Cu3P/CoP Heterostructure for Efficient Electrosynthesis of Ammonia from Nitrate Reduction Reaction

Abstract

Electrocatalytic nitrate reduction (ENO₃RR) for ammonia production is one of the potential alternatives to Haber–Bosch technology for the realization of artificial ammonia synthesis. However, efficient ammonia production remains challenging due to the complex electron transfer process in ENO₃RR. In this study, we fabricated a Cu₃P/CoP heterostructure on carbon cloth (CC) by electrodeposition and vapor deposition, which exhibits an exceptional ENO₃RR performance in alkaline medium, and showcases a Faradaic efficiency of ammonia (FE_NH3) and an ammonia yield rate as high as 97.95% and 17,637.3 μg h^–1 cm^–2 at −0.9 V vs RHE. Moreover, Cu₃P/CoP also has excellent catalytic activity for nitrite reduction to ammonia, with an FE_NH3 up to 98.31% at −0.7 V vs RHE. The experimental and theoretical calculations reveal and confirm that the formation of a heterogeneous interface between Cu₃P and CoP effectively promotes the electron transfer, where Cu₃P as an electron donor induces the decrease of electron density around Cu and results in an enhancement of NO₂^– adsorption, thereby accelerating the ENO₃RR process while inhibiting the competitive hydrogen evolution reaction (HER). Moreover, the metal phosphide catalyst facilitates the water dissociation, which accelerates the abundant *H generation, thus enhancing the subsequent hydrogenation process toward ENO₃RR.