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; Buxing Han

doi:10.1038/s41467-024-52825-1

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

Nat Commun. 2024 Oct 3;15(1):8567. doi: 10.1038/s41467-024-52825-1.

Authors

Shunhan Jia^{1

2}, Libing Zhang^{1

2}, Hanle Liu^{1

2

3}, Ruhan Wang^{1

2}, Xiangyuan Jin^{1

2}, Limin Wu^{1

2}, Xinning Song^{1

2}, Xingxing Tan¹, Xiaodong Ma¹, Jiaqi Feng^{1

4}, Qinggong Zhu^{1

2}, Xinchen Kang^{1

2}, Qingli Qian^{1

2}, Xiaofu Sun^{5

6}, Buxing Han^{7

8

9}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
² School of Chemical Sciences, University of Chinese Academy of Sciences, 100049, Beijing, China.
³ College of Chemistry, Nankai University, 300071, Tianjin, China.
⁴ College of Chemical Engineering and Environment, China University of Petroleum, 102249, Beijing, China.
⁵ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China. [email protected].
⁶ School of Chemical Sciences, University of Chinese Academy of Sciences, 100049, Beijing, China. [email protected].
⁷ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China. [email protected].
⁸ School of Chemical Sciences, University of Chinese Academy of Sciences, 100049, Beijing, China. [email protected].
⁹ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, 200062, Shanghai, China. [email protected].

Abstract

Nitrogen oxides (NO_x) 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 NO_x to multi-nitrogen products (e.g., N₂H₄) via precise construction of a single N-N bond. Herein, we propose a strategy for NO_x-to-N₂H₄ under ambient conditions, involving electrochemical NO_x upgrading to NH₃, followed by ketone-mediated NH₃ to N₂H₄. It can achieve an impressive overall NO_x-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.

Abstract

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