Computational Study of Double Transition Metal Atom Anchored on Graphdiyne Monolayer for Nitrogen Electroreduction

Abstract Converting N 2 to NH 3 is an essential reaction but remains a great challenge for industries. Developing more efficient catalysts for N 2 reduction under mild conditions is of vital importance. In this work, double transition metal atoms (TM=Mo, W, Nb and Ru) anchored on graphdiyne monolayer (TM 2 @GDY) as electrocatalysts are designed, and the corresponding reaction mechanisms of N 2 electroreduction are systematically investigated by means of first‐principles calculations. The results show that the double TM atoms can be strongly anchored on the acetylenic ring of GDY and Ru 2 @GDY exhibits the highest catalytic activity for NRR with a maximum free energy change of 0.55 eV through the enzymatic pathway. The significant charge transfer between the substrate and the adsorbed N 2 molecule is responsible for the superior catalytic activity. This work could provide a new approach for the rational design of double‐atom catalysts for NRR and other related reduction reactions.