Boosting Electrochemical Nitrate Reduction at Low Concentrations Through Simultaneous Electronic States Regulation and Proton Provision.

ABSTRACT

Electrochemically converting nitrate (NO3 -) into ammonia (NH3) has emerged as an alternative strategy for NH3 production and effluent treatment. Nevertheless, the electroreduction of dilute NO3 - is still challenging due to the competitive adsorption between various aqueous species and NO3 -, and unfavorable water dissociation providing *H. Herein, a new tandem strategy is proposed to boost the electrochemical nitrate reduction reaction (NO3RR) performance of Cu nanoparticles supported on single Fe atoms dispersed N-doped carbon (Cu@Fe1-NC) at dilute NO3 - concentrations (≤100 ppm NO3 --N). The optimized Cu@Fe1-NC presents a FENH3 of 97.7% at -0.4 V versus RHE, and a significant NH3 yield of 1953.9 mmol h-1 gCu -1 at 100 ppm NO3 --N, a record-high activity for dilute NO3RR. The metal/carbon heterojunctions in Cu@Fe1-NC enable a spontaneous electron transfer from Cu to carbon substrate, resulting in electron-deficient Cu. As a result, the electron-deficient Cu facilitates the adsorption of NO3 - compared with the pristine Cu. The adjacent atomic Fe sites efficiently promote water dissociation, providing abundant *H for the hydrogenation of *NOx e at Cu sites. The synergistic effects between Cu and single Fe atom sites simultaneously decrease the energy barrier for NO3 - adsorption and hydrogenation, thereby enhancing the overall activity of NO3 - reduction.