Rational Design of Graphene-Supported Single-Atom Catalysts for Electroreduction of Nitrogen

Critically, the central metal atoms along with their coordination environment play a significant role in the catalytic performance of single-atom catalysts (SACS). Herein, 12 single Fe, Mo, and Ru atoms supported on defective graphene are theoretically deigned for investigation of their structural and electronic properties and catalytic nitrogen reduction reaction (NRR) performance using first-principles calculations. Our results reveal that graphene with vacancies can be an ideal anchoring site for stabilizing isolated metal atoms owing to the strong metal-support interaction, forming stable TMCx or TMNx active centers (x = 3 or 4). Six SACs are screened as promising NRR catalyst candidates with excellent activity and selectivity during NRR, and RuN3 is identified as the optimal one with an overpotential of >= 0.10 V via the distal mechanism.

Automated summary

The study investigates the structural and electronic properties as well as the catalytic nitrogen reduction reaction (NRR) performance of 12 single Fe, Mo, and Ru atoms supported on defective graphene through theoretical design and first-principles calculations. Graphene with vacancies is found to be an ideal anchoring site for stabilizing isolated metal atoms, forming stable TMCx or TMNx active centers. Six promising NRR catalyst candidates with excellent activity and selectivity are screened, with RuN3 identified as the optimal catalyst with an overpotential of >= 0.10 V via the distal mechanism.