Enhanced activity in layered-metal-oxide-based oxygen evolution catalysts by layer-by-layer modulation of metal ion identity

Few-layered potassium nickel and cobalt oxides show drastic differences in catalytic activity based on metal ion preorganization. Uniform compositions $[(\mathrm{CoO}_2/\mathrm{K})_6$ or $(\mathrm{NiO}_2/\mathrm{K})_6]$ show limited activity, while homogenously-mixed-metal cobalt/nickel oxides $[(\mathrm{Co}_n\mathrm{Ni}_{1-n}\mathrm{O}_2/\mathrm{K})_6]$ display moderate improvement. However, a layer-by-layer arrangement of cobalt and nickel oxide sheets [e.g., $(\mathrm{CoO}_2/\mathrm{K}/\mathrm{NiO}_2/\mathrm{K})$] provides superior catalytic performance, reducing the oxygen evolution overpotential by more than 400 mV. Density functional theory simulations provide an illustration of the electronic properties (density of states and localization of orbitals) that promote catalysis in the layer-segregated materials over those of homogeneous composition. This study reveals that atomic preorganization of metal ions within layered catalysts plays a more crucial role than overall metal composition in enhancing catalytic efficiency for oxygen evolution.