Cathodic electrochemiluminescence of Ru(bpy)(3)(2+)/Nafion coated on graphite oxide electrode in purely aqueous solution.

Two cathodic electrochemiluminescence (ECL) peaks have been obtained at -0.99 and -1.80 V (vs. SCE), respectively, from Ru(bpy)(3)(2+)/Nafion coated onto a graphite oxide electrode in purely aqueous solution under cyclic voltammetric (CV) conditions, without addition of any reducing or oxidative reagents. These two ECL peaks were found to correlate to initial scan direction, pH, and reversal potential. Nafion played an important role in the generation of these two ECL peaks because no cathodic emission was observed in the system without Nafion. It seems that a part of Ru(bpy)(3) (3+) electrogenerated at positive potential can remain in the Nafion, even at negative potentials. It was con fi rmed that Ru(bpy)(+) was formed at -1.80 V by addition of S(2)O(8) (2-). The ECL peak at -0.99 V is attributed to the reaction of Ru(bpy)(3+) and OH(-). The ECL peak at -1.80 V is probably due to the annihilation reaction of Ru(bpy)(3+) and Ru(bpy)(+).