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Electrosynthesis of hydroxylamine from nitrate reduction in water

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Abstract

Hydroxylamine (NH2OH), a vital but unstable industrial feedstock, is presently prepared under harsh conditions that cause environmental and energy concerns. Here, we report an electrochemical method to prepare oximes, which serve as precursors for NH2OH after facile hydrolysis. The carbon-supported amorphous Mn electrocatalyst delivers a current density of ∼100 mA cm−2 with a Faradaic efficiency of 40.92% and a yield rate of 0.251 mmol cm−2 h−1 for formaldoxime (CH2NOH) generation by using nitrate and formaldehyde as reactants. Formaldoxime can be easily released to produce NH2OH via hydrolysis. Impressively, this method exhibits an economic advantage over conventional manufacturing based on techno-economic analysis. A series of control experiments, in situ characterizations, and theoretical simulations unveil the reaction mechanism via the spontaneous reaction between an aldehyde and *NH2OH intermediate derived from nitrate electroreduction. The high activity of Mn originates from its inhibitory effects on the further reduction of key *NH2OH intermediate. This strategy opens a sustainable and green way for NH2OH synthesis under mild conditions using renewable energy.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22271213 (B.Z.) and 22071173 (Y.Y.)), the Haihe Laboratory of Sustainable Chemical Transformations, and the National Postdoctoral Science Foundation of China (2022M722357 (Y.W.)). The authors appreciate Ms. Yang Liu in the Analysis and Testing Center at Tianjin University for in situ ATR-SEIRAS measurements. The authors do appreciate Dr. Kongying Zhu in the Nuclear Magnetic Resonance Testing Center at Tianjin University for NMR measurements.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Institute of Molecular Plus, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, China

    Xianen Lan, Chengying Guo, Minghao Guo, Tieliang Li, Yongmeng Wu, Yifu Yu & Bin Zhang

  2. Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Chuanqi Cheng

  3. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, China

    Yifu Yu & Bin Zhang

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  1. Xianen Lan
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  2. Chuanqi Cheng
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  3. Chengying Guo
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  4. Minghao Guo
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  6. Yongmeng Wu
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Correspondence to Yongmeng Wu, Yifu Yu or Bin Zhang.

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Conflict of interest The authors declare no conflict of interest.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Lan, X., Cheng, C., Guo, C. et al. Electrosynthesis of hydroxylamine from nitrate reduction in water. Sci. China Chem. 66, 1758–1762 (2023). https://doi.org/10.1007/s11426-023-1580-2

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  • DOI: https://doi.org/10.1007/s11426-023-1580-2

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