Skip to main content
SpringerLink
Log in

Direct imaging and determination of the crystal structure of six-layered graphdiyne

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Since its discovery, the direct imaging and determination of the crystal structure of few-layer graphdiyne has proven difficult because it is too delicate under irradiation by an electron beam. In this work, the crystal structure of a six-layered graphdiyne nanosheet was directly observed by low-voltage transmission electron microscopy (TEM) using low current density. The combined use of high-resolution TEM (HRTEM) simulation, electron energy-loss spectroscopy, and electron diffraction revealed that the as-synthesized nanosheet was crystalline graphdiyne with a thickness of 2.19 nm (corresponding to a thickness of six layers) and showed ABC stacking. Thus, this work provides direct evidence for the existence and crystal structure of few-layer graphdiyne, which is a new type of two-dimensional carbon material complementary to graphene.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Baughman, R. H.; Zakhidov, A. A.; de Heer, W. A. Carbon nanotubes-the route toward applications. Science 2002, 297, 787–792.

    Article  Google Scholar 

  2. Baughman, R. H.; Eckhardt, H.; Kertesz, M. Structure-property predictions for new planar forms of carbon: Layered phases containing sp2 and sp atoms. J. Chem. Phys. 1987, 87, 6687–6699.

    Article  Google Scholar 

  3. Coluci, V. R.; Galvão, D. S.; Baughman, R. H. Theoretical investigation of electromechanical effects for graphyne carbon nanotubes. J. Chem. Phys. 2004, 121, 3228–3237.

    Article  Google Scholar 

  4. Li, Y. J.; Xu, L.; Liu, H. B.; Li, Y. L. Graphdiyne and graphyne: From theoretical predictions to practical construction. Chem. Soc. Rev. 2014, 43, 2572–2586.

    Article  Google Scholar 

  5. Chen, J. M.; Xi, J. Y.; Wang, D; Shuai, Z. G. Carrier mobility in graphyne should be even larger than that in graphene: A theoretical prediction. J. Phys. Chem. Lett. 2013, 4, 1443–1448.

    Article  Google Scholar 

  6. Jin, Z. W.; Zhou, Q.; Chen, Y. H.; Mao, P.; Li, H.; Liu, H. B.; Wang, J. Z.; Li, Y. L. Graphdiyne: ZnO nanocomposites for high-performance UV photodetectors. Adv. Mater. 2016, 28, 3697–3702.

    Article  Google Scholar 

  7. Xiao, J. Y.; Shi, J. J.; Liu, H. B.; Xu, Y. Z.; Lv, S. T.; Luo, Y. H.; Li, D. M.; Meng, Q. B.; Li, Y. L. Efficient CH3NH3PbI3 perovskite solar cells based on graphdiyne (GD)-modified P3HT hole-transporting material. Adv. Energy Mater. 2015, 5, 1401493.

    Google Scholar 

  8. Li, G. X.; Li, Y. L.; Qian, X. M.; Liu, H. B.; Lin, H. W.; Chen, N.; Li, Y. J. Construction of tubular molecule aggregations of graphdiyne for highly efficient field emission. J. Phys. Chem. C 2011, 115, 2611–2615.

    Article  Google Scholar 

  9. Huang, C. S.; Zhang, S. L.; Liu, H. B.; Li, Y. J.; Cui, G. L.; Li, Y. L. Graphdiyne for high capacity and long-life lithium storage. Nano Energy 2015, 11, 481–489.

    Article  Google Scholar 

  10. Zhang, S. L.; Liu, H. B.; Huang, C. S.; Cui, G. L.; Li, Y. L. Bulk graphdiyne powder applied for highly efficient lithium storage. Chem. Commun. 2015, 51, 1834–1837.

    Article  Google Scholar 

  11. Yang, N. L.; Liu, Y. Y.; Wen, H.; Tang, Z. Y.; Zhao, H. J.; Li, Y. L.; Wang, D. Photocatalytic properties of graphdiyne and graphene modified TiO2: From theory to experiment. ACS Nano 2013, 7, 1504–1512.

