Theoretical Calculations on Hexagonal-Boron-Nitride-(h-BN)-Supported Single-Atom Cu for the Reduction of Nitrate to Ammonia

Nitrate (NO₃^-), as a stable nitrogen-containing compound, has caused serious harm to the ecological environment and human health. To reduce nitrate pollution, the catalytic reduction of nitrate (NO₃RR) to ammonia (NH₃) is a very promising solution. Recently, single-atom catalysts (SACs) have received extensive attention due to their excellent activity and stability. Here, we study the nitrate catalytic reduction properties of hexagonal-boron-nitride-(h-BN)-supported single-atom Cu systematically and theoretically and compare it with monolayer h-BN. We find that (1) due to the stronger electronegativity of the N atom, Cu atom is preferentially doped at the N top site, resulting in the significant electron rearrangement; (2) the doped Cu atom at the N top site for monolayer h-BN can provide extra 3d-orbital electrons at the Fermi level, which can significantly enhance the conductivity, reduce the bandgap width, and increase the reducibility; (3) the NO₃^- ion preferentially adsorbs at the hollow site of monolayer h-BN, while the NO₃^- ion is adsorbed more strongly at the Cu top site of h-BN-supported single-atom Cu due to the abundant d-electron supply from the Cu atom; (4) single-atom Cu can significantly reduce the energy barrier of the rate-determining step (RDS) and increase the probability of nitrate reduction. In conclusion, h-BN-supported single-atom Cu exhibits excellent catalytic performance of NO₃RR.