Mesoporous Manganese Oxides with High-Valent Mn Species and Disordered Local Structures for Efficient Oxygen Electrocatalysis

Active and nonprecious-metal bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are vital components of clean energy conversion devices such as regenerative fuel cells and rechargeable metal–air batteries. Porous manganese oxides (MnOx) are promising electrocatalyst candidates because of their high surface area and the abundance of Mn. MnOx catalysts exhibit various oxidation states and crystal structures, which critically affect their electrocatalytic activity. These effects remain elusive mainly because the synthesis of oxidation-state-controlled porous MnOx with similar structural properties is challenging. In this work, four different mesoporous manganese oxides (m-MnOx) were synthesized and used as model catalysts to investigate the effects of local structures and Mn valence states on the activity toward oxygen electrocatalysis. The following activity trends were observed: m-Mn2O3 > m-MnO2 > m-MnO > m-Mn3O4 for the ORR and m-MnO2 > m-Mn2O3 > m-MnO ≈ m-Mn3O4 for the OER. These activity trends suggest that high-valent Mn species (Mn(III) and Mn(IV)) with disordered atomic arrangements induced by nanostructuring significantly influence electrocatalysis. In situ X-ray absorption spectroscopy was used to analyze the changes in the oxidation states under the ORR and OER conditions, which showed the surface phase transformation and generation of active species during electrocatalysis.