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Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework

Nature Chemistry volume 7, pages 121–129 (2015)Cite this article

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Abstract

Supramolecular interactions are fundamental to host–guest binding in many chemical and biological processes. Direct visualization of such supramolecular interactions within host–guest systems is extremely challenging, but crucial to understanding their function. We report a comprehensive study that combines neutron scattering, synchrotron X-ray and neutron diffraction, and computational modelling to define the detailed binding at a molecular level of acetylene, ethylene and ethane within the porous host NOTT-300. This study reveals simultaneous and cooperative hydrogen-bonding, π···π stacking interactions and intermolecular dipole interactions in the binding of acetylene and ethylene to give up to 12 individual weak supramolecular interactions aligned within the host to form an optimal geometry for the selective binding of hydrocarbons. We also report the cooperative binding of a mixture of acetylene and ethylene within the porous host, together with the corresponding breakthrough experiments and analysis of adsorption isotherms of gas mixtures.

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Figure 1: Hydrocarbon adsorption isotherms and selectivity data for NOTT-300, quasi-elastic neutron scattering (QENS) spectra and variation of thermodynamic parameters for hydrocarbon adsorption in NOTT-300.
Figure 4: INS spectra for bare NOTT-300 and NOTT-300 loaded with a C2H2/C2H4 hydrocarbon mixture and views of the adsorption isotherms of the C2H2/C2H4 mixture and the corresponding experimental breakthrough plot.
Figure 3: Views of the structural models for the adsorption of C2H2, C2H4 and C2H6 in NOTT-300.
Figure 2: INS spectra for NOTT-300 as a function of hydrocarbon loadings.
Figure 5: Views of the calculated structural models for NOTT-300 loaded with a C2H2/C2H4 mixture (NOTT-300·2.4C2H2·0.8C2H4).

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Acknowledgements

S.Y. acknowledges receipt of a Nottingham Research Fellowship and a Leverhulme Trust Early Career Research Fellowship, and M.S. the receipt of a European Research Council Advanced Grant and an Engineering and Physical Sciences Research Council Programme Grant. We are especially grateful to STFC and the ISIS Neutron Facility for access to Beamlines TOSCA, WISH, IRIS and the SCARF supercomputer resources, and to Diamond Light Source for access to Beamline I11. We thank C. Goodway and M. Kibble of the user support group at ISIS and J. Potter at Diamond for the technical help with the beamlines. We also thank J. Ke for helpful discussions on the implementation of IAST. This research used resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC05-00OR22725.

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Authors and Affiliations

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

    Sihai Yang, Ruth Newby & Martin Schröder

  2. The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    Anibal J. Ramirez-Cuesta

  3. ISIS Neutron Facility, STFC Rutherford Appleton Laboratory, Chilton, OX11 0QX, Oxfordshire, UK

    Victoria Garcia-Sakai, Pascal Manuel & Samantha K. Callear

  4. Neutron Data Analysis and Visualization Division (NDAV), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    Stuart I. Campbell

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

    Chiu C. Tang

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  1. Sihai Yang
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Contributions

S.Y. and R.N. carried out syntheses, characterization of MOF samples, measurements and analysis of adsorption isotherms. S.Y., S.K.C. and C.C.T. collected and analysed the synchrotron X-ray powder diffraction data. S.Y., A.J.R-C., R.N., V.G-S., P.M., S.K.C. and S.I.C. carried out the collection, analysis, refinement and DFT modelling of neutron-scattering data. S.Y. and M.S. provided the overall direction and supervision of the project and prepared the manuscript.

Corresponding authors

Correspondence to Sihai Yang or Martin Schröder.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 17989 kb)

Supplementary information

Crystallographic data for compound NOTT-300·4C2H2. (CIF 1 kb)

Supplementary information

Crystallographic data for compound NOTT-300·2.5C2H4. (CIF 2 kb)

Supplementary information

Crystallographic data for compound NOTT-300·2.7C2D2. (CIF 2 kb)

Supplementary information

Crystallographic data for compound NOTT-300·1.8C2D4. (CIF 2 kb)

Supplementary information

Crystallographic data for compound NOTT-300·1.3C2D6. (CIF 2 kb)

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Yang, S., Ramirez-Cuesta, A., Newby, R. et al. Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework. Nature Chem 7, 121–129 (2015). https://doi.org/10.1038/nchem.2114

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