Periodic Defect Engineering of Iron–Nitrogen–Carbon Catalysts for Nitrate Electroreduction to Ammonia

Abstract

AbstractIron–nitrogen–carbon single atom catalyst (SAC) is regarded as one of the promising electrocatalysts for NO3− reduction reaction (NO3RR) to NH3 due to its high activity and selectivity. However, synergistic effects of topological defects and FeN4 active moiety in Fe–N–C SAC have rarely been investigated. By performing density functional theory (DFT) calculations, 13 defective graphene FeN4 with 585, 484, and 5775 topological line defects are constructed, yielding 585‐68‐FeN4 with optimal NO3RR catalytic activity, high selectivity, as well as robust anti‐dissolution stability. The high NO3RR activity on 585‐68‐FeN4 is well explained by the high valence state of Fe center as well as asymmetric charge distribution on FeN4 moiety influenced by 5‐ and 8‐member rings. This DFT work provides theoretical guidance for engineering NO3RR performance of iron–nitrogen–carbon catalysts by modulating periodic topological defects.