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Synthesis of hydroxylamine from air and water via a plasma-electrochemical cascade pathway

Nature Sustainability (2024)Cite this article

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Abstract

Hydroxylamine is an important nitrogenous feedstock for the chemical industry. Conventional hydroxylamine synthesis methods utilize ammonia as the nitrogen source and require harsh reaction conditions, leading to unfavourable environmental footprint. Here we develop a plasma-electrochemical cascade pathway (PECP) powered by electricity for sustainable hydroxylamine synthesis directly from ambient air and water at mild conditions. In the first step, the plasma treatment of ambient air and water delivers a nitric acid solution with a concentration of up to 120.1 mM. Subsequently, the obtained nitric acid is selectively electroreduced to hydroxylamine using a bismuth-based catalyst. The faradaic efficiency for hydroxylamine reached 81.0% at −1.0 V versus reversible hydrogen electrode. As a result, this PECP method achieves a high hydroxylamine yield rate of 713.1 μmol cm−2 h−1 with a selectivity of 95.8%. Notably, both steps of the PECP method are operated at room temperature. Overall, our work provides a viable approach for efficient hydroxylamine synthesis from simpler feedstock at milder conditions, contributing to the sustainability transformation of the chemical industry.

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Fig. 1: Schematic illustration of the synthetic pathways for NH2OH production.
Fig. 2: Plasma synthesis of HNO3 from ambient air and H2O.
Fig. 3: Characterization of the Bi film/CFP catalyst.
Fig. 4: Catalytic performance of NO3− electroreduction using Bi film/CFP.
Fig. 5: Mechanistic study of NO3− electroreduction into NH2OH.

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All data in this work are available in the text and Supplementary Information. The relevant raw data for each figure or table (in the text and Supplementary Information) are listed in Excel documents and provided as source or supplementary data files. Source data are provided with this paper.

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Acknowledgements

Z.G. acknowledges the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0450401), the National Natural Science Foundation of China (22322901), the CAS Project for Young Scientists in Basic Research (YSBR-022), and the National Key Research and Development Program of China (2022YFC2106000). J. Zeng acknowledges the National Key Research and Development Program of China (2021YFA1500500), the CAS Project for Young Scientists in Basic Research (YSBR-051), the National Science Fund for Distinguished Young Scholars (21925204), the National Science Fund for Distinguished Young Scholars (21925204), the National Natural Science Foundation of China (22221003, 22250007 and 22361162655), the Fundamental Research Funds for the Central Universities, the Provincial Key Research and Development Program of Anhui (202004a05020074), the Collaborative Innovation Program of Hefei Science Center, CAS (2022HSC-CIP004), and the USTC Research Funds of the Double First-Class Initiative (YD2340002002). X.K. acknowledges the National Natural Science Foundation of China (22209163). This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication, and the Instruments Center for Physical Science, University of Science and Technology of China.

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  1. These authors contributed equally: Xiangdong Kong, Jie Ni.

Authors and Affiliations

  1. Hefei National Research Center for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, P. R. China

    Xiangdong Kong, Jie Ni, Zhimin Song, Zhengwu Yang, Jiana Zheng, Zifan Xu, Lang Qin, Hongliang Li, Zhigang Geng & Jie Zeng

  2. School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan, Anhui, P. R. China

    Jie Zeng

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Contributions

J. Zeng, Z.G. and X.K. conceived the idea and co-wrote the paper. X.K. and J.N. synthesized catalysts, conducted structural characterizations and performed electroreduction tests with the help of J. Zheng and Z.X. Z.S. and X.K. designed the plasma discharge device and performed the N2 plasma fixation tests with the help of L.Q. Z.Y. performed the theoretical calculations. H.L. made suggestions on the paper. All authors discussed the results and commented on the paper.

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Correspondence to Zhigang Geng or Jie Zeng.

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Nature Sustainability thanks Chang Hyuck Choi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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30 s absorption of NOx in the aqueous absorbent containing 0.02 mM methyl orange

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Kong, X., Ni, J., Song, Z. et al. Synthesis of hydroxylamine from air and water via a plasma-electrochemical cascade pathway. Nat Sustain (2024). https://doi.org/10.1038/s41893-024-01330-w

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