Kinetics-Based Computational Catalyst Design Strategy for the Oxygen Evolution Reaction on Transition-Metal Oxide Surfaces

Density functional theory was used to examine the oxygen evolution reaction on a large number of active sites formed by doping three different surfaces of Co3O4 with various 3d transition-metal atoms. By combining the scaling and Brønsted–Evans–Polanyi (BEP) relationships that are determined for these sites, it is shown that the activity of a site is controlled by the redox potential for oxidation of the site. On the basis of this, a kinetics-based design strategy is presented for identifying the optimal active site at a given electrode potential. This design strategy is shown to be valid regardless of whether the rate-limiting water addition step occurs electrochemically or nonelectrochemically, as long as certain conditions are met. Another finding is that the BEP relations are sensitive to the structure of the active site, with sites reacting through μ3-oxo species having the most favorable relations. Finally, the kinetics-based design strategy is compared with the commonly used thermodynamics-based design strategy, and it is shown that the former is able to identify a site with equal or greater activity than the latter at the same computational cost.