Alkaline-stable nickel manganese oxides with ideal band gap for solar fuel photoanodes

Combinatorial (photo)electrochemical studies of the (Ni-Mn)O_x system reveal a range of promising materials for oxygen evolution photoanodes. X-ray diffraction, quantum efficiency, and optical spectroscopy mapping reveal stable photoactivity of NiMnO₃ in alkaline conditions with photocurrent onset commensurate with its 1.9 eV direct band gap. The photoactivity increases upon mixture with 10-60% Ni₆MnO₈ providing an example of enhanced charge separation via heterojunction formation in mixed-phase thin film photoelectrodes. Density functional theory-based hybrid functional calculations of the band edge energies in this oxide reveal that a somewhat smaller than typical fraction of exact exchange is required to explain the favorable valence band alignment for water oxidation.