Voltammetric Studies Of The Mechanism Of The Oxygen Reduction In Alkaline Media At The Spinels Co3o4 And Nico2o4

The mechanism of O-2 reduction at the spinels, Co3O4 and NiCo2O4, in KOH electrolyte is probed using voltammetry at rotating disc and rotating ring-disc electrodes by examination of the rotation rate dependent limiting currents. The analysis shows that the products and mechanisms at the two spinels are quite different. At the cobalt spinel, a substantial amount of the 2e(-) reduction product, H2O2, is formed while at NiCo2O4 the 4e(-) reduction strongly predominates. In terms of both the overpotential for reduction and its limiting current density, the mixed spinel is a substantially better electrocatalyst. It is proposed that the differences arise from an enhanced rate of O-O bond cleavage early in the reduction process at NiCo2O4. (C) The Author(s) 2016. Published by ECS. All rights reserved.