Skip to main content

Thank you for visiting 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.

Tuning clathrate hydrates for hydrogen storage


The storage of large quantities of hydrogen at safe pressures1 is a key factor in establishing a hydrogen-based economy. Previous strategies—where hydrogen has been bound chemically2, adsorbed in materials with permanent void space3 or stored in hybrid materials that combine these elements3—have problems arising from either technical considerations or materials cost2,3,4,5. A recently reported6,7,8 clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures ( 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material9, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

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

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Raman spectra of the THF + H2 double hydrates.
Figure 2: Magic angle spinning 1H NMR spectra of the THF + H2 double hydrates formed at 120 bar and 270 K as a function of concentration of THF.
Figure 3: H2 gas content as a function of THF concentration, and a schematic diagram of H2 distribution in the cages of THF + H2 hydrate.
Figure 4: Formation/release kinetics of the H2 + THF double hydrate in the pores of silica beads.


  1. Berry, G. D. & Aceves, S. M. Onboard storage alternatives for hydrogen vehicles. Energy Fuels 12, 49–55 (1998)

    Article  CAS  Google Scholar 

  2. Schlapbach, L. & Zuttel, A. Hydrogen-storage materials for mobile applications. Nature 414, 353–358 (2001)

    Article  ADS  CAS  Google Scholar 

  3. Weitkamp, J., Fritz, M. & Ernst, S. Zeolites as media for hydrogen storage. Int. J. Hydrogen Energy 20, 967–970 (1995)

    Article  CAS  Google Scholar 

  4. Schimmel, H. G. et al. Hydrogen adsorption in carbon nanostructures: Comparison of nanotubes, fibers, and coals. Chem. Eur. J. 9, 4764–4770 (2003)

    Article  CAS  Google Scholar 

  5. Rosi, N. L. et al. Hydrogen storage in microporous metal-organic frameworks. Science 300, 1127–1129 (2003)

    Article  ADS  CAS  Google Scholar 

  6. Mao, W. L. et al. Hydrogen clusters in clathrate hydrate. Science 297, 2247–2249 (2002)

    Article  ADS  CAS  Google Scholar 

  7. Patchkovskii, S. & Tse, J. S. Thermodynamic stability of hydrogen clathrates. Proc. Natl Acad. Sci. USA 100, 14645–14650 (2003)

    Article  ADS  CAS  Google Scholar 

  8. Mao, W. L. & Mao, H. Hydrogen storage in molecular compounds. Proc. Natl Acad. Sci. USA 101, 708–710 (2004)

    Article  ADS  CAS  Google Scholar 

  9. Florusse, L. J. et al. Stable low-pressure hydrogen clusters stored in a binary clathrate hydrate. Science 306, 469–471 (2004)

    Article  ADS  CAS  Google Scholar 

  10. Jeffrey, G. A. in Comprehensive Supramolecular Chemistry Vol. 6 (eds MacNicol, D. D, Toda, F. & Bishop, R.) 757–788 (Pergamon, Oxford, 1996)

    Google Scholar 

  11. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds 4th edn (Wiley, New York, 1986)

    Google Scholar 

  12. Nakahara, J. et al. C. C. Raman spectra of natural clathrates in deep ice cores. Phil. Mag. B 3, 421–430 (1988)

    Article  ADS  Google Scholar 

  13. Lokshin, K. A. et al. Structure and dynamics of hydrogen molecules in the novel clathrate hydrate by high pressure neutron diffraction. Phys. Rev. Lett. 93, 125503 (2004)

    Article  ADS  Google Scholar 

Download references


This work was supported by the Korea Research Foundation and the Brain Korea 21 Project.

Author information

Authors and Affiliations


Corresponding authors

Correspondence to Huen Lee or John A. Ripmeester.

Ethics declarations

Competing interests

The authors declare that they have no competing financial interests.

Supplementary information

Supplementary Methods

Describes the additional information on the experimental methods of XRD and Raman spectroscopy to obtain the structural information and identify the molecular behaviour of H2 in hydrate cages. (DOC 28 kb)

Supplementary Figures S1-S3

Contains three Supplementary Figures. Figure S1 shows the powder XRD pattern for the double hydrate. Supplementary Figure S2 shows the phase behaviour of the double hydrate for 5.56 mol% THF concentration. As it can be seen in Supplementary Figure S3, the effect of the extinction coefficient in this study can be treated as a constant value regardless of THF concentrations. (DOC 122 kb)

Supplementary Table S1

This table shows the powder XRD patterns of THF + H2 double hydrate. Indexed results show that the formed structure of THF + H2 double hydrate is sII hydrate. (DOC 33 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Lee, H., Lee, Jw., Kim, D. et al. Tuning clathrate hydrates for hydrogen storage. Nature 434, 743–746 (2005).

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI:

This article is cited by


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.


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