Letter | Published:

Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template

Nature volume 535, pages 131135 (07 July 2016) | Download Citation

Abstract

Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure1,2,3,4,5,6. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures7,8,9,10,11,12,13,14,15. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst supports.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , , , & Porous graphene materials for advanced electrochemical energy storage and conversion devices. Adv. Funct. Mater. 26, 849–864 (2014)

  2. 2.

    & Design of advanced porous graphene materials: from graphene nanomesh to 3D architectures. Nanoscale 6, 1922–1945 (2014)

  3. 3.

    , & Three-dimensional graphene materials: preparation, structures and application in supercapacitors. Energy Environ. Sci. 7, 1850–1865 (2014)

  4. 4.

    & Negative-curvature fullerene analog of C60. Phys. Rev. Lett. 68, 511–513 (1992)

  5. 5.

    & Diamond from graphite. Nature 352, 762 (1991)

  6. 6.

    , , & Energetics of negatively curved graphitic carbon. Nature 355, 333–335 (1992)

  7. 7.

    , & Preparation of a high surface area microporous carbon having the structural regularity of Y zeolite. Chem. Commun. 23, 2365–2366 (2000)

  8. 8.

    , , , & Very high surface area microporous carbon with a three-dimensional nano-array structure: synthesis and its molecular structure. Chem. Mater. 13, 4413–4415 (2001)

  9. 9.

    et al. A possible buckybowl-like structure of zeolite templated carbon. Carbon 47, 1220–1230 (2009)

  10. 10.

    et al. Formation of crosslinked-fullerene-like framework as negative replica of zeolite Y. Carbon 62, 455–464 (2013)

  11. 11.

    , , , & Structure and sorption properties of a zeolite-templated carbon with the EMT structure type. Langmuir 30, 297–307 (2014)

  12. 12.

    , & Template synthesis of novel porous carbons using various types of zeolites. Carbon 41, 1451–1459 (2003)

  13. 13.

    , & Enhanced hydrogen storage capacity of high surface area zeolite-like carbon materials. J. Am. Chem. Soc. 129, 1673–1679 (2007)

  14. 14.

    , , & Preparation and hydrogen storage properties of zeolite-templated carbon materials nanocast via chemical vapor deposition: effect of the zeolite template and nitrogen doping. J. Phys. Chem. B 110, 18424–18431 (2006)

  15. 15.

    et al. Effect of cation nature of zeolite on carbon replicas and their electrochemical capacitance. Electrochim. Acta 89, 763–770 (2013)

  16. 16.

    From microporous to mesoporous molecular sieve materials and their use in catalysis. Chem. Rev. 97, 2373–2420 (1997)

  17. 17.

    & Zeolite and molecular sieve synthesis. Chem. Mater. 4, 756–768 (1992)

  18. 18.

    Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)

  19. 19.

    State of the art and future challenges of zeolites as catalysts. J. Catal. 216, 298–312 (2003)

  20. 20.

    , , & Formation of new type of porous carbon by carbonization in zeolite nanochannels. Chem. Mater. 9, 609–615 (1997)

  21. 21.

    , , & Effect of micropore topology on the structure and properties of zeolite polymer replicas. Chem. Mater. 9, 2448–2458 (1997)

  22. 22.

    & Organic chemistry of coke formation. Appl. Catal. A Gen. 212, 83–96 (2001)

  23. 23.

    et al. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR. Nature Mater. 12, 351–358 (2013)

  24. 24.

    et al. Synthesis of new, nanoporous carbon with hexagonally ordered mesostructured. J. Am. Chem. Soc. 122, 10712–10713 (2000)

  25. 25.

    , & A facile molten-salt route to graphene synthesis. Small 10, 193–200 (2014)

  26. 26.

    et al. Gram-scale synthesis of nanomesh graphene with high surface area and its application in supercapacitor electrodes. Chem. Commun. 47, 5976–5978 (2011)

  27. 27.

    , & Hydrogen storage in yttrium-decorated single walled carbon nanotube. J. Phys. Chem. 116, 22502–22508 (2012)

  28. 28.

    et al. Calcium as the superior coating metal in functionalization of carbon fullerenes for high-capacity hydrogen storage. Phys. Rev. Lett. 100, 206806 (2008)

  29. 29.

    et al. Negatively curved carbon as the anode for lithium ion batteries. Carbon 66, 39–47 (2014)

  30. 30.

