Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Conversion of non-van der Waals solids to 2D transition-metal chalcogenides

Nature volume 577, pages 492–496 (2020)Cite this article

Subjects

Abstract

Although two-dimensional (2D) atomic layers, such as transition-metal chalcogenides, have been widely synthesized using techniques such as exfoliation1,2,3 and vapour-phase growth4,5, it is still challenging to obtain phase-controlled 2D structures6,7,8. Here we demonstrate an effective synthesis strategy via the progressive transformation of non-van der Waals (non-vdW) solids to 2D vdW transition-metal chalcogenide layers with identified 2H (trigonal prismatic)/1T (octahedral) phases. The transformation, achieved by exposing non-vdW solids to chalcogen vapours, can be controlled using the enthalpies and vapour pressures of the reaction products. Heteroatom-substituted (such as yttrium and phosphorus) transition-metal chalcogenides can also be synthesized in this way, thus enabling a generic synthesis approach to engineering phase-selected 2D transition-metal chalcogenide structures with good stability at high temperatures (up to 1,373 kelvin) and achieving high-throughput production of monolayers. We anticipate that these 2D transition-metal chalcogenides will have broad applications for electronics, catalysis and energy storage.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic illustration of the conversion of non-vdW solids to 2D vdW transition-metal chalcogenides.
Fig. 2: Structural characterization of 2D transition-metal chalcogenides derived from MAX phases.
Fig. 3: Structural characterization of 2D heteroatom-doped transition-metal chalcogenides with 2H phase derived from quaternary MAX phases.
Fig. 4: Structural characterization and electrical properties of 2D heteroatom (Y and P) co-doped WS2 with 1T phase derived from quaternary MAX-(W2/3Y1/3)2AlC.

Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request.

References

  1. Coleman, J. N. et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 331, 568–571 (2011).

    Article  ADS  CAS  Google Scholar 

  2. Lin, Z. et al. Solution-processable 2D semiconductors for high-performance large-area electronics. Nature 562, 254–258 (2018).

    ADS  PubMed  CAS  Google Scholar 

  3. Huang, Y. et al. Reliable exfoliation of large-area high-quality flakes of graphene and other two-dimensional materials. ACS Nano 9, 10612–10620 (2015).

    Article  CAS  Google Scholar 

  4. Zhou, J. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).

    Article  ADS  CAS  Google Scholar 

  5. Chen, X. et al. CVD-grown monolayer MoS2 in bioabsorbable electronics and biosensors. Nat. Commun. 9, 1690–1701 (2018).

    Article  ADS  CAS  Google Scholar 

  6. Voiry, D. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 12, 850–855 (2013).

    Article  ADS  CAS  Google Scholar 

  7. Zhu, J. et al. Argon plasma induced phase transition in monolayer MoS2. J. Am. Chem. Soc. 139, 10216–10219 (2017).

    Article  CAS  Google Scholar 

  8. Eda, G. et al. Photoluminescence from chemically exfoliated MoS2. Nano Lett. 11, 5111–5116 (2011).

    Article  ADS  CAS  Google Scholar 

  9. Zhang, J. et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction. Nat. Catal. 1, 985–992 (2018).

    Article  CAS  Google Scholar 

  10. Kundu, D., Adams, B. D., Ort, V. D., Vajargah, S. H. & Nazar, L. F. A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode. Nat. Energy 1, 16119–16126 (2016).

    Article  ADS  CAS  Google Scholar 

  11. Zhang, C. et al. High capacity silicon anodes enabled by MXene viscous aqueous ink. Nat. Commun. 10, 849–857 (2019).

    Article  ADS  Google Scholar 

  12. Yan, M. et al. Water-lubricated intercalation in V2O5·nH2O for high-capacity and high-rate aqueous rechargeable zinc batteries. Adv. Mater. 30, 1703725–1703730 (2018).

    Article  CAS  Google Scholar 

  13. Wang, Y. et al. In situ exfoliated, N-doped, and edge-rich ultrathin layered double hydroxides nanosheets for oxygen evolution reaction. Adv. Funct. Mater. 28, 1703363–1703368 (2018).