    Article  Google Scholar 

  12. Zhang, X.; Zhu, M. S.; Chen, P. L.; Li, Y. J.; Liu, H. B.; Li, Y. L.; Liu, M. H. Pristine graphdiyne-hybridized photocatalysts using graphene oxide as a dual-functional coupling reagent. Phys. Chem. Chem. Phys. 2015, 17, 1217–1225.

    Article  Google Scholar 

  13. Li, J.; Gao, X.; Liu, B.; Feng, Q. L.; Li, X. B.; Huang, M. Y.; Liu, Z. F.; Zhang, J.; Tung, C. H.; Wu, L. Z. Graphdiyne: A metal-free material as hole transfer layer to fabricate quantum dot-sensitized photocathodes for hydrogen production. J. Am. Chem. Soc. 2016, 138, 3954–3957.

    Article  Google Scholar 

  14. Li, G. X.; Li, Y. L.; Liu, H. B.; Guo, Y. B.; Li, Y. J.; Zhu, D. B. Architecture of graphdiyne nanoscale films. Chem. Commun. 2010, 46, 3256–3258.

    Article  Google Scholar 

  15. Qian, X. M.; Ning, Z. Y.; Li, Y. L.; Liu, H. B.; Ouyang, C. B.; Chen, Q.; Li, Y. J. Construction of graphdiyne nanowires with high-conductivity and mobility. Dalton Trans. 2012, 41, 730–733.

    Article  Google Scholar 

  16. Zhou, J. Y.; Gao, X.; Liu, R.; Xie, Z. Q.; Yang, J.; Zhang, S. Q.; Zhang, G. M.; Liu, H. B.; Li, Y. L.; Zhang, J. et al. Synthesis of graphdiyne nanowalls using acetylenic coupling reaction. J. Am. Chem. Soc. 2015, 137, 7596−7599.

    Article  Google Scholar 

  17. Matsuoka, R.; Sakamoto, R.; Hoshiko, K.; Sasaki, S.; Masunaga, H.; Nagashio, K.; Nishihara, H. Crystalline graphdiyne nanosheets produced at a gas/liquid or liquid/liquid interface. J. Am. Chem. Soc. 2017, 139, 3145–3152.

    Article  Google Scholar 

  18. Li, J. Q.; Xie, Z. Q.; Xiong, Y.; Li, Z. Z.; Huang, Q. X.; Zhang, S. Q.; Zhou, J. Y.; Liu, R.; Gao, X.; Chen, C. Q. et al. Architecture of β-graphdiyne-containing thin film using modified glaser–hay coupling reaction for enhanced photocatalytic property of TiO2. Adv. Mater. 2017, 29, 1700421.

    Article  Google Scholar 

  19. Ivanovskii, A. L. Graphynes and graphdyines. Prog. Solid State Chem. 2013, 41, 1–19.

    Article  Google Scholar 

  20. Xia, J.; Wang, X. L.; Tay, B. K.; Chen, S. S.; Liu, Z.; Yan, J. X.; Shen, Z. X. Valley polarization in stacked MoS2 induced by circularly polarized light. Nano Res. 2017, 10, 1618–1626.

    Article  Google Scholar 

  21. Lu, X.; Luo, X.; Zhang, J.; Quek, S. Y.; Xiong, Q. H. Lattice vibrations and Raman scattering in two-dimensional layered materials beyond graphene. Nano Res. 2016, 9, 3559–3597.

    Article  Google Scholar 

  22. Sánchez-Royo, J. F.; Muñoz-Matutano, G.; Brotons-Gisbert, M.; Martínez-Pastor, J. P.; Segura, A.; Cantarero, A.; Mata, R.; Canet-Ferrer, J.; Tobias, G.; Canadell, E. et al. Electronic structure, optical properties, and lattice dynamics in atomically thin indium selenide flakes. Nano Res. 2014, 7, 1556–1568.

