Activating Mn3O4 by Morphology Tailoring for Oxygen Reduction Reaction

Oxygen reduction reaction (ORR) is becoming increasingly important with the development of fuel cells and metal-air batteries. Manganese oxides have been one of the focuses of recent research for Pt-alternative ORR catalysts. However, the structure-activity relationships of manganese oxides have not been well studied or understood. In the present work, we report a new finding that there is a strong dependence of the ORR activity of Mn 3 O 4 on its morphology. By adopting different solvents in the wet-chemical synthesis, we are able to tailor the morphology of Mn 3 O 4 from nanoparticles (NP-L, 12.5 nm and NP-S, 5.95 nm) to nanorods (NR, exposure of Mn 3 O 4 (101)) and nanoflake (NF, exposure of Mn 3 O 4 (001)). Surprisingly, surface-specific activity of NF toward the ORR was found to be one order of magnitude higher than NP-L. The morphology-activity relationships of Mn 3 O 4 were further studied through a combination of electrochemical experiments and density functional theory (DFT) calculations. It was discovered that the formation of *OOH, concomitant with the first electron transfer, is the potential determining step, which is thermo-dynamically more facile on Mn 3 O 4 (001) than (101) plane. The underlying mechanism could be ascribed to the strong interaction between O 2 and Mn 3 O 4 (001) surface as indicated by the DFT calculations. The study enlarges our understanding of Mn 3 O 4 catalysis and provides clues for rational design of highly efficient transitional metal oxide electrocatalysts for the ORR.