Double-Exchange-Induced in situ Conductivity in Nickel-Based Oxyhydroxides: An Effective Descriptor for Electrocatalytic Oxygen Evolution

Motivated by in silico predictions that Co, Rh, and Ir dopants would lead to low overpotentials to improve OER activity of Ni-based hydroxides, we report here an experimental confirmation on the altered OER activities for a series of metals (Mo, W, Fe, Ru, Co, Rh, Ir) doped into gamma-NiOOH. The in situ electrical conductivity for metal doped gamma-NiOOH correlates well with the trend in enhanced OER activities. Density functional theory (DFT) calculations were used to rationalize the in situ conductivity of the key intermediate states of metal doped gamma-NiOOH during OER. The simultaneous increase of OER activity with intermediate conductivity was later rationalized by their intrinsic connections to the double exchange (DE) interaction between adjacent metal ions with various d orbital occupancies, serving as an indicator for the key metal-oxo radical character, and an effective descriptor for the mechanistic evaluation and theoretical guidance in design and screening of efficient OER catalysts.

Automated summary

The study demonstrates that doping metals such as Co, Rh, and Ir can alter the OER activity of γ-NiOOH, and the in situ electrical conductivity shows a good correlation with enhanced OER activity. Density functional theory calculations are used to explain the in situ conductivity of metal-doped γ-NiOOH during OER, and the simultaneous increase of OER activity with intermediate conductivity is rationalized by the intrinsic connections to the double exchange interaction between adjacent metal ions.