Tuning clathrate hydrates for hydrogen storage

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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.

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

Author information

Author notes

    • Yu-Taek Seo

    Present address: Conversion Process Research Center, Korea Institute of Energy Research, PO Box 103, Jang-dong, Yuseong-gu, Daejeon 305-343, Republic of Korea


  1. Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea

    • Huen Lee
    • , Jong-won Lee
    • , Do Youn Kim
    •  & Jeasung Park
  2. Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, Ontario, Canada K1A 0R6

    • Yu-Taek Seo
    • , Huang Zeng
    • , Igor L. Moudrakovski
    • , Christopher I. Ratcliffe
    •  & John A. Ripmeester


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Competing interests

The authors declare that they have no competing financial interests.

Corresponding authors

Correspondence to Huen Lee or John A. Ripmeester.

Supplementary information

Word documents

  1. 1.

    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.

  2. 2.

    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.

  3. 3.

    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.


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