Electrocatalytic Mechanism of N₂ Reduction Reaction by Single-Atom Catalyst Rectangular TM-TCNQ Monolayers

Herein, the catalytic properties and reaction mechanisms of the 3d, 4d, and 5d transition metals embedded in 2D rectangular tetracyanoquinodimethane (TM-rTCNQ) monolayers as single-atom catalysts (SACs) for the electrocatalytic N2 reduction reaction (NRR) were systematically investigated, using first-principles calculations. A series of high-throughput screenings were carried out on 30 TM-rTCNQ monolayers, and all possible NRR pathways were explored. Three TM-rTCNQ (TM = Mo, Tc, and W) SACs were selected as promising new NRR catalyst candidates because of their high structural stability and good catalytic performance (low onset potential and high selectivity). Our results show that the Mo-rTCNQ monolayer can catalyze NRR through a distal mechanism with an onset potential of −0.48 V. Surprisingly, the NH3 desorption energy on the Mo-rTCNQ monolayer is only 0.29 eV, the lowest one reported in the literature so far, which makes the Mo-rTCNQ monolayer a good NRR catalyst candidate. In-depth research studies on the structures of N2–TM-rTCNQ (TM = Mo, Tc, and W) found that strong adsorption and activation performance of TM-rTCNQ for N2 may be due to the strong charge transfer and orbital hybridization between the TM-rTCNQ catalyst and the N2 molecules. Our work provides new ideas for achieving N2 fixation under environmental conditions.