Crystallization design of MnO2via acid towards better oxygen reduction activity

Manganese dioxide is one of the important electrode materials used for oxygen reduction reaction (ORR) in fuel-cell and metal-air batteries, and its electrochemical activity is greatly influenced by its crystalline structure. To elucidate the crystalline structure effect on the ORR, herein, we designed a facile method to obtain α-MnO2 and γ-MnO2via adjusting the acid under hydrothermal conditions using the same starting materials and reagents. The prepared α-MnO2 and γ-MnO2 have a similar morphology composed of 3D microscopic spheres made up of numerous nanorods. X-ray photoelectron spectroscopy, temperature programmed desorption of oxygen characterization and conductivity measurements demonstrate that the α-MnO2 material has a relatively higher ratio of surface oxygen species, higher oxygen mobility and higher electrical conductivity. When compared with γ-MnO2, α-MnO2 displays superior ORR activity with a higher electron transfer number and lower yield of peroxide species in alkaline solutions. The obtained results shed new light on the crystalline structure-dependent ORR activity of MnO2.