Temperature-Dependent Electronic Structure of Bixbyite α-Mn2O3 and the Importance of a Subtle Structural Change on Oxygen Electrocatalysis

α-Mn2O3 is an inexpensive Earth-abundant mineral that is used as an electrode material in various kinds of electrochemical devices. The complex bixbyite structure of α-Mn2O3, and its subtle orthorhombic → cubic phase transformation near room temperature has made it challenging to accurately determine its electronic proper- ties. We used high-resolution X-ray diffraction to study the temperature-dependent structures of phase-pure α-Mn2O3 prisms. Our measurements show a clear change in the crystal phase from orthorhombic → cubic between 293K and 300K. We input the Rietveld refined high-resolution crystal structures collected at various temperatures (273, 293, 300, 330K) directly into density functional theory (DFT) calculations to model their electronic properties. These calculations indicate that the orthorhombic phase α-Mn2O3 is a narrow bandgap semiconductor as expected. However, temper- atures higher than 300K transform the α-Mn2O3 into the cubic phase, causing the molecular orbitals of the Mn 3d and O 2p bands to overlap and mix covalently, mak- ing the material behave as a semimetal. This subtle change in crystal structure will affect the bulk conductivity of the material as well as Mn-O-Mn bond distances that influence the quality of its catalytic active sites for oxygen electrochemistry. Elec- trochemical oxygen evolution (OER) and oxygen reduction reaction (ORR) experi- ments performed at various temperatures (∼ 288K to 323K) using the same prepared electrode show a marked enhancement in both OER and ORR performance that is attributed to the higher activity of the cubic phase.