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.

  • Article
  • Published:

Advanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugation

Abstract

Existing methods for growing single-walled carbon nanotubes produce samples with a range of structures and electronic properties, but many potential applications require pure nanotube samples. Density-gradient ultracentrifugation has recently emerged as a technique for sorting as-grown mixtures of single-walled nanotubes into their distinct (n,m) structural forms, but to date this approach has been limited to samples containing only a small number of nanotube structures, and has often required repeated density-gradient ultracentrifugation processing. Here, we report that the use of tailored nonlinear density gradients can significantly improve density-gradient ultracentrifugation separations. We show that highly polydisperse samples of single-walled nanotubes grown by the HiPco method are readily sorted in a single step to give fractions enriched in any of ten different (n,m) species. Furthermore, minor variants of the method allow separation of the mirror-image isomers (enantiomers) of seven (n,m) species. Optimization of this approach was aided by the development of instrumentation that spectroscopically maps nanotube contents inside undisturbed centrifuge tubes.

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

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

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

Figure 1: Sorting of HiPco SWNTs by (n,m) structure using single-step nonlinear DGU.
Figure 2: Optical characterization of sorted SWNT fractions.
Figure 3: In situ vertical spectral mapping of a centrifuge tube after nonlinear DGU.
Figure 4: Nonlinear DGU separation of optically active enantiomers of (6,5).
Figure 5: Nonlinear DGU separation of optically active enantiomers of (8,3) and (8,4).
Figure 6: Nonlinear DGU separation of optically active enantiomers of (6,4) and (7,3).

Similar content being viewed by others

References

  1. Reich, S., Janina, J. & Thomsen, C. Carbon Nanotubes: Basic Concepts and Physical Properties (Wiley, 2004).

    Google Scholar 

  2. Javey, A., Guo, J., Wang, Q., Lundstrom, M. & Dai, H. J. Ballistic carbon nanotube field-effect transistors. Nature 424, 654–657 (2003).

    Article  CAS  Google Scholar 

  3. Barone, P. W., Baik, S., Heller, D. A. & Strano, M. S. Near-infrared optical sensors based on single-walled carbon nanotubes. Nature Mater. 4, 86–92 (2005).

    Article  CAS  Google Scholar 

  4. Wu, Z. C. et al. Transparent, conductive carbon nanotube films. Science 305, 1273–1276 (2004).

    Article  CAS  Google Scholar 

  5. Green, A. A. & Hersam, M. C. Colored semitransparent conductive coatings consisting of monodisperse metallic single-walled carbon nanotubes. Nano Lett. 8, 1417–1422 (2008).

    Article  CAS  Google Scholar 

  6. Weisman, R. B. Fluorimetric characterization of single-walled carbon nanotubes. Anal. Bioanal. Chem. 396, 1015–1023 (2010).

    Article  CAS  Google Scholar 

  7. Krupke, R., Hennrich, F., von Lohneysen, H. & Kappes, M. M. Separation of metallic from semiconducting single-walled carbon nanotubes. Science 301, 344–347 (2003).

    Article  CAS  Google Scholar 

  8. Zheng, M. et al. Structure-based carbon nanotube sorting by sequence-dependent DNA assembly. Science 302, 1545–1548 (2003).

    Article  CAS  Google Scholar 

  9. Zheng, M. & Semke, E. D. Enrichment of single chirality carbon nanotubes. J. Am. Chem. Soc. 129, 6084–6085 (2007).

    Article  CAS  Google Scholar 

  10. Tu, X., Manohar, S., Jagota, A. & Zheng, M. DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes. Nature 460, 250–253 (2009).

    Article  CAS  Google Scholar 

  11. Arnold, M. S., Stupp, S. I. & Hersam, M. C. Enrichment of single-walled carbon nanotubes by diameter in density gradients. Nano Lett. 5, 713–718 (2005).

    Article  CAS  Google Scholar 

  12. Davies, I. & Graham, J. M. The use of self-generated gradients of iodixanol for the purification of macromolecules and macromolecular complexes. FASEB J. 11, A908 (1997).

    Google Scholar 

  13. Graham, J. M. Biological Centrifugation (BIOS Scientific, 2001).

    Google Scholar 

  14. Arnold, M. S., Green, A. A., Hulvat, J. F., Stupp, S. I. & Hersam, M. C. Sorting carbon nanotubes by electronic structure using density differentiation. Nature Nanotech. 1, 60–65 (2006).

    Article  CAS  Google Scholar 

  15. Kitiyanan, B., Alvarez, W. E., Harwell, J. H. & Resasco, D. E. Controlled production of single-wall carbon nanotubes by catalytic decomposition of CO on bimetallic CoMo catalysts. Chem. Phys. Lett. 317, 497–503 (2000).

    Article  CAS  Google Scholar 

  16. Ciuparu, D., Chen, Y., Lim, S., Haller, G. L. & Pfefferle, L. D. Uniform-diameter single-walled carbon nanotubes catalytically grown in cobalt-incorporated MCM-41. J. Phys. Chem. B 108, 503–507 (2004).

