Theoretical evaluation of nitrate reduction reaction on single‐atom anchored boron nitride fullerene

Abstract Nitrate reduction reaction (NO 3 RR) is a powerful technique for eliminating pollution. Here, NO 3 RRs on transition metal‐doped boron nitride fullerene (TM/B 11 N 12 ) were thoroughly examined utilizing density functional theory (DFT). Co/B 11 N 12 , a potential single‐atom catalyst (SAC) with a low thermal barrier for NO 3 RR toward NH 3 synthesis with good stability, activity, and selectivity, was successfully screened out. Co/B 11 N 12 has the lowest limiting potential ( U L ) of −0.45 V and good NO 3 RR performance. Due to the comparatively restrained adsorption of proton on Co/B 11 N 12 , competitive hydrogen evolution reaction (HER) is substantially limited. The excellent selectivity for the production of NH 3 is ensured by significant energy barrier prerequisite for the formation of by‐products (NO, NO 2 , N 2 O, and N 2 ) on Co/B 11 N 12 . By ab initio molecular dynamics (AIMD) simulations, Co/B 11 N 12 exhibits remarkable structural stability at 400 K with minimal distortion as compared to its initial shape. Our research may not only offer a fundamental understanding of the activity origin of NO 3 RR and catalytic mechanism on TM/B 11 N 12 but also open up opportunities for rational designing of SACs for NO 3 RR toward the NH 3 synthesis.