The Activation and Reduction of N 2 by Single/Double‐Atom Electrocatalysts: A First‐Principle Study

Abstract Developing low‐cost and highly efficient electrocatalysts for nitrogen reduction reaction (NRR) is one of the most attractive challenges. In this work, we systematically investigated the catalytic properties of the single atom catalysts (SAC) and the double atom catalysts (DAC) for NRR via First‐Principle calculations. The SAC and DAC were formed by single and double transition metal (TM) atoms anchored on N‐doped graphene monolayers (TM x N 3x ‐graphene, x=1, 2; TM=Mo, Fe, Co, Ni and Cu). It is shown that both the SAC and the DAC have exhibited high catalytic properties for NRR. Moreover, when N 2 is absorbed by its side‐on sites, SAC even performs better than DAC. And in five kinds of TM atoms, Fe‐complexes exhibit significantly improved catalytic properties. Especially, Fe 1 N 3 ‐graphene has the best catalytic activity for NRR with the lowest free energy change of 0.04 eV in the rate determining step (RDS). This work not only proposes the differences of SAC and DAC but also provides a new kind of single atom catalysts (SAC) for NNR.