Computational Screening of Efficient Single‐Atom Catalysts Based on Graphitic Carbon Nitride (g‐C3N4) for Nitrogen Electroreduction

Abstract The development of low‐cost and efficient electrocatalysts for nitrogen reduction reaction (NRR) at ambient conditions is crucial for NH 3 synthesis and provides an alternative to the traditional Harber‐Bosch process. Herein, by means of density functional theory (DFT) computations, the catalytic performance of a series of single metal atoms supported on graphitic carbon nitride (g‐C 3 N 4 ) for NRR is evaluated. Among all the candidates, the Gibbs free energy change of the potential‐determining step for five single‐atom catalysts (SACs), namely Ti, Co, Mo, W, and Pt atoms supported on g‐C 3 N 4 monolayer, is lower than that on the Ru(0001) stepped surface. In particular, the single tungsten (W) atom anchored on g‐C 3 N 4 (W@g‐C 3 N 4 ) exhibits the highest catalytic activity toward NRR with a limiting potential of −0.35 V via associative enzymatic pathway, and can well suppress the competing hydrogen evolution reaction. The high NRR activity and selectivity of W@g‐C 3 N 4 are attributed to its inherent properties, such as significant positive charge and large spin moment on the W atom, excellent electrical conductivity, and moderate adsorption strength with NRR intermediates. This work opens up a new avenue of N 2 reduction for renewable energy supplies and helps guide future development of single‐atom catalysts for NRR and other related electrochemical process.