Active MnOx Electrocatalysts Prepared by Atomic Layer Deposition for Oxygen Evolution and Oxygen Reduction Reactions

The ability to deposit conformal catalytic thin films enables opportunities to achieve complex nanostructured designs for catalysis. Atomic layer deposition (ALD) is capable of creating conformal thin films over complex substrates. Here, ALD-MnOx on glassy carbon is investigated as a catalyst for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), two reactions that are of growing interest due to their many applications in alternative energy technologies. The films are characterized by X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, ellipsometry, and cyclic voltammetry. The as-deposited films consist of Mn(II)O, which is shown to be a poor catalyst for the ORR, but highly active for the OER. By controllably annealing the samples, Mn2O3 catalysts with good activity for both the ORR and OER are synthesized. Hypotheses are presented to explain the large difference in the activity between the MnO and Mn2O3 catalysts for the ORR, but similar activity for the OER, including the effects of surface oxidation under experimental conditions. These catalysts synthesized though ALD compare favorably to the best MnOx catalysts in the literature, demonstrating a viable way to produce highly active, conformal thin films from earth-abundant materials for the ORR and the OER.