    Article  CAS  Google Scholar 

  14. Liu, J., Qian, X. & Fu, L. Crystal field effect induced topological crystalline insulators in monolayer IV–VI semiconductors. Nano Lett. 15, 2657–2661 (2015).

    Article  ADS  CAS  Google Scholar 

  15. Balan, A. P. et al. Exfoliation of a non-van der Waals material from iron ore hematite. Nat. Nanotechnol. 13, 602–609 (2018).

    Article  ADS  CAS  Google Scholar 

  16. Naguib, M. et al. Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2. Adv. Mater. 23, 4248–4253 (2011).

    Article  CAS  Google Scholar 

  17. Barsoum, M. W. MAX Phases: Properties of Machinable Ternary Carbides and Nitrides (Wiley, 2013).

  18. Sokol, M., Natu, V., Kota, S. & Barsoum, M. W. On the chemical diversity of the MAX phases. Trends Chem. 1, 210–223 (2019).

    Article  Google Scholar 

  19. Xuan, J. et al. Organic-base-driven intercalation and delamination for the production of functionalized titanium carbide nanosheets with superior photothermal therapeutic performance. Angew. Chem. Int. Ed. 55, 14569–14574 (2016).

    Article  CAS  Google Scholar 

  20. Ghidiu, M., Lukatskaya, M. R., Zhao, M. Q., Gogotsi, Y. & Barsoum, M. W. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature 516, 78–81 (2014).

    Article  ADS  CAS  Google Scholar 

  21. Lukatskaya, M. R. et al. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 341, 1502–1505 (2013).

    Article  ADS  CAS  Google Scholar 

  22. Li, M. et al. Element replacement approach by reaction with Lewis acidic molten salts to synthesize nanolaminated MAX phases and MXenes. J. Am. Chem. Soc. 141, 4730–4737 (2019).

    Article  CAS  Google Scholar 

  23. Barin, I. Thermochemical Data of Pure Substances 3rd edn (VCH, 1995).

  24. Yaws, C. L. The Yaws Handbook of Physical Properties for Hydrocarbons and Chemicals 2nd edn (Elsevier, 2015).

  25. Winterbone, D. E. Advanced Thermodynamics for Engineers (Butterworth-Heinemann, 1997).

  26. Naguib, M., Mochalin, V. N., Barsoum, M. W. & Gogotsi, Y. 25th anniversary article: MXenes: a new family of two-dimensional materials. Adv. Mater. 26, 992–1005 (2014).

    Article  CAS  Google Scholar 

  27. Anasori, B., Lukatskaya, M. R. & Gogotsi, Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat. Rev. Mater. 2, 16098–16114 (2017).

    Article  ADS  CAS  Google Scholar 

  28. Anasori, B. et al. Two-dimensional, ordered, double transition metals carbides (MXenes). ACS Nano 9, 9507–9516 (2015).

    Article  CAS  Google Scholar 

  29. Meshkian, R. et al. W-based atomic laminates and their 2D derivative W1.33C MXene with vacancy ordering. Adv. Mater. 30, 1706409–1706416 (2018).

    Article  CAS  Google Scholar 

  30. Naguib, M. et al. Two-dimensional transition metal carbides. ACS Nano 6, 1322–1331 (2012).

    Article  CAS  Google Scholar 

  31. Deepak, F. L. et al. Fullerene-like (IF) NbxMo1-xS2 nanoparticles. J. Am. Chem. Soc. 129, 12549–12562 (2007).

    Article  CAS  Google Scholar 

  32. Yang, S. Z. et al. Rhenium-doped and stabilized MoS2 atomic layers with basal-plane catalytic activity. Adv. Mater. 30, 1803477–1803483 (2018).

    Article  CAS  Google Scholar 

  33. Liu, Q. et al. Stable metallic 1T-WS2 nanoribbons intercalated with ammonia ions: the correlation between structure and electrical/optical properties. Adv. Mater. 27, 4837–4844 (2015).

    Article  CAS  Google Scholar 

  34. Radhakrishnan, S. et al. An insight into the phase transformation of WS2 upon fluorination. Adv. Mater. 30, 1803366–1803375 (2018).

