Configuration Sensitivity of Electrocatalytic Oxygen Reduction Reaction on Nitrogen-Doped Graphene

As one of the most promising nonprecious metal catalysts for the oxygen reduction reaction (ORR), the structure of the active site on nitrogen-doped carbon materials is still under debate. Here, we report that the sensitivity of the ORR on the local configuration of multiple nitrogen dopants may be overlooked. Combining global structure searching with density functional theory calculations, we established the structure-activity relationship for 19 and 298 possible configurations of graphitic nitrogen-doped graphene with N content of 2 and 3%, respectively. It was revealed that the stability cannot be a screener to determine the major contributor to the activity. 77.5% of current density is contributed by the active configuration with 4.59% population on the graphene containing 3% nitrogen. It unambiguously demonstrates the configuration sensitivity of N-doped graphene for ORR and opens a new window to identifying the optimal structure of N-doped carbons for various applications.