Prediction of Highly Selective Electrocatalytic Nitrogen Reduction at Low Overpotential on a Mo-Doped g‑GaN Monolayer

Identifying efficient electrocatalysts with low overpotential and high selectivity for producing ammonia from nitrogen gas is essential for any future electrocatalytic nitrogen reduction reaction (NRR)-based ammonia synthesis. Via density functional theory calculations and the computational hydrogen electrode model, we systematically examine the prospect of using a single-transition-metal (TM)-atom-doped graphene-like GaN (g-GaN) monolayer as an electrocatalyst for artificial nitrogen reduction. Among 15 TMs investigated, the Mo-doped g-GaN (Mo@g-GaN) monolayer is the only electrocatalyst predicted to be feasible for the NRR. The Mo@g-GaN monolayer satisfies all screening criteria considered for activating the inert NN triple bond effectively, including stabilization of the adsorbed (*) NRR intermediate *NNH and destabilization of the *NH2 species. This monolayer also possesses sufficient overall stability. A complete analysis of the likely mechanisms involved in the NRR on this catalyst suggests that the Mo@g-GaN monolayer could exhibit promising NRR catalytic activity. It achieves this via one specific (distal) pathway, which has a very low onset potential of −0.33 V vs the reversible hydrogen electrode (RHE), corresponding to a low overpotential of 0.42 V vs the RHE, defined using the measured equilibrium potential for NRR of 0.09 V vs the RHE. The potential-determining step, conversion of *NH2 to *NH3, also exhibits a surmountable barrier of 0.42 eV, suggesting kinetics will be facile. Finally, the Mo@g-GaN monolayer is predicted to exhibit substantial selectivity (∼31%) toward ammonia synthesis over the competing hydrogen evolution reaction. These findings may open a potential route for artificial ammonia synthesis using a single-atom catalyst under ambient conditions.