Structural insight into [Fe-S₂-Mo] motif in electrochemical reduction of N₂ over Fe₁-supported molecular MoS₂

The catalytic synthesis of NH₃ from the thermodynamically challenging N₂ reduction reaction under mild conditions is currently a significant problem for scientists. Accordingly, herein, we report the development of a nitrogenase-inspired inorganic-based chalcogenide system for the efficient electrochemical conversion of N₂ to NH₃, which is comprised of the basic structure of [Fe-S₂-Mo]. This material showed high activity of 8.7 mg_NH mg_Fe ^-1 h^-1 (24 μg_NH cm^-2 h^-1) with an excellent faradaic efficiency of 27% for the conversion of N₂ to NH₃ in aqueous medium. It was demonstrated that the Fe₁ single atom on [Fe-S₂-Mo] under the optimal negative potential favors the reduction of N₂ to NH₃ over the competitive proton reduction to H₂. Operando X-ray absorption and simulations combined with theoretical DFT calculations provided the first and important insights on the particular electron-mediating and catalytic roles of the [Fe-S₂-Mo] motifs and Fe₁, respectively, on this two-dimensional (2D) molecular layer slab.