Dynamic Level Diagrams: A New Tool for Predicting Isolation of Reaction Intermediates through Joint Density-Functional Theory

The oxygen reduction reaction (ORR) features prominently and is of fundamental importance in the field of electrocatalysis, with direct applications to fuel cells. The alkaline ORR on metal oxide surfaces shows great promise to reduce/eliminate the need for costly platinum group metals (PGMs). Building on the results we presented last year, we present convincing evidence that we have identified the actual reaction pathway on the Co3O4 surface through ab initio calculations, finding excellent agreement with experiment. Using a new tool we have developed, a dynamic interactive energy level diagram, we also demonstrate how 3 out of 4 of the reaction intermediates can be isolated by applying appropriate voltages to the surface for direct confirmation of the pathway via operando experimental tools. Finally, we present results for related spinel materials.