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Water-filled single-wall carbon nanotubes as molecular nanovalves

Nature Materials volume 6, pages 135–141 (2007)Cite this article

Abstract

It is known that at low temperature, water inside single-wall carbon nanotubes (water–SWNTs) undergoes a structural transition to form tube-like solid structures. The resulting ice NTs are hollow cylinders with diameters comparable to those of typical gas molecules. Hence, the gas-adsorption properties of ice– and water–SWNTs are of interest. Here, we carry out the first systematic investigation into the stability of water–SWNTs in various gas atmospheres below 0.1 MPa by means of electrical resistance, X-ray diffraction, NMR measurements and molecular dynamics calculations. It is found that the resistivity of water–SWNTs exhibits a significant increase in gas atmospheres below a critical temperature Tc, at which a particular type of atmospheric gas molecule enters the SWNTs in an on–off fashion. On the basis of this phenomenon, it is proposed that water–SWNTs can be used to fabricate a new type of molecular nanovalve.

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Figure 1: Schematic illustration of SWNTs, SWNTs with ice NTs and SWNTs with hydrates.
Figure 2: Temperature dependence of resistance.
Figure 3: Temperature (T) dependence of electrical resistance of wet SWNT (sample L) film in various gases.
Figure 4: The XRD patterns of wet SWNTs (sample L), both with and without CH4 at a pressure of 0.1 MPa for several temperatures.
Figure 5: 1H-NMR spectra of CH4 in the dry and wet SWNTs (sample L).
Figure 6: Temperature dependence of the 1H NMR intensity (multiplied by temperature) in the D2O-exposed SWNTs (sample L) in CH4 at a pressure of 0.1 MPa.
Figure 7: Filling–ejecting phenomena for CH4 and Ne.
Figure 8: Valve function of water–SWNTs.

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Acknowledgements

This work was supported in part by a Grant-in-Aid for Scientific Research by the Ministry of Education, Culture, Sports, Science and Technology of Japan.

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Authors and Affiliations

  1. Department of Physics, Faculty of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo, 192-0397, Japan

    Yutaka Maniwa, Kazuyuki Matsuda, Haruka Kyakuno, Syunsuke Ogasawara, Toshihide Hibi & Hiroaki Kadowaki

  2. CREST, Japan Science and Technology Corporation (JST), 4-1-8 Honcho, Kawaguchi, 322-0012, Japan

    Yutaka Maniwa

  3. Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo, 192-0397, Japan

    Shinzo Suzuki & Yohji Achiba

  4. Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Central 4, Higashi 1-1-1, Tsukuba, Ibaraki, 305-8562, Japan

    Hiromichi Kataura

Authors
  1. Yutaka Maniwa
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  2. Kazuyuki Matsuda
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Contributions

The main contribution of each author to the present work was as follows. K.M. contributed to the NMR and resisitivity measurements, S.O. to the resisitivity and XRD measurements, H. Kyakuno to MD calculations, T.H. to the NMR measurements, H. Kadowaki to the data analysis, S.S. and Y.A. to the sample preparation, H. Kataura to the high-purity sample preparation and characterization and Y.M. to the project planning and data analysis.

Corresponding author

Correspondence to Yutaka Maniwa.

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Supplementary information

Supplementary Information

Supplementary information I, II and II; figures S1, S2, S3, S4 and S5 (PDF 1032 kb)

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Maniwa, Y., Matsuda, K., Kyakuno, H. et al. Water-filled single-wall carbon nanotubes as molecular nanovalves. Nature Mater 6, 135–141 (2007). https://doi.org/10.1038/nmat1823

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