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Plasma-coupled electrochemical ammonia synthesis from air and water under ambient conditions

Abstract

Decentralized, sustainable ammonia production could have an immense global impact. Here we describe an electrolytic approach to synthesizing ammonia directly from air and water under ambient conditions, which could be developed and optimized toward this goal. The system integrates a gliding arc discharge plasma reactor for generating \({\rm{NO}}_{\rm{x}}\) from air with a membrane electrode assembly reactor for the electrochemical reduction of \({\rm{NO}}_{\rm{x}}^{-}\) to ammonia, enhancing both the efficiency and scalability of the process. Furthermore, the plasma-generated \({\rm{NO}}_{\rm{x}}\) feedstock can be substituted with \({\rm{NO}}_{\rm{x}}\) derived from industrial waste, further extending the potential of this system. In this Protocol, we describe the fundamental principles of this plasma-electrochemical nitrogen reduction reaction (PE-N2RR) system and provide advice for experimental standardization, operational mechanisms and data analysis methods. The procedure starts with the synthesis of the catalyst—a La1.5Sr0.5Ni0.5Fe0.5O4 perovskite oxide—at either laboratory or industrial scale. This catalyst is sufficiently stable to enable the \({\rm{NO}}_{\rm{x}}^{-}\) RR to continuously work under strongly acidic conditions. We highlight the key operating parameters that are necessary for plasma-based \({\rm{NO}}_{\rm{x}}\) production and electrochemical \({\rm{NO}}_{\rm{x}}^{-}\) reduction reaction systems. This information and framework can be used to optimize and streamline the entire PE-N2RR system. A moderate level of expertise in electrochemistry, plasma systems and catalyst synthesis is recommended to ensure successful execution. The setup of the entire PE-N2RR system, from catalyst synthesis to the configuration of plasma and electrochemical, is estimated to take 72 h. The full reaction operation test requires 200 h, whereas in situ electrochemical characterizations take 3 h.

Key points

  • This Protocol describes a plasma-coupled electrochemical approach for ammonia synthesis using air and water as feedstocks. The system integrates a gliding arc discharge plasma system for generating \({\rm{NO}}_{\rm{x}}\) and a membrane electrode assembly electrochemical system to reduce \({\rm{NO}}_{\rm{x}}^{-}\) into ammonia.

  • This integrated strategy overcomes the low efficiency limitations of conventional electrochemical nitrogen reduction reaction while retaining broad adaptability across diverse application scenarios.

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Fig. 1: A flow diagram of electrochemical ammonia synthesis from air and water.
Fig. 2: A schematic illustration of the PE-N2RR system.
Fig. 3: Photographs of the reactor of plasma system.
Fig. 4: A schematic illustration of the MEA reactor.
Fig. 5: Data analysis and mechanism of GAD plasma system.
Fig. 6: Photographs of the components used in stacked MEA reactor.
Fig. 7: A schematic and photograph of a stacked MEA reactor.
Fig. 8: Standard curve of nitrate, nitrite and ammonia.
Fig. 9: 1H NMR measurement for ammonia detection.
Fig. 10: Performance test of PE-N2RR.
Fig. 11: Performance test of the plasma system.
Fig. 12: A performance test of the electrochemical system.
Fig. 13: Mechanism studies for the electrochemical system.

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Data availability

All data generated or analyzed during this study are available from the corresponding author upon reasonable request. All the data that support the plots within this paper have been published previously44,45,46. Source data are provided with this paper.

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Acknowledgements

We acknowledge financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDB0450401), the National Key R&D Program of China (grant nos. 2020YFA0406103 and 2022YFE0126500) and the National Natural Science Foundation of China (grant nos. 21725102, 51925703, 22232003, 22150610467 and 52261135635).

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Authors

Contributions

J.L., T.S. and Y.X. supervised the project. X.G. and J.L. designed the experiments. X.G., Y.G., Z.C., S.Z., S.S. and J.M. carried out the experiments and analyzed the results. X.G., J.L., T.S. and Y.X. wrote the manuscript. D.M. contributed to manuscript modification. All authors read and approved the manuscript. X.G., Y. G. and C.Z. contributed equally.

Corresponding authors

Correspondence to Jingxiang Low, Tao Shao or Yujie Xiong.

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Nature Protocols thanks Angela Daisley and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Key references

Guo, X. et. al. Angew. Chem. Int. Ed. 63, e202410517 (2024): https://doi.org/10.1002/anie.202410517

Zhang, C. et. al. Angew. Chem. Int. Ed. 63, e202317628 (2024): https://doi.org/10.1002/anie.202317628

Zhang, S. et. al. Green Chem. 24, 1534−1544 (2022): https://doi.org/10.1039/D1GC03859A

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Guo, X., Gao, Y., Zhang, C. et al. Plasma-coupled electrochemical ammonia synthesis from air and water under ambient conditions. Nat Protoc (2026). https://doi.org/10.1038/s41596-026-01332-2

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