Efficient Nitrate Conversion to NH 3 on Core/Shell‐Like Structured Cu−Co Heterogeneous Catalyst With Surface‐Enriched Atomically‐Dispersed Co Dopant

ABSTRACT Electrocatalytic nitrate reduction reaction (NO 3 RR) to NH 3 provides a sustainable strategy to address energy and environmental challenges by converting waste into valuable resources. In the present work, a series of core/shell‐like structured Cu−Co heterogeneous catalyst with CoSn(OH) 6 as the core and surface‐enriched atomically dispersed Co‐doped CuSn(OH) 6 as the shell have been synthesized for highly efficient NH 3 synthesis via NO 3 RR. The atomically dispersed Co atoms have been confirmed by experimentally and theoretically to provide catalytic sites for NO 3 RR and *H supply with moderate hydrogen evolution activity, and the low limiting potential for NO 3 RR arising from the strong electronic interaction between CuSn(OH) 6 as support and Co active sites. Benefiting from the advantages above, the optimal Cu−Co heterogeneous catalyst exhibits remarkable NO 3 − −to−NH 3 conversion performances over a wide concentration range from 20 to 1000 mM, especially achieving the high Faradaic efficiency of NH 3 of 79.19% (±2.36) and a corresponding NH 3 yield rate of 2.39 mmol h −1 mg cat −1 (±0.07) at −0.8 V in 0.1 M KOH with 1 M KNO 3 . Moreover, a high‐efficiency Zn−NO 3 − battery can also be achieved for simultaneous generation of NH 3 and electricity.