Boosting Electrocatalytic Nitrate-to-Ammonia Conversion via Plasma Enhanced CuCo Alloy–Substrate Interaction

Electrocatalytic conversion of widely distributed nitrate from industrial wastewater into value-added ammonia was proposed as an attractive and sustainable alternative to harvesting green ammonia. Herein, CuCo alloys were facilely synthesized for nitrate conversion, while nonthermal Ar-plasma was employed to enhance the adhesion strength between the electrocatalyst and substrate interface via regulating the surface hydrophobicity and roughness. Based on Ar-plasma treatment, a high ammonia yield rate (5129.29 μg cm–2 h–1) was achieved using Cu30Co70 electrocatalyst −0.47 V vs RHE, while nearly 100% of Faradaic efficiency was achieved using Cu50Co50 electrocatalyst at −0.27 V vs RHE (reversible hydrogen electrode). Validated by in situ spectroscopy and density functional theory calculations, the high activity of the CuCo alloy was derived from the regulation of Co to weaken the strong adsorption capacity of Cu and the shift of the d-band center to lower the energy barrier, while Ar-plasma modification promoted the formation of *NO to boost nitrate conversion.