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 (similar to 4 angstrom 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 MN 4 duo in the NRR provides new insight into circumventing the limitations of scaling relationships in heterogeneous catalysis.

Automated summary

This study elucidates how the cooperation of two adjacent active centers can attenuate the linear scaling effect in the nitrogen reduction reaction. Bridge-on adsorption of dinitrogen-containing species shifts the adsorption balance between N2H and NH2 towards N2H, thus loosening the constraints of scaling relationships in the NRR.