Importance of Correlation in Determining Electrocatalytic Oxygen Evolution Activity on Cobalt Oxides

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Abstract

Co-based oxides are suitable electrode materials for the electrocatalytic oxygen evolution reaction (OER) with promising activity and stability, in addition to being widely available and relatively cheap. We investigate OER on Co3O4(001) and β-CoOOH (011̅2) surfaces using density functional theory calculations (DFT). We construct surface Pourbaix diagrams and investigate the theoretical overpotential for the elementary steps involved in OER on these surfaces. We show that inclusion of the Hubbard-U correction to DFT (DFT+U) is necessary to recover experimentally observed trends in the activity for the strongly correlated cobalt oxides. We find that the inclusion of the Hubbard-U correction lowers the activity of both Co3O4(001) and β-CoOOH(011̅2) when compared to results from pure DFT. In addition, the Hubbard-U correction shifts the location of Co3O4 and β-CoOOH from the strong binding leg to the weak binding leg of the OER volcano plot. The calculations also suggest that the theoretical overpotentials for Co3O4 and β-CoOOH are very nearly the same. We ascribe this to a similar local coordination environment of the active Co site in Co3O4 and CoOOH under OER conditions.

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