Citation: Yuwei Liu, Yihui Zhu, Weijian Duan, Yizhuo Yang, Haorui Tuo, Chunhua Feng. Electrocatalytic nitrate reduction on Fe, Fe₃O₄, and Fe@Fe₃O₄ cathodes: Elucidating structure-sensitive mechanisms of direct electron versus hydrogen atom transfer[J]. Chinese Chemical Letters, ;2025, 36(6): 110347. doi: 10.1016/j.cclet.2024.110347 shu

Electrocatalytic nitrate reduction on Fe, Fe₃O₄, and Fe@Fe₃O₄ cathodes: Elucidating structure-sensitive mechanisms of direct electron versus hydrogen atom transfer

The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, China

202310189796@mail.scut.edu.cn

chfeng@scut.edu.cn

Received Date: 19 March 2024
Revised Date: 18 July 2024
Accepted Date: 16 August 2024
Available Online: 17 August 2024

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Electrochemical nitrate reduction (NO₃RR) offers a promising avenue for treating nitrate-contaminated water and recovering ammonia (NH₃), yet the complexities of direct electron transfer (DET) and hydrogen atom transfer (HAT) mechanisms crucial for efficiency remain elusive. This study bridges the gap with a combined experimental and theoretical approach, elucidating the impact of catalyst structure on NO₃RR pathways. We discover that catalysts favoring strong NO₃⁻ adsorption and efficient water dissociation were more inclined towards DET, enhancing denitrification. The Fe@Fe₃O₄/FF cathode, leveraging the synergistic interplay between metallic Fe and Fe₃O₄, excelled in NO₃RR via DET, achieving an NH₃ yield of 0.28 mmol h⁻¹ cm⁻² and a Faradaic efficiency of 95.7% for NH₃ at -1.6 V (vs. SCE), with minimal nitrite accumulation at 100 mmol/L nitrate. Conversely, the Fe/FF and Fe₃O₄/CC cathodes showed reduced NH₃ production and increased nitrite levels, attributed to the lack of Fe₃O₄ and metallic Fe, respectively, resulting in a dominant HAT mechanism. Moreover, Fe@Fe₃O₄/FF facilitated complete denitrification in real wastewater treatment by harnessing Cl⁻ for electrochemically mediated breakpoint chlorination. This research not only deepens our understanding of NO₃RR mechanisms but also paves the way for designing superior nitrate reduction catalysts.
- Electrochemical nitrate reduction,
- Fe electrocatalysts,
- Electron transfer mechanism,
- Hydrogen atom,
- Ammonia synthesis
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Electrocatalytic nitrate reduction on Fe, Fe3O4, and Fe@Fe3O4 cathodes: Elucidating structure-sensitive mechanisms of direct electron versus hydrogen atom transfer

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通讯作者: 陈斌, bchen63@163.com

Electrocatalytic nitrate reduction on Fe, Fe₃O₄, and Fe@Fe₃O₄ cathodes: Elucidating structure-sensitive mechanisms of direct electron versus hydrogen atom transfer