Computational screening of single-atom catalysts supported on Al12N12 nanocage for nitrogen reduction reaction

Abstract

The electrochemical nitrogen reduction reaction (NRR) on TM@Al12N12(TM=Sc∼Cu, Mo, Ru∼Pd) nanocages are investigated by density functional theory (DFT) study. TM@Al12N12(TM=Cr, Co, Ni, Ru, Mo, Rh) are evaluated as potential candidate using N2 adsorption (ΔG(*N2)), protonation reactions in first step (ΔG(*N2-*NNH)) and final step (ΔG(*NH2-*NH3)). Among all the screened deposition systems, the NRR performance shows an increase over the pure Al12N12 nanocage and the first hydrogenation step (*N2-*NNH) is the potential determining step. The electronic effect and charge transfer of the system are analyzed by the density of states (DOS) and natural bond orbital (NBO) charge. The electron density difference and the frontier orbitals analysis reveal that the screened deposition nanocages exhibit a significantly improved activation of N2 compared to the pure Al12N12 nanocage. Especially, the Ru@Al12N12 has excellent reactivity for NRR with the limiting potential of −0.80 V via distal pathway.