Unraveling the Activity Trends and Design Principles of Single-Atom Catalysts for Nitrate Electrocatalytic Reduction.

Electrocatalytic nitrate (NO3-) reduction represents one of the most promising approaches to mitigate NO3- pollution and yield NH3, but it is still challenged by the atomic economy and selectivity issues of substantial active sites. Here, we describe a comprehensive investigation on a series of single-atom catalysts (SACs) using nitrogen-doped carbon as substrate (metal/NC). The essence of activity is related to the extent of the electron transfer capacity (SAs → NO3-). Among these examined SACs, the Cu/NC presents good performance toward NH3 synthesis, i.e., a maximum NH3 Faradaic efficiency of 100% with a high NH3 yield rate of up to 32,300 μg h-1 mgcat.-1. X-ray absorption fine structure spectra and density functional theory calculations provide evidence that the electronic structure of Cu-N4 coordination prohibits the formation of N2, N2O, and H2 and facilitates the orbital hybridization between the 2p orbitals of NO3- and 3d orbitals of Cu single-atom sites. Our study is believed to provide fundamental guidance for the future design of highly efficient electrocatalysts in NO3- reduction to NH3.