Theoretical and Computational Chemistry

Direct and indirect role of Fe doping in NiOOH monolayer for water oxidation catalysis

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Abstract

The oxygen evolution reaction (OER) activity of pristine NiOOH is enhanced by doping with Fe. However, the precise role of Fe is still being debated. Here, we use first-principles DFT+U approach to study three different types of active sites: one on pristine and the other two on Fe-doped NiOOH monolayers to account for the direct and indirect roles of Fe. To compare the activity of the active sites, we consider two mechanisms of OER based on the source of O-O bond formation. Our results show that the mechanism involving the coupling of lattice oxygen is generally more favorable than water nucleophilic attack on lattice oxygen. On doping with Fe, the overpotential of NiOOH is reduced by 0.29 V in excellent agreement with experimental findings. Doping Fe in NiOOH results in different potential determining steps (PDS) in the two mechanisms, whereas pristine NiOOH has the same PDS regardless of the mechanism.

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Electronic supplementary information for Direct and indirect role of Fe doping in NiOOH monolayer for water oxidation catalysis
This file contains supplementary information, including the tables of energies of various structures in different magnetic states, image highlighting oxo and hydroxo sites on NiOOH, comparison of transition state structure and free energy barriers of step E at all active sites, and spin density plot of HOO* atAS-3.