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A partially interpenetrated metal–organic framework for selective hysteretic sorption of carbon dioxide

Nature Materials volume 11, pages 710–716 (2012)Cite this article

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Abstract

The selective capture of carbon dioxide in porous materials has potential for the storage and purification of fuel and flue gases. However, adsorption capacities under dynamic conditions are often insufficient for practical applications, and strategies to enhance CO2–host selectivity are required. The unique partially interpenetrated metal–organic framework NOTT-202 represents a new class of dynamic material that undergoes pronounced framework phase transition on desolvation. We report temperature-dependent adsorption/desorption hysteresis in desolvated NOTT-202a that responds selectively to CO2. The CO2 isotherm shows three steps in the adsorption profile at 195 K, and stepwise filling of pores generated within the observed partially interpenetrated structure has been modelled by grand canonical Monte Carlo simulations. Adsorption of N2, CH4, O2, Ar and H2 exhibits reversible isotherms without hysteresis under the same conditions, and this allows capture of gases at high pressure, but selectively leaves CO2 trapped in the nanopores at low pressure.

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Figure 1: Chemical structure of H4L.
Figure 2: X-ray crystal structures of NOTT-202 and NOTT-202a.
Figure 3: Representation of self-assembly and interpenetration in three-dimensional MOF materials.
Figure 4: CO2 sorption isotherms and variation of thermodynamic parameters Qst and ΔS as a function of CO2 uptake in NOTT-202a.
Figure 5: In situ synchrotron X-ray powder diffraction patterns and Le Bail refinement results for NOTT-202a.
Figure 6: Comparisons of low-pressure CO2, CH4, N2, Ar, O2 and H2 sorption isotherms at 195 K.

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Acknowledgements

S.Y. thanks EPSRC for a PhD Plus Fellowship and the Leverhulme Trust for an Early Career Fellowship. We thank EPSRC (UKSHEC) and the University of Nottingham for support and financial support of X-ray equipment, STFC for awarding access to Station 9.8 of the Daresbury Synchrotron Radiation Source, Diamond Light Source for beam time on Beamlines I11 and I19, and J. Potter for technical help at Diamond Beamline I11. We thank J. Sun (University of Stockholm) for helpful discussions on powder diffraction and A. Linden (University of Zürich) for discussions on the structural analysis of NOTT-202. N.R.C. gratefully acknowledges receipt of a Royal Society Leverhulme Trust Senior Research Fellowship. E.B. gratefully acknowledges financial support from an EPSRC Career Acceleration Fellowship (EP/G005060). M. Schröder gratefully acknowledges receipt of a Royal Society Wolfson Merit Award and an ERC Advanced Grant.

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Authors and Affiliations

  1. School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK

    Sihai Yang, Xiang Lin, William Lewis, Mikhail Suyetin, Elena Bichoutskaia, Peter Hubberstey, Neil R. Champness, Alexander J. Blake & Martin Schröder

  2. Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, UK

    Julia E. Parker, Chiu C. Tang & David R. Allan

  3. STFC Daresbury Laboratory, Warrington WA4 4AD, UK

    Pierre J. Rizkallah

  4. Northern Carbon Research Laboratories, Sir Joseph Swan Institute for Energy Research and School of Chemical Engineering and Advanced Materials, University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, UK

    K. Mark Thomas

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Contributions

S.Y., X.L., K.M.T., M. Schröder: syntheses, characterization, measurements and analysis of adsorption isotherms. E.B. and M. Suyetin: grand canonical Monte Carlo modelling. S.Y., A.J.B., C.C.T. and J.E.P.: synchrotron X-ray powder data analysis. S.Y., A.J.B., W.L., D.R.A. and P.J.R.: single-crystal X-ray structural data analyses. S.Y., A.J.B., P.H., N.R.C., K.M.T. and M. Schröder: overall design, direction and supervision of project. All authors contributed to the writing of the paper.

Corresponding authors

Correspondence to Sihai Yang or Martin Schröder.

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Supplementary information

Supplementary Information

Supplementary Information (PDF 4358 kb)

Supplementary information

Crystallographic information for NOTT-202 at 120K (CIF 17 kb)

Supplementary information

Crystallographic information for NOTT-202a at 120K (CIF 24 kb)

Supplementary information

Crystallographic information for NOTT-202a at 150K (CIF 24 kb)

Supplementary information

Crystallographic information for NOTT-202a at 180K (CIF 23 kb)

Supplementary information

Crystallographic information for NOTT-202a at 200K (CIF 24 kb)

Supplementary information

Crystallographic information for NOTT-202a at 220K (CIF 23 kb)

Supplementary information

Crystallographic information for NOTT-202a at 260K (CIF 24 kb)

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Yang, S., Lin, X., Lewis, W. et al. A partially interpenetrated metal–organic framework for selective hysteretic sorption of carbon dioxide. Nature Mater 11, 710–716 (2012). https://doi.org/10.1038/nmat3343

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