Surface Reconstruction on Uniform Cu Nanodisks Boosted Electrochemical Nitrate Reduction to Ammonia

The Haber-Bosch (HB) process has provided most of commercial ammonia at the expense of high energy consumption and high CO2 emission. Nitrate electroreduction is showing great potential as an alternative route for the green and scale-up synthesis of ammonia at ambient conditions. However, the performance has lagged due to lack of efficient electrocatalysts. In this work, we present the facile synthesis of uniform Cu nanodisks with exposed (111) facets as highly active electrocatalyst for electrochemical ammonia synthesis, delivering a high ammonia yield of 2.16 mg mg-1cat h-1 and a maximum Faradaic efficiency of 81.1% at -0.5 V versus a reversible hydrogen electrode (RHE). The remarkable activity is originated from the surface reconstructed triatomic Cu clusters due to the cathodic deoxygenation process. As a result, the reconstructed surface shows enhanced affinity to the adsorption of nitrate ions which undergo successive break of three N-O bonds, followed by subsequent formation of three N-H bonds to finally form NH3. The present study provides the feasible preparation of Cu based advanced catalysts and a unique insight into the mechanism of nitrate electroreduction.