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 (NO3 RR) 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 2360µg h-1 cm-2 at -0.60V 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 NO3 RR process to produce ammonia efficiently.