Cu1−Fe Dual Sites for Superior Neutral Ammonia Electrosynthesis from Nitrate

• Published in: Angewandte Chemie 2024-07, Vol.136 (31), p.n/a
• Main Authors: Zhou, Biao, Yu, Linghao, Zhang, Weixing, Liu, Xupeng, Zhang, Hao, Cheng, Jundi, Chen, Ziyue, Li, Meiqi, Shi, Yanbiao, Jia, Falong, Huang, Yi, Zhang, Lizhi, Ai, Zhihui
• Format: Article
• Language: English
• Subjects: Ammonia; Ammonia Recovery; Catalysts; Chemical reduction; Dual sites; Electrochemistry; Hydrogen atoms; Intermediates; Iron oxides; Nitrate Electroreduction; Nitrate reduction; Nitrate-pollution Treatment; Nitrates; Resource utilization; Single Atom Copper; Synergistic effect; Wastewater treatment
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202406046

The electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3−) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3− to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen‐containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH‐neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3−. Herein, we constructed a Cu1‐Fe dual‐site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero‐valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3− removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L−1 NO3−−N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3− adsorption on Fe sites and strengthened water activation on single‐atom Cu sites, decreasing the energy barrier for the rate‐determining step of *NO‐to‐*NOH. This work develops a novel strategy of fabricating dual‐site catalysts to enhance the electrosynthesis of NH3 from NO3−, and presents an environmentally sustainable approach for neutral nitrate wastewater treatment. Single‐atom Cu is anchored on the oxide layer of Fe@Cu1FeOx to form Cu1‐Fe dual‐sites. The synergistic effect of enhanced NO3− adsorption on Fe sites and the strengthened water activation on Cu sites decreases the energy barrier for the rate‐determining step of *NO hydrogenation, resulting in superior electroreduction of nitrate to ammonia.