Modeling Non-Precious Metal Catalyst Structures and Their Relationship to ORR

In this manuscript, we discuss the application of periodic density functional theory to modeling non-precious metal catalysts with a focus on the potential energy surfaces of the oxygen reduction reaction on two likely active-site-structures. Determination of the thermodynamic PES and overpotential are estimated for these sites. The role of van der Waals and its effect on predicted overpotential are addressed. It is found that overbinding of O-2 reactants and subsequent overbinding of *OH moieties lead to major sources of deviations from ideal thermodynamic behavior. As such, minor structural and chemical modifications are suggested to improve the studied active site candidates.