Electrochemical water-based energy cycles provide a most promising alternative to fossil-fuel sources of energy. However, current electrocatalysts are not adequate (high overpotential, lack of selectivity toward O_2 production, catalyst degradation). We propose here mechanistic guidelines for experimental examination of modified catalysts based on the dependence of kinetic rates on the solvent dielectric constant. To illustrate the procedure we consider the fcc(111) platinum surface and show that the individual steps for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) change systematically with the polarizability of the medium. Thus changing this environmental variable can be used to tune the rate determining steps and the barriers, providing a means for screening and validating new systems to optimize the rate determining steps for the ORR and OER reaction pathways
