On the Origin of the OER Activity of Ultrathin Manganese Oxide Films

There is an urgent need for cheap, stable, and abundant catalyst materials for photoelectrochemical water splitting. Manganese oxide is an interesting candidate as an oxygen evolution reaction (OER) catalyst, but the minimum thickness above which MnOx thin films become OER-active has not yet been established. In this work, ultrathin (<10 nm) manganese oxide films are grown on silicon by atomic layer deposition to study the origin of OER activity under alkaline conditions. We found that MnO_x films thinner than 1.5 nm are not OER-active. X-ray photoelectron spectroscopy shows that this is due to electrostatic catalyst-support interactions that prevent the electrochemical oxidation of the manganese ions close to the interface with the support, while in thicker films, Mn^III and Mn^IV oxide layers appear as OER-active catalysts after oxidation and electrochemical treatment. From our investigations, it can be concluded that one Mn^III,IV-O monolayer is sufficient to establish oxygen evolution under alkaline conditions. The results of this study provide important new design criteria for ultrathin manganese oxide oxygen evolution catalysts. © 2021 American Chemical Society.