Electrocatalysis Beyond the Computational Hydrogen Electrode

Abstract

The computational hydrogen electrode approach allows the alignment of theoretical electrochemical potentials calculated with ab initio methods to those measured in experiment. It contributed greatly to opening up the fields of electrochemistry and photo-electrochemistry to theoretical treatment. Yet, virtually all practical implementations of the computational hydrogen electrode relied on a number of simplifications and approximations, which are not necessarily always justified. This chapter highlights three of these approximations as well as the challenges prompting them and gives a brief review of the computational methods available to overcome each. Specifically, it addresses the effects of the electrolyte, the important choice of the model reactive site – including surface defects and co-catalysts – and the evaluation of kinetic barriers.