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Direct plasma synthesis of a high-value C–N–O compound with inert N2 and CH4

Nature Synthesis (2026)Cite this article

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Abstract

Direct co-conversion of earth-abundant N2 and CH4 to high-value C–N–O compounds is a promising synthetic method but remains challenging, as the activation of N2 and CH4 typically requires high-energy conditions that can cause product decomposition. Here we report a plasma-cascade process for synthesizing cyclohexanone cyanohydrin (Cy(OH)CN) via direct coupling of N2 and CH4 plasma with cyclohexanone. This catalyst-free process achieves a Cy(OH)CN formation rate of 0.60 mmol h−1 with a high selectivity of 95.8% towards the cyclohexanone-derived products under mild conditions, concurrently generating ammonia as a valuable coproduct. Comprehensive mechanistic studies reveal that plasma-generated ·CHx and hydrogen radicals enable direct α-carbonyl functionalization of cyclohexanone to α-CHx cyclohexanol intermediates, which then coupled mainly with excited-state N2 and are further activated by hydrogen radicals to generate Cy(OH)CN. This plasma-cascade strategy decouples the activation of inert molecules from the formation of relatively unstable C–N–O compounds, enabling selective cyanohydrin synthesis that avoids using high-cost NH3 and toxic HCN.

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Fig. 1: Direct synthesis of cyclohexanone cyanohydrin with N2, CH4 and cyclohexanone.
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Fig. 2: Investigation of plasma-generated reactive species and the C–C or C–N coupling reaction mechanism.
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Fig. 3: Investigation of C–N coupling and N–N bond cleavage reaction mechanism.
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Fig. 4: Radical relay mechanism for the plasma-driven C–N–O compound assembly.
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The data supporting the findings of this study are available within the article and its Supplementary information. Source data are provided with this paper.

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Acknowledgements

We acknowledge financial support from the National Natural Science Foundation of China (grant nos. 22588201 and 22225204 to D.D., 22372019 and U24A20487 to R.H. and 22272170 to L.Y.), the National Key R&D Program of China (grant nos. 2022YFA1504500 to D.D. and 2024YFA1510103 to R.H.), the State Key Laboratory of Catalysis in the Dalian Institute of Chemical Physics (DICP) (grant nos. 2024SKL-A-002 and N-22-02) and the DICP (grant no. DICP I202506). We thank A. Goldbach from DICP for providing valuable suggestions.

Author information

Author notes

  1. These authors contributed equally: Hao Zhang, Ziming Liu, Di Li.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Hao Zhang, Ziming Liu, Di Li, Rui Huang, Liang Yu & Dehui Deng

  2. University of Chinese Academy of Sciences, Beijing, China

    Ziming Liu, Rui Huang, Liang Yu & Dehui Deng

  3. State Key Laboratory of Medical Proteomics, Liaoning Key Laboratory for Mass Spectrometry Technology and Instrumentation, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Chenxin Wu, Lei Hua & Haiyang Li

  4. State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, China

    Yanhui Yi

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Contributions

D.D., R.H. and L.Y. conceived and supervised the project. H.Z. carried out the experiments. Z.L. and L.Y. performed DFT calculations. D.L. and H.Z. conducted in situ MBMS characterization. C.W., L.H. and H.L. provided technical support for in situ MBMS device. Y.Y. conducted optical emission spectroscopy experiments. D.L. performed plasma kinetics simulation. H.Z., Z.L., D.L., R.H., L.Y. and D.D. discussed the results, wrote and revised the paper. All authors contributed to scientific discussion.

Corresponding authors

Correspondence to Rui Huang, Liang Yu or Dehui Deng.

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Nature Synthesis thanks Xiaolei Fan, Ali Mesbah, Richard van de Sanden and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary Methods, Figs. 1–21, Tables 1–6 and Refs. 1–8.

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Detailed configuration of DBD plasma reactor.

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Statistical source data.

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Statistical source data.

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Zhang, H., Liu, Z., Li, D. et al. Direct plasma synthesis of a high-value C–N–O compound with inert N2 and CH4. Nat. Synth (2026). https://doi.org/10.1038/s44160-026-01055-y

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