    Article  CAS  Google Scholar 

  17. Bachilo, S. M. et al. Narrow (n,m)-distribution of single-walled carbon nanotubes grown using a solid supported catalyst. J. Am. Chem. Soc. 125, 11186–11187 (2003).

    Article  CAS  Google Scholar 

  18. Nikolaev, P. et al. Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide. Chem. Phys. Lett. 313, 91–97 (1999).

    Article  CAS  Google Scholar 

  19. Bachilo, S. M. et al. Structure-assigned optical spectra of single-walled carbon nanotubes. Science 298, 2361–2366 (2002).

    Article  CAS  Google Scholar 

  20. Kim, W.-J., Nair, N., Lee, C. Y. & Strano, M. S. Covalent functionalization of single-walled carbon nanotubes alters their densities allowing electronic and other types of separation. J. Phys. Chem. C 112, 7326–7331 (2008).

    Article  CAS  Google Scholar 

  21. Backes, C., Hauke, F., Schmidt, C. D. & Hirsch, A. Fractioning HiPco and CoMoCAT SWCNTs via density gradient ultracentrifugation by the aid of a novel perylene bisimide derivative surfactant. Chem. Commun. 2643–2645 (2009).

  22. Kato, Y., Niidome, Y. & Nakashima, N. Efficient separation of (6,5) single-walled carbon nanotubes using a ‘nanometal sinker’. Angew. Chem. Int. Ed. 48, 5435–5438 (2009).

    Article  CAS  Google Scholar 

  23. Patsch, J. R. et al. Separation of the main lipoprotein density classes from human plasma by rate-zonal ultracentrifugation. J. Lipid Res. 15, 356–366 (1974).

    CAS  Google Scholar 

  24. Green, A. A., Duch, M. C. & Hersam, M. C. Isolation of single-walled carbon nanotube enantiomers by density differentiation. Nano Research 2, 69–77 (2009).

    Article  CAS  Google Scholar 

  25. Nair, N., Kim, W. J., Braatz, R. D. & Strano, M. S. Dynamics of surfactant-suspended single-walled carbon nanotubes in a centrifugal field. Langmuir 24, 1790–1795 (2008).

    Article  CAS  Google Scholar 

  26. Cognet, L. et al. Stepwise quenching of exciton fluorescence in carbon nanotubes by single-molecule reactions. Science 316, 1465–1468 (2007).

    Article  CAS  Google Scholar 

  27. Weisman, R. B. & Bachilo, S. M. Dependence of optical transition energies on structure for single-walled carbon nanotubes in aqueous suspension: an empirical Kataura plot. Nano Lett. 3, 1235–1238 (2003).

    Article  CAS  Google Scholar 

  28. Hebling, C. M. et al. Sodium cholate aggregation and chiral recognition of the probe molecule (R,S)-1,1′-binaphthyl-2,2′-diylhydrogenphosphate (BNDHP) observed by 1H and 31P spectroscopy. Langmuir 24, 13866–13874 (2008).

    Article  CAS  Google Scholar 

  29. Peng, X. et al. Optically active single-walled carbon nanotubes. Nature Nanotech. 2, 361–365 (2007).

    Article  CAS  Google Scholar 

  30. Haroz, E. H., Bachilo, S. M., Weisman, B. & Doorn, S. K. Curvature effects on the E33 and E44 exciton transitions in semiconducting single-walled carbon nanotubes. Phys. Rev. B 77, 125405 (2008).

    Article  Google Scholar 

  31. Samsonidze, G. G. et al. Interband optical transitions in left- and right-handed single-wall carbon nanotubes. Phys. Rev. B 69, 205402 (2004).

    Article  Google Scholar 

  32. Peng, X., Komatsu, N., Kimura, T. & Osuka, A. Improved optical enrichment of SWNTs through extraction with chiral nanotweezers of 2,6-pyridylene-bridged diporphyrins. J. Am. Chem. Soc. 129, 15947–15953 (2007).

    Article  CAS  Google Scholar 

  33. Peng, X., Komatsu, N., Kimura, T. & Osuka, A. Simultaneous enrichments of optical purity and (n,m) abundance of SWNTs through extraction with 3,6-carbazolylene-bridged chiral diporphyrin nanotweezers. ACS Nano 2, 2045–2050 (2008).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to thank W. Rice, R. Simonette and K.M. Beckingham for experimental advice. We are grateful to the National Science Foundation (grant no. CHE-09098097) and the Welch Foundation (grant no. C-0807) for supporting this research.

Author information

Authors and Affiliations

Authors

Contributions

S.G. performed the experiments. S.M.B. and R.B.W. planned the experiments. All authors analysed data and discussed the results. R.B.W. and S.M.B. constructed the vertical mapping spectrofluorometer. S.G. and R.B.W. co-wrote the paper.

Corresponding author

Correspondence to R. Bruce Weisman.

Ethics declarations

Competing interests

R.B.W. has an equity interest in a company that produces one of the instruments used in this study.

Supplementary information

Supplementary information

Supplementary information (PDF 6890 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ghosh, S., Bachilo, S. & Weisman, R. Advanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugation. Nature Nanotech 5, 443–450 (2010). https://doi.org/10.1038/nnano.2010.68

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2010.68

This article is cited by

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