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Cascade electrosynthesis of LiTFSI and N-containing analogues via a looped Li–N2 battery

Nature Catalysis volume 7, pages 55–64 (2024)Cite this article

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Abstract

The synthesis of N-containing chemicals directly from N2 is highly desirable in chemistry but has been challenged by inert N2 molecules and limited product scope. Herein we propose a cascade electrosynthesis strategy for the facile reduction of N2 and subsequent conversion to various N-containing chemicals via a looped Li–N2 battery. The electrosynthesis of lithium bis(trifluoromethanesulfonyl)imide is illustrated as a prototype using cascade reactions involving electrocatalytic N2 reduction to Li3N on discharge, a relay reaction of Li3N acylation to lithium bis(trifluoromethanesulfonyl)imide and finally the elimination of the LiCl by-product on charge to complete the synthesis loop. This strategy provides direct access to analogues with different N–X bonds (X = S, C and so on) and metal cations (Li+, Zn2+ and so on) by extending the substrate scope, and can be scaled up for improved energy efficiency and atom economy. This work provides a general electrosynthesis protocol for the practical production of N-containing chemicals and has potential implications for a wider field of sustainable chemistry.

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Fig. 1: Schematic comparison.
Fig. 2: Electrochemical reduction of N2 to Li3N.
Fig. 3: S–N acylation reaction between Li3N and CF3SO2Cl.
Fig. 4: Looped Li–N2 battery for LiTFSI electrosynthesis.
Fig. 5: Scope of the expended substrate.

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Data availability

All data supporting the findings of this study are available in the article and its Supplementary Information. Data are also available from the corresponding author upon request. Source data are provided with this paper.

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Acknowledgements

We acknowledge support from the National Natural Science Foundation of China (grant nos 22022110 (Y.W.), 22279141 (Y.W.), 22205238 (X.Z.) and 22209182 (Y.F.)), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (no. ZDBS-LY-SLH028 (Y.W.)) and the National Key Research & Development Program of China (no. 2021YFA1501500 (Y.W.)). We gratefully thank, for the financial support, the Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China (nos 2021ZZ106 (Y.W.) and 2021ZR123 (J.L.)), Fujian Provincial Science and Technology Service Network Initiative programme supporting project of the Chinese Academy of Sciences (no. 2022T3001 (M.W.)) and the Nature Science Foundation of Fujian Province (nos 2023I0033 (X.Z.) and 2022J05094 (J.L.)). This work was also supported by Fujian Shaowu Chuangxin New Materials Co., Ltd. (no. HX-JS-2023-007 (Y.W.)).

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, P. R. China

    Xiang Zhang, Wenping Xiong, Tao Wang, Erchong Chai, Jing Lin, Lanting Huang, Yangyang Feng, Maoxiang Wu & Yaobing Wang

  2. Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, P. R. China

    Xiang Zhang, Jing Lin & Yaobing Wang

  3. University of Chinese Academy of Sciences, Beijing, P. R. China

    Xiang Zhang, Wenping Xiong, Tao Wang, Yangyang Feng, Maoxiang Wu & Yaobing Wang

  4. Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, P. R. China

    Xiang Zhang, Wenping Xiong, Tao Wang, Erchong Chai, Jing Lin, Lanting Huang, Yangyang Feng, Maoxiang Wu & Yaobing Wang

  5. College of Chemistry, Fuzhou University, Fuzhou, P. R. China

    Erchong Chai & Lanting Huang

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Contributions

Y.W. conceived the idea and supervised the project. X.Z. designed the experiments. W.X., T.W., E.C. and X.Z. carried out the electrochemical measurements and characterization. L.H. assisted with the experiments. J.L. performed the computational calculation. X.Z. wrote the paper. Y.W., Y.F. and M.W. revised the paper, with comments from all authors.

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Correspondence to Yaobing Wang.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–36, Tables 1 and 2, Notes 1 and 2 and references.

Supplementary Data 1

Atomic coordinates of optimized models.

Source data

Source Data Fig. 2

Electrocatalytic N2 reduction to Li3N.

Source Data Fig. 3

S–N acylation reaction.

Source Data Fig. 4

Cascade electrosynthesis and performance metrics.

Source Data Fig. 5

Extensibility verification.

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Zhang, X., Xiong, W., Wang, T. et al. Cascade electrosynthesis of LiTFSI and N-containing analogues via a looped Li–N2 battery. Nat Catal 7, 55–64 (2024). https://doi.org/10.1038/s41929-023-01067-3

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