Simulations to Cover the Waterfront for Iron Oxide Catalysis

Hematite has been widely studied for catalytic water splitting, but the role of the interactions between catalytic sites is unknown. In this paper, we calculate the oxygen evolution reaction free energies and the surface adsorption distribution using a combination of density functional theory and Monte Carlo simulations to “cover the waterfront,” or cover a wide range of properties with a simulation of the hematite surface under working conditions. First, we show that modeling noninteracting catalytic sites provides a poor explanation of hematite's slow reaction kinetics. The interactions between the catalytic site may hinder catalysis through the strong interactions of *OH(2) and *OOH intermediates, which cause the reaction to revert back to the *O intermediate. Hence, neighboring interactions may be a possible reason for the abundant, experimentally observed *O intermediate on the surface. This study demonstrates how neighboring sites impact the energy required for catalytic steps, thus providing new avenues to improve catalysis by controlling neighboring site interactions.