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High-yield production of mono- or few-layer transition metal dichalcogenide nanosheets by an electrochemical lithium ion intercalation-based exfoliation method

Abstract

Transition metal dichalcogenide (TMD) nanomaterials, especially the mono- or few-layer ones, have received extensive research interest owing to their versatile properties, ranging from true metals (e.g., NbS2 and VSe2) and semimetals (e.g., WTe2 and TiSe2) to semiconductors (e.g., MoS2 and We2) and insulators (e.g., HfS2). Therefore, the reliable production of these nanomaterials with atomically thin thickness and laterally uniform dimension is essential for their promising applications in transistors, photodetectors, electroluminescent devices, catalysis, energy conversion, environment remediation, biosensing, bioimaging, and so on. Recently, the electrochemical lithium ion intercalation-based exfoliation method has emerged as a mature, efficient and promising strategy for the high-yield production of mono- or few-layer TMD nanosheets; monolayer MoS2 (yield of 92%), monolayer TaS2 (yield of 93%) and bilayer TiS2 (yield of 93%) with lateral dimensions of ~1 µm (refs. 1,2,3). This Protocol describes the details of experimental procedures for the high-yield synthesis of mono- or few-layer TMDs and other inorganic nanosheets such as MoS2, WS2, TiS2, TaS2, ZrS2, graphene, h-BN, NbSe2, WSe2, Sb2Se3 and Bi2Te3 by using the electrochemical lithium ion intercalation-based exfoliation method, which involves the electrochemical intercalation of lithium ions into layered inorganic crystals and a mild sonication process. The whole protocol takes 26–38 h for the successful production of ultrathin inorganic nanosheets.

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Fig. 1: Schematic illustrations of the electrochemical lithium ion intercalation-based exfoliation process.
Fig. 2: The electrochemical lithium ion-intercalation experimental setup.
Fig. 3: Schematic illustrations of the whole procedure for the preparation of mono- or few-layer TMD nanosheets.
Fig. 4: The opaque suspension of the exfoliated MoS2, WS2, TiS2, TaS2, BN and NbSe2 nanosheets.
Fig. 5: TEM images, selected area electron diffraction (SAED) patterns and high-resolution transmission electron microscopy (HRTEM) images of the exfoliated nanosheets.
Fig. 6: AFM images of the exfoliated nanosheets.
Fig. 7: AFM images of large-area nanosheets.
Fig. 8: XPS spectra of the exfoliated nanosheets.
Fig. 9: Raman spectra of various samples.
Fig. 10: Absorption spectra of various samples.

Data availability

The main data supporting the findings of this study were previously published1,2,3. Additional imaging data are in the Supplementary Figs. 1–9 or are available from the corresponding author upon reasonable request.

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Acknowledgements

Z.Z. thanks the Start-Up Grant from CityU (CityU9610435) and ECS scheme (CityU9048163) from RGC in Hong Kong, and the Basic Research Project from Shenzhen Science and Technology Innovation Committee in Shenzhen, China (JCYJ20210324134012034). H.S.S. acknowledges support by research funds (2020M3D1A1110548 and 2019M1A2A2065616) through NRF, Republic of Korea.

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Contributions

Z.Z. developed the protocol and performed the experiments. R.Y., L.M. and Z.Z. drafted the manuscript. R.Y., L.M. and Q.Z. performed some experiments. H.S.S. and D.V. provided constructive comments on the manuscript. All authors reviewed the manuscript.

Corresponding authors

Correspondence to Hyeon Suk Shin, Damien Voiry or Zhiyuan Zeng.

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The authors declare no competing interests.

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Key references using this protocol

Huang, X. et al. Nat. Commun. 4, 1444 (2013): https://www.nature.com/articles/ncomms2472#citeas

Zhu, C. et al. J. Am. Chem. Soc. 135, 5998–6001 (2013): https://pubs.acs.org/doi/10.1021/ja4019572

Mei, L. et al. Chem. Commun. 57, 2879 (2021): https://doi.org/10.1039/D0CC08091H

Key data used in this protocol

Zeng, Z. et al. Angew. Chem. Int. Ed. 50, 11093–11097 (2011): https://onlinelibrary.wiley.com/doi/10.1002/anie.201106004

Zeng, Z. et al. Angew. Chem. Int. Ed. 51, 9052–9056 (2012): https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201204208

Zeng, Z. et al. Energy Environ. Sci. 7, 797–803 (2014): https://doi.org/10.1039/C3EE42620C

Supplementary information

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Supplementary Figs. 1–9 and Supplementary Tables 1 and 2.

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Yang, R., Mei, L., Zhang, Q. et al. High-yield production of mono- or few-layer transition metal dichalcogenide nanosheets by an electrochemical lithium ion intercalation-based exfoliation method. Nat Protoc 17, 358–377 (2022). https://doi.org/10.1038/s41596-021-00643-w

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