The Electrocatalysis of Oxygen Evolution on Perovskites

Author: O’M. Bockris, John; Otagawa, Takaaki

Description: Measurements of the oxygen evolution reaction have been made on eighteen substituted perovskites containing first‐row transition metal ions. Rates are reported at equilibrium and at an overpotential of 0.3V. Electrode kinetic parameters are given, including roughness factors. The rate does not depend on semiconductor‐type properties. It increases as the pH of zero charge, at which the occupancy of OH⁻ and H⁺ at the interface becomes equal, moves in an alkaline direction, with decrease of magnetic moment, with decrease of stability of the perovskite lattice, with decrease of the enthalpy of formation of the transition metal hydroxides, and with increase in the number of d‐electrons in the transition metal ion. The accuracy of the roughness factor measurements are affected by weakness in knowledge of true double layer capacities. The value assumed here, 60 μF cm⁻², may be accurate to only ± 100%. Models are given which suggest that the pores are active throughout. The correlations between the rate and electronic properties are consistent with rate‐determining steps which involve desorption of OH radicals, e.g.,

M – OH + OH + -> r.d.s. Mz … H2O2 + e-

An MO discussion suggests that the electrocatalysis increases with increased occupancy of the antibonding orbitals of M^Z‒OH. Earlier interpretations include the concept that an increase of the rate occurs because of increasing overlap between the orbitals of the transition metal ion and the sp_σorbital of O. However, this theory is based on only three different materials, in which rate‐determining step changes. An interpretation based upon nonstoichiometry is shown to be consistent with observed trends, but insufficient to explain their magnitude. The electrical and chemical contributions to the rate are analyzed. The value of agr; is related via bond strength considerations to the M^Z‒OH bond strengths. The relative electrocatalysis discussed is limited to an overpotential which corresponds to a practical range of rates on the faster catalysts. A volcano relation for oxygen evolution on perovskites seems likely. Future electrocatalysts are predicted.