Altering the rate-determining step over cobalt single clusters leading to highly efficient ammonia synthesis

Activation of high-energy triple-bonds of N₂ is the most significant bottleneck of ammonia synthesis under ambient conditions. Here, by importing cobalt single clusters as strong electron-donating promoter into the catalyst, the rate-determining step of ammonia synthesis is altered to the subsequent proton addition so that the barrier of N₂ dissociation can be successfully overcome. As revealed by density functional theory calculations, the N₂ dissociation becomes exothermic over the cobalt single cluster upon the strong electron backdonation from metal to the N₂ antibonding orbitals. The energy barrier of the positively shifted rate-determining step is also greatly reduced. At the same time, advanced sampling molecular dynamics simulations indicate a barrier-less process of the N₂ approaching the active sites that greatly facilitates the mass transfer. With suitable thermodynamic and dynamic property, a high ammonia yield rate of 76.2 μg h^-1 mg[Formula: see text] and superior Faradaic efficiency of 52.9% were simultaneously achieved.