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

Nitrate reduction reaction (NO₃RR) is a powerful technique for eliminating ${\mathrm{NO}}_3^{-}$ pollution. Here, NO₃RRs on transition metal-doped boron nitride fullerene (TM/B₁₁N₁₂) were thoroughly examined utilizing density functional theory (DFT). Co/B₁₁N₁₂, a potential single-atom catalyst (SAC) with a low thermal barrier for NO₃RR toward NH₃ synthesis with good stability, activity, and selectivity, was successfully screened out. Co/B₁₁N₁₂ has the lowest limiting potential (U_L) of −0.45 V and good NO₃RR performance. Due to the comparatively restrained adsorption of proton on Co/B₁₁N₁₂, competitive hydrogen evolution reaction (HER) is substantially limited. The excellent selectivity for the production of NH₃ is ensured by significant energy barrier prerequisite for the formation of by-products (NO, NO₂, N₂O, and N₂) on Co/B₁₁N₁₂. By ab initio molecular dynamics (AIMD) simulations, Co/B₁₁N₁₂ 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 NO₃RR and catalytic mechanism on TM/B₁₁N₁₂ but also open up opportunities for rational designing of SACs for NO₃RR toward the NH₃ synthesis.