Abstract
Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal-air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2 O4 , the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including Mnx Co3-x O4 (x = 2, 2.5, 3), Lix Mn2 O4 (x = 0.7, 1), XCo2 O4 (X = Co, Ni, Zn), and XFe2 O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.
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