Transition metal single-atom supported on W2N3 as efficient electrocatalysts for the nitrogen reduction reaction: A DFT study

The problems of poor Faraday efficiency and high overpotential usually limit electrochemical nitrogen reduction (NRR) catalysts. In this paper, 28 different transition metal single-atoms (TM-SAs) supported on W2N3 (TM@W2N3) were designed by density functional theory (DFT) for catalytic N2 reduction. The stability, N2 activation capacity, selectivity and NRR mechanism of TM@W2N3 were analyzed. Following the screening process, only 9 TM@W2N3 (TM=Sc, Ti, V, Co, Cu, Y, Mo, Ag, W) structures were identified as exhibiting high stability, strong activation capacity and high NRR selectivity. And then N2 activation mechanism of V@W2N3, Mo@W2N3 and W@W2N3, as well as the Gibbs free energies of its four NRR reaction pathways were further discussed. The overpotentials (t)) of Mo@W2N3 and V@W2N3 to NRR are 0.129 V and 0.470 V, respectively. The overpotential (t)) of W@W2N3 is the lowest at 0.059 V, while its catalytic activity is the highest. V@W2N3 and W@W2N3 are more likely to follow the distal pathway for NRR, while Mo@W2N3 is more likely to follow the enzymatic pathway. This study offers some theoretical foundation and reference for the design of new and efficient electrocatalytic NRR catalysts.