A Bi‐Co Corridor Construction Effectively Improving the Selectivity of Electrocatalytic Nitrate Reduction toward Ammonia by Nearly 100%

Abstract Improving the selective ammonia production capacity of electrocatalytic nitrate reduction reaction (NO 3 RR) at ambient conditions is critical to the future development and industrial application of electrosynthesis of ammonia. However, the reaction involves multi‐proton and electron transfer as well as the desorption and underutilization of intermediates, posing a challenge to the selectivity of NO 3 RR. Here the electrodeposition site of Co is modulated by depositing Bi at the bottom of the catalyst, thus obtaining the Co+Bi@Cu NW catalyst with a Bi‐Co corridor structure. In 50 m m NO 3 − , Co+Bi@Cu NW exhibits a highest Faraday efficiency of ≈100% (99.51%), an ammonia yield rate of 1858.2 µg h −1 cm −2 and high repeatability at −0.6 V versus the reversible hydrogen electrode. Moreover, the change of NO 2 − concentration on the catalyst surface observed by in situ reflection absorption imaging and the intermediates of the NO 3 RR process detected by electrochemical in situ Raman spectroscopy together verify the NO 2 − trapping effect of the Bi‐Co corridor structure. It is believed that the measure of modulating the deposition site of Co by loading Bi element is an easy‐to‐implement general method for improving the selectivity of NH 3 production as well as the corresponding scientific research and applications.