Secondary Transition-Metal Dopants for Enhanced Electrochemical O2 Formation and Desorption on Fe-Doped β‑NiOOH

Previously we outlined possible doping strategies to improve the aqueous electrocatalytic oxygen evolving activity of iron-doped nickel oxyhydroxide (Ni1–xFexOOH). The strategies are based on two central mechanistic features of its efficient water oxidation: (1) metal-oxo bond formation and (2) three-electron reductive elimination of O2. Here, we explore secondary dopants that may promote the latter by enhancing O–O bond formation. From periodic slab models using screened-exchange hybrid density functional theory, we predict that Fe3+-doped β-NiOOH codoped with Cu2+ or Ag3+ will have even more favorable O–O coupling and molecular O2 desorption activity at the Fe sites. This work illustrates a mechanism-oriented design principle in the development of oxygen evolution catalysts.