Reimagining the eg1 Electronic State in Oxygen Evolution Catalysis: Oxidation‐State‐Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis.

The discovery of solid‐phase, inexpensive transition‐metal‐based water oxidation catalysts is a central goal for renewable energy, and has led to a general consensus that a partially populated metal eg d‐electronic state is desirable, leading to favorable catalysis for certain elements in specific oxidation states. In manganese systems, the key species is manganese(III), whose high‐spin d4 electronic configuration places an unpaired electron in the eg orbital, which is postulated to contribute to electronic and structural features that support catalysis. Based on density functional theory calculations, it is predicted that electron transfer would be facilitated by a catalyst with alternating low‐ and high‐MnIII‐content sheets, which positions neighboring band edges in closer energetic proximity. The preparation of such catalysts is demonstrated for the first time and it is shown that the catalytic activity is maximized in these systems over more uniform, but more MnIII‐rich systems. The best catalyst possesses alternating high‐and low‐average oxidation state sheets with interlayer Cs+ ions, and has an overpotential of 450 mV at 10 mA, which represents an improvement of 250 mV over the best unmodified synthetic potassium birnessites. Using scanning tunneling spectroscopy, bandgap modulations consistent with the theoretically predicted band edge shifts are detected. [ABSTRACT FROM AUTHOR]