Tetrahedral W₄cluster confined in graphene-like C₂N enables electrocatalytic nitrogen reduction from theoretical...

Exploring the format of active site is essential to further the understanding of an electrocatalyst working under ambient conditions. Herein, we present a DFT study of electrocatalytic nitrogen reduction (eNRR) on W₄tetrahedron embedded in graphene-like C₂N (denoted as W₄@C₂N). Our results demonstrate that N-affinity of active sites on W₄dominate over single-atom site, rendering *NH₂ + (H⁺ + e^-) →*NH₃invariably the potential-determining step (PDS) of eNRR via consecutive or distal route (U_L = -0.68 V) to ammonia formation. However, *NHNH₂ + (H⁺ + e^-) →*NH₂NH₂has become the PDS (U_L = -0.54 V) via enzymatic route towards NH₂NH₂formation and thereafter desorption, making W₄@C₂N a potentially promising catalyst for hydrazine production from eNRR. Furthermore, eNRR is competitive with hydrogen evolution reaction (U_L = -0.78 V) on W₄@C₂N, which demonstrated sufficient thermal stability and electric property for electrode application.