    , & Carbon-based nanostructures for advanced catalysis. ChemCatChem 7, 2806–2815 (2015)

  31. 31.

    Zeolite Molecular Sieves (Wiley, 1974)

  32. 32.

    , , & Synthesis of new silica-rich cubic and hexagonal faujasites using crown-ether-based supramolecules as templates. Zeolites 10, 546–552 (1990)

  33. 33.

    , & Direct synthesis of zeolite Y with large particle size. Int. J. Inorg. Mater. 3, 773–780 (2001)

  34. 34.

    APEX2 and SAINT (Bruker AXS, 2014)

  35. 35.

    SADABS (Univ. Göttingen, 2008)

  36. 36.

    , & Crystallographic computing system JANA2006: general features. Z. Kristallogr. 229, 345–352 (2014)

  37. 37.

    & SUPERFLIP—a computer program for the solution of crystal structures by charge flipping in arbitraray dimensions. J. Appl. Cryst. 40, 786–790 (2007)

  38. 38.

    & Symmetry determination following structure solution in P1. J. Appl. Cryst. 41, 975–984 (2008)

  39. 39.

    , & , & Rietveld refinement guidelines. J. Appl. Cryst. 32, 36–50 (1999)

  40. 40.

    , & Structure of the borosilicate zeolite catalyst SSZ-82 solved using 2D-XPD charge flipping. J. Am. Chem. Soc. 133, 20604–20610 (2011)

  41. 41.

    et al. Macroscopic 3D nanographene with dynamically tunable bulk properties. Adv. Mater. 24, 5083–5087 (2012)

Download references

Acknowledgements

This work was supported by IBS-R004-D1. The authors thank D. Ahn at the Pohang Accelerator Laboratory (PLS) for discussions on powder XRD measurements. X-ray crystallography was carried out with help from D. Moon at PLS and H. J. Lee at Korea Basic Science Institute.

Author information

Affiliations

  1. Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon 305-701, Korea

    • Kyoungsoo Kim
    • , Taekyoung Lee
    • , Yonghyun Kwon
    • , Yongbeom Seo
    • , Hyunsoo Lee
    • , Jeong Young Park
    • , Hyotcherl Ihee
    •  & Ryong Ryoo
  2. Department of Chemistry, KAIST, Daejeon 34141, Korea

    • Taekyoung Lee
    • , Yonghyun Kwon
    • , Hyotcherl Ihee
    •  & Ryong Ryoo
  3. Department of Chemical and Biomolecular Engineering, KAIST, Daejeon 34141, Korea

    • Jongchan Song
    •  & Jung Ki Park
  4. Graduate School of EEWS, KAIST, Daejeon 34141, Korea

    • Jeong Young Park
  5. Clean Energy Technology Laboratory and Department of Chemical Engineering, Chonnam National University, Gwangju 61186, Korea

    • Sung June Cho

Authors

  1. Search for Kyoungsoo Kim in:

  2. Search for Taekyoung Lee in:

  3. Search for Yonghyun Kwon in:

  4. Search for Yongbeom Seo in:

  5. Search for Jongchan Song in:

  6. Search for Jung Ki Park in:

  7. Search for Hyunsoo Lee in:

  8. Search for Jeong Young Park in:

  9. Search for Hyotcherl Ihee in:

  10. Search for Sung June Cho in:

  11. Search for Ryong Ryoo in:

Contributions

R.R. selected metal-ion catalysts intuitively, initiated single-crystal investigation, and led the project. K.K. led the synthesis and characterization work, with T.L. and Y.K. Y.S. carried out NMR measurements. J.S. and J.K.P. carried out electrochemical analysis. H.L. and J.Y.P. analysed the electrical conductivity of the carbon product. S.J.C. and T.L. carried out the X-ray crystallography. H.I. investigated the mechanism of carbon formation. R.R. and K.K. wrote the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Ryong Ryoo.

Reviewer Information

Nature thanks P. de Jongh, L. Solovyov and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Extended data

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    This file contains a Supplementary Discussion and Supplementary Figures 1-9.

Crystallographic information files

  1. 1.

    Supplementary Information

    This cif file contains the crystallographic information files.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature18284

Further reading

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.