Revealing Energetics of Surface Oxygen Redox from Kinetic Fingerprint in Oxygen Electrocatalysis.

The key step for rational catalyst design in heterogeneous electrocatalysis is to reveal the distinctive energy profile of redox reactions of a catalyst that give rise to specific activity. However, it is challenging to experimentally obtain the energetics of oxygen redox in oxygen electrocatalysis because of the liquid reaction environment. Here we develop a kinetic model that constructs a quantitative relation between the energy profile of oxygen redox and electrochemical kinetic fingerprints. The detailed study here demonstrates that the kinetic fingerprints observed from experiments can be well described by different energetics of oxygen redox. On the basis of the model, a feasible methodology is demonstrated to derive binding energies of the oxygen intermediates from electrochemical data. The surface property of different catalysts derived from our model well rationalizes the experimental trends and predicts potential directions for catalyst design.