Catalysis of dinitrogen activation and reduction by a single Fe₁₃ cluster and its doped systems

Catalyzing N₂ reduction to ammonia under ambient conditions is known to be significant both in the fertilizer industry and life sciences. To unveil the synergy of multiple sites, here, we have studied the catalysis of ammonia synthesis using a typical Fe₁₃ cluster and its doped systems, Fe₁₂X (X = V, Cr, Mn, Co, Ni, Cu, Zn, Nb, Mo, Ru, and Rh). The energetics analysis showed that center substitution (X@Fe₁₂) was favored while doping single V, Cr, Co, and Mo atoms, whereas Mn, Ni, Cu, Zn, Nb, Ru, and Rh tended to form shell-doped structures (Fe₁₂X). Among all the 13 clusters, Fe₁₂Nb exhibited the lowest activation energy for N₂ dissociation; moreover, in the hydrogenation process, Fe₁₂Nb could convert N₂ to ammonia efficiently. We have fully illustrated the reaction dynamics and structural chemistry essence of these diverse 13-atom systems and propose Fe₁₂Nb as an ideal candidate for catalytic ammonia synthesis.