Capturing copper single atom in proton donor stimulated O-end nitrate reduction

Abstract

Ammonia (NH3) is vital in global production and energy cycles. Electrocatalytic nitrate reduction (e-NO3RR) offers a promising route for nitrogen (N) conversion and NH3 synthesis, yet it faces challenges like competing reactions and low catalyst activity. This study proposes a synergistic mechanism incorporating a proton donor to mediate O-end e-NO3RR, addressing these limitations. A novel method combining ultraviolet radiation reduction, confined synthesis, and microwave treatment was developed to create a model catalyst embedding Cu single atoms on La-based nanoparticles (p-CNCusLan-m). DFT analysis emphasizes the critical role of La-based clusters as proton donors in e-NO3RR, while in situ characterization reveals an O-end adsorption reduction mechanism. The catalyst achieves a remarkable Faraday efficiency (FENH3) of 97.7%, producing 10.6 mol gmetal−1 h−1 of NH3, surpassing most prior studies. In a flow cell, it demonstrated exceptional stability, with only a 9% decrease in current density after 111 hours and a NH3 production rate of 1.57 mgNH3/h/cm−2. The proton donor mechanism's effectiveness highlights its potential for advancing electrocatalyst design. Beyond NH3 production, the O-end mechanism opens avenues for exploring molecular-oriented coupling reactions in e-NO3RR, paving the way for innovative electrochemical synthesis applications.