Chloride-Derived Bimetallic Cu-Fe Nanoparticles for High-Selective Nitrate-to-Ammonia Electrochemical Catalysis

Cu-based bimetallic materials have been widely reported as efficient catalysts for electrocatalytic nitrate reduction. However, the faradaic efficiency and selectivity are still far from satisfactory. Herein, Cu-Fe bimetallic nanoalloys with adjustable Cu/Fe ratios are successfully prepared through a reactive mechanical milling approach with CuCl2, FeCl3 and Na as the starting materials. The optimized Cu3Fe exhibits excellent nitrate conversion efficiency of 81.1% and 70.3% ammonia selectivity at −0.7 V vs. RHE within 6 h under 0.1 M Na2SO4 and 100 ppm NO3−. The Fe-introduction-induced upshift of the d-band center is identified to be beneficial for promoting nitrate adsorption on Cu3Fe. Moreover, favorable H generation under the assistance of Fe could effectively accelerate the stepwise hydrogenation during electrocatalytic nitrate reduction, resulting in significantly improved NH4+ selectivity. This work supplies valuable insights for the rational design of transition-metal-based bimetallic catalysts for electrocatalytic nitrate reduction.