Evidence that Crystal Facet Orientation Dictates Oxygen Evolution Intermediates on Rutile Manganese Oxide

Abstract Elucidating the mechanism that differentiates the oxygen‐evolving center of photosystem II with its inorganic counterpart is crucial to develop efficient catalysts for the oxygen evolution reaction (OER). Previous studies have suggested that the larger overpotential for MnO₂ catalysts under neutral conditions may result from the instability of the Mn³⁺ intermediate to charge disproportionation. Here, by monitoring the surface intermediates of electrochemical OER on rutile MnO₂ with different facet orientations, a correlation between the stability of the intermediate species and crystal facets is confirmed explicitly for the first time. The coverage of the Mn³⁺ intermediate is found to be 11‐fold higher on the metastable (101) surfaces compared to (110) surfaces, leading to the superior OER activity of (101) surfaces. The difference in OER activity may result from the difference in surface electronic states of Mn³⁺, where interlayer charge comproportionation of Mn²⁺ and Mn⁴⁺ to generate two Mn³⁺ species is favored on (101) facets. Considering the fact that the OER enzyme accommodates Mn³⁺ stably during the Kok cycle, the enhanced OER activity of the rutile MnO₂ catalyst with a metastable surface highlights the importance of mimicking not only the crystal structure but also the electronic structure of the targeted natural enzyme.