Upgrading of nitrate to hydrazine through cascading electrocatalytic ammonia production with controllable N-N coupling

Shunhan Jia, Libing Zhang, Hanle Liu, Ruhan Wang, Xiangyuan Jin, Limin Wu, Xinning Song, Xingxing Tan, Xiaodong Ma, Jiaqi Feng, Qinggong Zhu, Xinchen Kang, Qingli Qian, Xiaofu Sun () and Buxing Han ()
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Shunhan Jia: Chinese Academy of Sciences
Libing Zhang: Chinese Academy of Sciences
Hanle Liu: Chinese Academy of Sciences
Ruhan Wang: Chinese Academy of Sciences
Xiangyuan Jin: Chinese Academy of Sciences
Limin Wu: Chinese Academy of Sciences
Xinning Song: Chinese Academy of Sciences
Xingxing Tan: Chinese Academy of Sciences
Xiaodong Ma: Chinese Academy of Sciences
Jiaqi Feng: Chinese Academy of Sciences
Qinggong Zhu: Chinese Academy of Sciences
Xinchen Kang: Chinese Academy of Sciences
Qingli Qian: Chinese Academy of Sciences
Xiaofu Sun: Chinese Academy of Sciences
Buxing Han: Chinese Academy of Sciences

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: Abstract Nitrogen oxides (NOx) play important roles in the nitrogen cycle system and serve as renewable nitrogen sources for the synthesis of value-added chemicals driven by clean electricity. However, it is challenging to achieve selective conversion of NOx to multi-nitrogen products (e.g., N2H4) via precise construction of a single N-N bond. Herein, we propose a strategy for NOx-to-N2H4 under ambient conditions, involving electrochemical NOx upgrading to NH3, followed by ketone-mediated NH3 to N2H4. It can achieve an impressive overall NOx-to-N2H4 selectivity of 88.7%. We elucidate mechanistic insights into the ketone-mediated N-N coupling process. Diphenyl ketone (DPK) emerges as an optimal mediator, facilitating controlled N-N coupling, owing to its steric and conjugation effects. The acetonitrile solvent stabilizes and activates key imine intermediates through hydrogen bonding. Experimental results reveal that Ph2CN* intermediates formed on WO3 catalysts acted as pivotal monomers to drive controlled N-N coupling with high selectivity, facilitated by lattice-oxygen-mediated dehydrogenation. Additionally, both WO3 catalysts and DPK mediators exhibit favorable reusability, offering promise for green N2H4 synthesis.

Date: 2024
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DOI: 10.1038/s41467-024-52825-1

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