Theoretical study of transition metal subphthalocyanine molecules (TM@C24H12N6) as highly active electrocatalysts for the nitrogen reduction to ammonia.

We design a series of transition metal phthalocyanine molecules (TM@C24H12N6, TM = Ti, V, Mn, etc.) as electrocatalysts for NRR. Our results indicates that Tc@C24H12N6 is the promising electrocatalyst with good adsorption, activation, low onset potential and high selectivity. [Display omitted] • A series of TM-phthalocyanine molecules (TM@C 24 H 12 N 6 , TM = Ti, V, Mn,Fe, Co, Ni, Zr, Nb, Mo, Tc, Ru, Rh, Pd, W, and Re) for NRR are investigated. • The onset potentials are −0.50, −0.43, and −0.65 V respectively for Nb/Mo/Tc@C 24 H 12 N 6. • Tc@C 24 H 12 N 6 exhibits high selectivity for NRR and a Faraday efficiency (FE) of 99.9 %. In this manuscript, we design a class of transition metal subphthalocyanine molecules as electrocatalysts for NRR. The results indicate that the Nb, Mo, and Tc systems can effectively absorb and activate a N 2 molecule and reduce onset potentials (−0.50, −0.43, and −0.65 V, respectively). Among them, the Tc@C 24 H 12 N 6 molecule has exceptionally high selectivity for NRR with the Faraday efficiency (FE) of ∼ 99.9 %. Therefore, the good stability, outstanding adsorption and activation properties of N 2 , very low onset potential, and high selectivity of Tc@C 24 H 12 N 6 indicate it possesses promising catalytic activity for NRR among the investigated catalysts. [ABSTRACT FROM AUTHOR]