Self-Triggering a Locally Alkaline Microenvironment of Co4Fe6 for Highly Efficient Neutral Ammonia Electrosynthesis

Electrochemical nitrate reduction reaction (eNO3-RR) to ammonia (NH3) holds great promise for the green treatment of NO3- and ambient NH3 synthesis. Although Fe-based electrocatalysts have emerged as promising alternatives, their excellent eNO3-RR-to-NH3 activity is usually limited to harsh alkaline electrolytes or alloying noble metals with Fe in sustainable neutral electrolytes. Herein, we demonstrate an unusual self-triggering localized alkalinity of the Co4Fe6 electrocatalyst for efficient eNO3-RR-to-NH3 activity in neutral media, which breaks down the conventional pH-dependent kinetics restrictions and shows a 98.6% NH3 Faradaic efficiency (FE) and 99.9% NH3 selectivity at -0.69 V vs RHE. The synergetic Co-Fe dual sites were demonstrated to enable the optimal free energies of eNO3-RR-to-NH3 species and balance water dissociation and protonation of adsorbed NO2-. Notably, the Co4Fe6 electrocatalysts can attain a high current density of 100 mA cm-2 with a high NH3 FE surpassing 96% and long-term stability for over 500 h eNO3-RR-to-NH3 in a membrane electrode assembly (MEA) electrolyzer. This work provides insight into tailoring the self-reinforced local-alkalinity on the Fe-based alloy electrocatalysts for eNO3-RR-to-NH3 and thus avoids alkaline electrolytes and noble metals for practical sustainable nitrate upcycling technology.