A Self-Consistent Framework for Tailored Single-Atom Catalysts in Electrocatalytic Nitrogen Reduction.

The catalytic activity of single-atom catalysts (SACs) is crucially affected by the actual ligand configurations under the reaction condition; thus, carefully considering the reaction condition is crucial for the theoretical design of SACs. With single metal atoms supported by g-C 3 N 4 as a model system, a self-consistent screening framework is proposed for the theoretical design of SACs with respect to the nitrogen reduction reaction (NRR). Pourbaix diagrams are constructed on the basis of various co-adsorption configurations of N 2 , H, and OH. Possible stable configurations containing N 2 under the expected reaction condition are considered to obtain the limiting potential of NRR, and the stability of the configuration at the calculated U L is rechecked. With this framework, AC stacking of double-layer g-C 3 N 4 -supported Nb and AA stacking and AB stacking of double-layer g-C 3 N 4 -supported W are predicted to exhibit superior NRR activity with U L values of -0.36, -0.45, and -0.52 V, respectively. This procedure can be widely applied to the screening of SACs for electrocatalytic reactions.