    Article  Google Scholar 

  23. Zheng, Q. Y.; Luo, G. F.; Liu, Q. H.; Quhe, R. G.; Zheng, J. X.; Tang, K. C.; Gao, Z. X.; Nagase, S.; Lu, J. Structural and electronic properties of bilayer and trilayer graphdiyne. Nanoscale 2012, 4, 3990–3996.

    Article  Google Scholar 

  24. Srinivasu, K.; Ghosh, S. K. Graphyne and graphdiyne: Promising materials for nanoelectronics and energy storage applications. J. Phys. Chem. C 2012, 116, 5951–5956.

    Article  Google Scholar 

  25. Long, M. Q.; Tang, L.; Wang, D.; Li, Y. L.; Shuai Z. G. Electronic structure and carrier mobility in graphdiyne sheet and nanoribbons: Theoretical predictions. ACS Nano 2011, 5, 2593–2600.

    Article  Google Scholar 

  26. Narita, N.; Nagai, S.; Suzuki, S.; Nakao, K. Electronic structure of three-dimensional graphyne. Phys. Rev. B 2000, 62, 11146–11151.

    Article  Google Scholar 

  27. Egerton, R. F. Electron Energy-Loss Spectroscopy in the Electron Microscope; Springer: New York, USA, 1995.

    Book  Google Scholar 

  28. Li, C.; Yao, Y.; Shen, X.; Wang, Y. G.; Li, J. J.; Gu, C. Z.; Yu, R. C.; Liu, Q.; Liu, M. Dynamic observation of oxygen vacancies in hafnia layer by in situ transmission electron microscopy. Nano Res. 2015, 8, 3571–3579.

    Article  Google Scholar 

  29. Li, C.; Gao, B.; Yao, Y.; Guan, X. X.; Shen, X.; Wang, Y. G.; Huang, P.; Liu, L. F.; Liu, X. Y.; Li, J. J. et al. Direct observations of nanofilament evolution in switching processes in HfO2-based resistive random access memory by in situ TEM studies. Adv. Mater. 2017, 29, 1602976.

    Article  Google Scholar 

  30. Gao, X.; Li, J.; Du, R.; Zhou, J. Y.; Huang, M. Y.; Liu, R.; Li, J.; Xie, Z. Q.; Wu, L. Z.; Liu, Z. F. et al. Direct synthesis of graphdiyne nanowalls on arbitrary substrates and its application for photoelectrochemical water splitting cell. Adv. Mater. 2017, 29, 1605308.

    Article  Google Scholar 

  31. Chang, L. Y.; Kirkland, A. I. Comparisons of linear and nonlinear image restoration. Microsc. Microanal. 2006, 12, 469–475.

    Article  Google Scholar 

  32. Marks, L. D. Wiener-filter enhancement of noisy HREM images. Ultramicroscopy 1996, 62, 43–52.

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 11604241, 21790052 and 21331007), the National Program for Thousand Young Talents of China, the Postdoctoral Science Foundation of China (No. 2015M580209), the Tianjin Municipal Education Commission, the Tianjin Municipal Science and Technology Commission (No. 15JCYBJC52600), and the Fundamental Research Fund of Tianjin University of Technology.

Author information

Author notes

  1. Chao Li and Xiuli Lu contributed equally to this work.

Authors and Affiliations

  1. Center for Electron Microscopy, TUT-FEI Joint Laboratory, Tianjin Key Laboratory of Advanced Porous Functional Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China

    Chao Li, Xiuli Lu, Yingying Han, Shangfeng Tang, Yi Ding, Ruirui Liu, Haihong Bao, Jun Luo & Tongbu Lu

  2. Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Yuliang Li

Authors
  1. Chao Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiuli Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yingying Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shangfeng Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yi Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ruirui Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Haihong Bao
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yuliang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Jun Luo
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Tongbu Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jun Luo or Tongbu Lu.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, C., Lu, X., Han, Y. et al. Direct imaging and determination of the crystal structure of six-layered graphdiyne. Nano Res. 11, 1714–1721 (2018). https://doi.org/10.1007/s12274-017-1789-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-017-1789-7

Keywords

Search

Navigation