Tetrahedral Wcluster confined in graphene-like CN enables electrocatalytic nitrogen reduction from theoretical perspective.

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 Wtetrahedron embedded in graphene-like CN (denoted as W@CN). Our results demonstrate that N-affinity of active sites on Wdominate over single-atom site, rendering *NH + (H + e) →*NHinvariably the potential-determining step (PDS) of eNRR via consecutive or distal route ( = -0.68 V) to ammonia formation. However, *NHNH + (H + e) →*NHNHhas become the PDS ( = -0.54 V) via enzymatic route towards NHNHformation and thereafter desorption, making W@CN a potentially promising catalyst for hydrazine production from eNRR. Furthermore, eNRR is competitive with hydrogen evolution reaction ( = -0.78 V) on W@CN, which demonstrated sufficient thermal stability and electric property for electrode application.