics in alkaline aqueous redox flow batteries.