Comparative density functional theory study for predicting oxygen reduction activity of single-atom catalyst

It has been well established that nitrogen coordinated transition metal, TM-N4-C (TM = Fe and Co) moieties, are responsible for the higher catalytic activity electrochemical oxygen reduction reaction. However, results obtained using density functional theory calculations vary from one to another, which can lead controversy. Herein, we assess accuracy of theoretical approach different class exchange-correlation functionals, i.e., Perdew-Burke-Ernzerhof (PBE) revised PBE (RPBE), those with Grimme’s semiempirical dispersion correction (PBE+D3 RPBE+D3), Bayesian error estimate nonlocal correlation (BEEF-vdW) on reaction energies TM-N4 moieties in graphene OH-termination. We found predicted overpotentials RPBE+D3 comparable consistent BEEF-vdW. Our finding indicates a proper choice is crucial precise description this system.