Oxygen evolving reactions catalyzed by different manganese oxides: the role of oxidation state and specific surface area

Abstract

Abstract A set of the four manganese oxide powders α-MnO2 (hollandite), δ-MnO2 (birnessite), Mn2O3 (bixbyite), and Mn3O4 (hausmannite) have been synthesized in a phase-pure form and tested as catalysts in three different oxygen evolution reactions (OER): electrochemical OER in KOH (1 mol L−1), chemical OER using aqueous cerium ammonium nitrate, and H2O2 decomposition. The trends in electrochemical (hollandite >> bixbyite > birnessite > hausmannite) and chemical OER (hollandite > birnessite > bixbyite > hausmannite) are different, which can be explained by differences in electric conductivity. H2O2 decomposition and chemical OER, on the other hand, showed the same trend and even a linear correlation of their initial OER rates. A linear correlation between the catalytic performance and the manganese oxidation state of the catalysts was observed. Another trend was observed related to the specific surface area, highlighting the importance of these properties for the OER. Altogether, hollandite was found to be the best performing catalyst in this study due to a combination of the high manganese oxidation state and a large specific surface area. Likely, due to a sufficient electrical conductivity, this intrinsically high OER performance is also found to some extent in electrocatalysis for this specific example.