    Article  CAS  Google Scholar 

  35. Lin, Y. C., Dumcencon, D. O., Huang, Y. S. & Suenaga, K. Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2. Nat. Nanotechnol. 9, 391–396 (2014).

    Article  ADS  CAS  Google Scholar 

  36. Sun, Z. M. Progress in research and development on MAX phases: a family of layered ternary compounds. Int. Mater. Rev. 56, 143–166 (2011).

    Article  CAS  Google Scholar 

  37. Barsoum, M. W. The MN+1AXN phases: a new class of solids: thermodynamically stable nanolaminates. Prog. Solid State Chem. 28, 201–281 (2000).

    Article  CAS  Google Scholar 

  38. Eklund, P., Beckers, M., Jansson, U., Hogberg, H. & Hultman, L. The Mn+1AXn phases: materials science and thin-film processing. Thin Solid Films 518, 1851–1878 (2010).

    Article  ADS  CAS  Google Scholar 

  39. Magnuson, M. & Mattesini, M. Chemical bonding and electronic-structure in MAX phases as viewed by X-ray spectroscopy and density functional theory. Thin Solid Films 621, 108–130 (2017).

    Article  ADS  CAS  Google Scholar 

  40. Naguib, M. et al. New two-dimensional niobium and vanadium carbides as promising materials for Li-ion batteries. J. Am. Chem. Soc. 135, 15966–15969 (2013).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant numbers 51622203 and 51572007), the Youth 1000-Talent Program of China and the 111 Project (grant number B17002). X.Z. also thanks Shenzhen Basic Research Projects (grant number JCYJ20170407155608882), the China Postdoctoral Science Foundation (grant number 2018M631458) and the Development and Reform Commission of Shenzhen Municipality for the development of the “Low-Dimensional Materials and Devices” Discipline, Guangdong Innovative and Entrepreneurial Research Team Program (grant number 2017ZT07C341). We thank the Shanghai Synchrotron Radiation Facility and Beijing Synchrotron Radiation Facility for support. We thank X. Chen, Q. Zhang, W. Zhou and M. Li for help with the TEM analysis; S. Chen and Y. Lin for help with the EXAFS analysis; and L. Ma for suggestions.

Author information

Authors and Affiliations

  1. Key Laboratory of Aerospace Advanced Materials and Performance of Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing, China

    Zhiguo Du, Shubin Yang, Songmei Li, Shuai Wang, Bin Li & Yongji Gong

  2. Department of Materials Science and NanoEngineering, Rice University, Houston, TX, USA

    Jun Lou & Pulickel M. Ajayan

  3. Shenzhen Geim Graphene Center and Low-Dimensional Materials and Devices Laboratory (LDMD), Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, Shenzhen, China

    Shuqing Zhang & Xiaolong Zou

  4. National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, China

    Li Song

Authors
  1. Zhiguo Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shubin Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Songmei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jun Lou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shuqing Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Shuai Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Bin Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yongji Gong
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Li Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Xiaolong Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Pulickel M. Ajayan
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

S.Y., S.L. and P.M.A. supervised the project. S.Y. and Z.D. designed and carried out all of the experiments. S.Z. and X.Z. carried out the density functional theory calculations. S.W. and B.L. performed the scanning electron microscope, TEM and X-ray diffraction measurements. B.L. carried out the X-ray photoelectron spectroscopy and Raman analysis. L.S. contributed to the XANES and EXAFS measurements. Z.D. performed the atomic force microscopy. Z.D. and Y.G. designed the film electrodes and carried out the electrical and electrocatalytic measurements. All authors discussed the results and assisted during manuscript preparation.

Corresponding authors

Correspondence to Shubin Yang or Pulickel M. Ajayan.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature thanks Per Eklund, Wei Sun Leong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

This file contains the Supplementary Information (sections 1-6), which includes Supplementary Materials and Methods, Supplementary Figures 1-73, Supplementary Tables 1-9, Supplementary Text and Supplementary References–see contents page for details.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Du, Z., Yang, S., Li, S. et al. Conversion of non-van der Waals solids to 2D transition-metal chalcogenides. Nature 577, 492–496 (2020). https://doi.org/10.1038/s41586-019-1904-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-019-1904-x

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing