Synergistic Effect of Ni/Ni(OH)2 Core‐Shell Catalyst Boosts Tandem Nitrate Reduction for Ampere‐Level Ammonia Production

Electrocatalytic reduction of nitrate to ammonia provides a green alternate to the Haber‐Bosch method, yet it suffers from sluggish kinetics and a low yield rate. The nitrate reduction follows a tandem reaction of nitrate reduction to nitrite and subsequent nitrite hydrogenation to generate ammonia, and the ammonia Faraday efficiency (FE) is limited by the competitive hydrogen evolution reaction. Herein, we design a heterostructure catalyst to remedy the above issues, which consists of Ni nanosphere core and Ni(OH)2 nanosheet shell (Ni/Ni(OH)2). In‐situ Raman spectroscopy reveals Ni and Ni(OH)2 are interconvertible according to the applied potential, facilitating the cascade nitrate reduction synergistically. Consequently, it attains superior electrocatalytic nitrate reduction performance with an ammonia FE of 98.50% and a current density of 0.934 A cm‐2 at ‐0.476 V versus reversible hydrogen electrode, and exhibits an average ammonia yield rate of 84.74 mg h‐1 cm‐2 during the 102‐hour stability test, which is highly superior to the reported catalysts tested under similar conditions. Density functional theory calculations corroborate the synergistic effect of Ni and Ni(OH)2 in the tandem reaction of nitrate reduction. Moreover, the Ni/Ni(OH)2 catalyst also possesses good capability for methanol oxidation and thus is used to establish a system coupling with nitrate reduction.