Single-atom catalysts modified by molecular groups for electrochemical nitrogen reduction

Electrochemical nitrogen reduction reaction (eNRR) is one of the most important chemical reactions for the production of ammonia under ambient environment. However, the lack of in-depth understanding of the structure-activity relationship impedes the development of high-performance catalysts for ammonia production. Herein, the density functional theory (DFT) calculations are performed to reveal the structure–activity relationship for the single-atom catalysts (SACs) supported on g-C₃N₄, which is modified by molecular groups (i.e., H, O, and OH). The computational results demonstrate that the W-based SACs are beneficial to produce ammonia with a low limiting potential (U_L). Particularly, the W-OH@g-C₃N₄ catalyst exhibits an ultralow U_L of −0.22 V for eNRR. And the competitive eNRR selectivity can be identified by the dominant *N₂ adsorption free energy than that of *H. Our findings provide a theoretical basis for the synthesis of efficient catalysts to produce ammonia.