Catalysis of dinitrogen activation and reduction by a single Fe 13 cluster and its doped systems.

Catalyzing N 2 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 Fe 13 cluster and its doped systems, Fe 12 X (X = V, Cr, Mn, Co, Ni, Cu, Zn, Nb, Mo, Ru, and Rh). The energetics analysis showed that center substitution (X@Fe 12 ) 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 (Fe 12 X). Among all the 13 clusters, Fe 12 Nb exhibited the lowest activation energy for N 2 dissociation; moreover, in the hydrogenation process, Fe 12 Nb could convert N 2 to ammonia efficiently. We have fully illustrated the reaction dynamics and structural chemistry essence of these diverse 13-atom systems and propose Fe 12 Nb as an ideal candidate for catalytic ammonia synthesis.