Lattice strain and atomic replacement of CoO6 octahedra in layered sodium cobalt oxide for boosted water oxidation electrocatalysis

Abstract

Layered alkali metal oxides have been emerged as an alternative group of low-cost and promising electrocatalysts in water oxidation. The distinct layered configuration may offer some interesting possibilities to tune the intrinsic activity by regulating the intralayer edge-shared CoO6 octahedra and the CoO2 interlayer spacing/strain. In this work, electrochemical desodiation tuning method is explored on intralayer Ag, Cu, Ce-doped Na0.7CoO2 for highly active OER catalysts. It is demonstrated that the ΔGOH* value in the volcano plot is optimized by proper desodiation. Meanwhile, the lattice strain introduced along with the desodiated process modulates the ΔGOH*, according to first principle calculations. It shows that ∼0.157 % compressive strain in the CoO2 layers and ∼1% tensile strain between CoO2 layers are introduced in the desodiated Ag doped Na0.7CoO2. Among these catalysts, the desodiated Ag-Na0.7CoO2 sample exhibits an optimal RuO2-beyond water oxidation (OER) activity with the lowest overpotential of 236 mV@10 mA/cm2, the smallest Tafel slope of 48 mV/dec and the highest mass current density of 227.8 A/g. This work provides an interesting avenues to optimize existing layered materials with inter/intralayer modifications for highly efficient water oxidation electrolysis.