Intermediates Regulation via Electron‐Deficient Cu Sites for Selective Nitrate‐to‐Ammonia Electroreduction

Abstract Ammonia (NH₃), known as one of the fundamental raw materials for manufacturing commodities such as chemical fertilizers, dyes, ammunitions, pharmaceuticals, and textiles, exhibits a high hydrogen storage capacity of ≈17.75%. Electrochemical nitrate reduction (NO₃RR) to valuable ammonia at ambient conditions is a promising strategy to facilitate the artificial nitrogen cycle. Herein, copper‐doped cobalt selenide nanosheets with selenium vacancies are reported as a robust and highly efficient electrocatalyst for the reduction of nitrate to ammonia, exhibiting a maximum Faradaic efficiency of ≈93.5% and an ammonia yield rate of 2360 µg h⁻¹ cm⁻² at −0.60 V versus reversible hydrogen electrode. The in situ spectroscopical and theoretical study demonstrates that the incorporation of Cu dopants and Se vacancies into cobalt selenide efficiently enhances the electron transfer from Cu to Co atoms via the bridging Se atoms, forming the electron‐deficient structure at Cu sites to accelerate NO₃⁻ dissociation and stabilize the *NO₂ intermediates, eventually achieving selective catalysis in the entire NO₃RR process to produce ammonia efficiently.