Role of Chemical Structure of Support in Enhancing the Catalytic Activity of a Single Atom Catalyst Toward NRR: A Computational Study

Using the periodic density functional theory–based methodology, we propose a potential catalytic system for dinitrogen activation, viz., single metal atoms (Mo, Fe, and V) supported on graphene-based sheets. Graphene-based sheets show an excellent potential toward the anchoring of single atoms on them (Mo, Fe, and V) with adsorption energies ranging between 1.048 and 10.893 eV. Factors such as defects and BN doping are noted to enhance the adsorption energies of single metal atoms on the support. The adsorption of a dinitrogen molecule on metal atom–anchored graphene-based supports is seen to be highly favorable, ranging between 0.620 and 2.278 eV. The adsorption is driven through a direct hybridization between the d orbitals of the metal atom (Mo, Fe, and V) on the support and the p orbital of the molecular nitrogen. Noticeably, BN-doped graphene supporting a single metal atom (Mo, Fe, and V) activates the N(2) molecule with a red shift in the N–N stretching frequency (1,597 cm(−1) as compared to 2,330 cm(−1) in the free N(2) molecule). This red shift is corroborated by an increase in the N–N bond length (1.23 Å from 1.09 Å) and charge transfer to an N(2) molecule from the catalyst.