Cooperative Single-Atom Active Centers for Attenuating the Linear Scaling Effect in the Nitrogen Reduction Reaction

Cooperative effects of adjacent active centers are critical for single-atom catalysts (SACs) as active site density matters. Yet, how it affects scaling relationships in many important reactions such as the nitrogen reduction reaction (NRR) is underexplored. Herein we elucidate how the cooperation of two active centers can attenuate the linear scaling effect in the NRR through a first-principle study on 39 SACs comprised of two adjacent (∼4 Å apart) four N-coordinated metal centers (MN₄ duo) embedded in graphene. Bridge-on adsorption of dinitrogen-containing species appreciably tilts the balance of adsorption of N₂H and NH₂ toward N₂H and thus substantially loosens the restraint of scaling relationships in the NRR, achieving low onset potential (V) and direct N≡N cleavage (Mo, Re) at room temperature, respectively. The potential of the MN₄ duo in the NRR provides new insight into circumventing the limitations of scaling relationships in heterogeneous catalysis.