Abstract

Abstract Coordination engineering strategy for optimizing the catalytic performance of single‐atom catalysts (SACs) has been rapidly developed over the last decade. However, previous reports on copper SACs for nitrate reduction reactions (NO 3 RR) have mostly focused on symmetric coordination configurations such as Cu‐N 4 and Cu‐N 3 . In addition, the mechanism in terms of the regulation of coordination environment and catalytic properties of SACs has not been well demonstrated. Herein, we disrupted the local symmetric structure of copper atoms by introducing unsaturated heteroatomic coordination of Cu−O and Cu−N to achieve the coordination desymmetrization of Cu‐N 1 O 2 SACs. The Cu‐N 1 O 2 SACs exhibit an efficient nitrate‐to‐ammonia conversion with a high FE of ~96.5 % and a yield rate of 3120 μg NH 3 h −1 cm −2 at −0.60 V vs RHE. As indicated by in situ Raman spectra, the catalysts facilitate the accumulation of NO 3 − and the selective adsorption of *NO 2 , which were further confirmed by the theoretical study of surface dipole moment and orbital hybridization. Our work illustrated the correlation between the coordination desymmetrization and the catalytic performance of copper SACs for NO 3 RR.