Computational Investigation of Transition Metal Atom‐Decorated C₈N₈ Monolayers for Nitrogen Reduction Reaction

The electrocatalytic nitrogen reduction reaction (NRR) is regarded as a promising approach for sustainable ammonia synthesis. Developing highly active and selective catalysts remains a key challenge for this technology. C 8 N 8 serves as an excellent support for anchoring the single atoms due to its unique structures and high porosity. In this work, the catalytic performance of transition metal single‐atom‐decorated C 8 N 8 monolayers toward the NRR using density functional theory calculations is comprehensively studied. Among varied combinations, 24 candidates are screened out that are expected to be stable as indicated by negative binding energy ( E b < 0) and negative formation energy ( E f < 0). Among these, TiC 8 N 8 , MoC 8 N 8 , and OsC 8 N 8 exhibit relatively low reaction barriers of 0.67, 0.50, and 0.21 eV, suggesting potential catalytic activities. Especially, OsC 8 N 8 shows relatively good selectivity for the NRR compared with TiC 8 N 8 and MoC 8 N 8 . Electronic structure analysis reveals that OsC 8 N 8 effectively weakens the NN bond, facilitating N 2 activation. This work provides valuable insights into the material design for nitrogen reduction electrocatalysis and offers feasible candidates for the experimental synthesis.