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Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

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Abstract

Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition1,2, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage3,4,5,6,7,8,9. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface10,11,12,13,14,15,16,17 and also amongst themselves within individual pores18,19,20,21,22 have been extensively studied, adsorbate–adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate–adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption–desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

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Figure 1: Three adsorbate-interaction regimes in mesoporous MOFs.
Figure 2: Structure of the IRMOF-74 series in three and two dimensions.
Figure 3: Mapping of argon distribution in IRMOF-74-V-hex.
Figure 4: Extra adsorption domains and argon adsorbate superlattice in IRMOF-74-V-hex.

Change history

  • 25 November 2015

    Minor updates were made to the Acknowledgements.

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Acknowledgements

The authors acknowledge K. Ito, K. Sasaki, M. Kuribayashi and N. Muroyama (Rigaku America and Japan) and K. Nakai (Japan Bel) for technical support; N. Fujita and T. Nishimatsu (Tohoku University, Japan), H. Furukawa and Y. Zhang (University of California at Berkeley, USA) for their input; and A. Sawada (Kyoto University, Japan) for advice in designing the gas cell. Financial support was provided by WCU/BK21+ (to H.S.C., K.M., J.K.K., O.M.Y. and O.T.); HIMC of Global Frontier Project (2013M3A6B1078884) funded by the Ministry of Science, ICT and Future Planning and Korea Center for Artificial Photosynthesis (to J.K.K.); Berzelii Centre EXSELENT on Porous Materials (to O.T.); and BASF (Ludwigshafen, Germany) (to O.M.Y.). H.D. and Z.D. were supported by the 1000 Talent Plan of China, National Natural Science Foundation of China (21471118) and National Key Basic Research Program of China (2014CB239203). A.V.N. acknowledges support from the NSF ERC ‘Structured Organic Particulate Systems’.

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Authors and Affiliations

Authors

Contributions

O.T., K.M. and J.K.K. designed and set up the experimental system. O.T. and O.M.Y. designed and led the project. H.S.C., K.M. and H.D. performed the SAXS experiments. H.D., Z.D. and M.C. prepared samples. A.V.N. contributed discussion of the gas adsorption–desorption process. H.D., H.S.C., J.K.K., O.M.Y. and O.T. prepared the first version of the manuscript and all authors contributed to the final version.

Corresponding authors

Correspondence to Omar M. Yaghi or Osamu Terasaki.

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The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 The five stages of gas adsorption in IRMOF-74s.

The five different adsorption stages are indicated in red at the top of the figure and their boundaries demarcated throughout all panels by grey dashed lines. a, The measured Ar adsorption by IRMOF-74-V-hex is shown; it can be compared against relevant SAXS profile features of IRMOF-74, measured as a function of Ar pressure, that are shown in the other panels. b, The appearance and disappearance of the broad peak indicates the formation of extra adsorption domains over pores (aggregation, red) and the even distribution of adsorbates (homogenization, blue). c, Intensity of 1 superlattice reflection, appearing as stage 3 turns to stage 4 (organization, green) and disappearing at the end of stage 4 (homogenization, blue). d, Change in the unit-cell parameter a of IRMOF-74. e, Change in the line-profile width of IRMOF-74.

Supplementary information

Supplementary Information

This file contains detailed instrumental set-up and results of in-situ SAXS measurements of the Ar, CO2 and N2 adsorption in IRMOF-74-III, -IV, -V, -V-hex and VII, Supplementary Figures 1-57 and Supplementary Tables 1-25. (PDF 8782 kb)

Collective behavior of adsorbate exemplified by Ar distribution along the isotherm in IRMOF-74-V-hex

This video shows systematic change of electron density map of Ar in IRMOF-74-V-hex during adsorption-desorption process. (MP4 6998 kb)

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Sung Cho, H., Deng, H., Miyasaka, K. et al. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks. Nature 527, 503–507 (2015). https://doi.org/10.1038/nature15734

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