Cocatalysis: Role of Organic Cations in Oxygen Evolution Reaction on Oxide Electrodes.

Cocatalysis is a promising approach toward enhanced electrocatalytic activity. We report such synergic catalysis involving organic xanthylium-based catalyst, Xan2+, and oxides formed on the electrode surface. The oxygen evolution reaction (OER) was observed on some working electrodes (gold, platinum, glassy carbon, boron-doped diamond), while others (titanium and fluorine-doped tin oxide) exhibited no OER activity. On the basis of experimental data and supported by calculations, we propose a mechanism in which oxidized Xan2+ activates electrode toward the rate-determining O-O bond formation. In light of our findings, efficient OER electrocatalysis can be achieved using materials that strongly bind oxygen species and electron-deficient organic cations.