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Selectivity and direct visualization of carbon dioxide and sulfur dioxide in a decorated porous host

Nature Chemistry volume 4, pages 887–894 (2012)Cite this article

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Abstract

Understanding the mechanism by which porous solids trap harmful gases such as CO2 and SO2 is essential for the design of new materials for their selective removal. Materials functionalized with amine groups dominate this field, largely because of their potential to form carbamates through H2N(δ−)···C(δ+)O2 interactions, thereby trapping CO2 covalently. However, the use of these materials is energy-intensive, with significant environmental impact. Here, we report a non-amine-containing porous solid (NOTT-300) in which hydroxyl groups within pores bind CO2 and SO2 selectively. In situ powder X-ray diffraction and inelastic neutron scattering studies, combined with modelling, reveal that hydroxyl groups bind CO2 and SO2 through the formation of O=C(S)=O(δ−)···H(δ+)–O hydrogen bonds, which are reinforced by weak supramolecular interactions with C–H atoms on the aromatic rings of the framework. This offers the potential for the application of new ‘easy-on/easy-off’ capture systems for CO2 and SO2 that carry fewer economic and environmental penalties.

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Figure 1: Comparison of gas-binding interactions in amine-functionalized materials and in hydroxyl-functionalized NOTT-300.
Figure 2: Structure of NOTT-300-solvate.
Figure 3: Gas sorption isotherms and variation of thermodynamic parameters Qst and ΔS as a function of CO2 uptake in NOTT-300.
Figure 4: In situ INS and simulated CO2 positions in the pore channel of NOTT-300.
Figure 5: In situ synchrotron X-ray powder diffraction patterns and refined SO2 positions in the pore channel of NOTT-300.
Figure 6: In situ INS and simulated SO2 positions in the pore channel of NOTT-300.

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Acknowledgements

S.Y. acknowledges receipt of a Leverhulme Trust Early Career Research Fellowship, and M.S. the receipt of an ERC Advanced Grant and EPSRC Programme Grant. The authors acknowledge funding from the EPSRC and the University of Nottingham, and are especially grateful to Diamond Light Source and ISIS Neutron Centre for access to Beamlines I11 and TOSCA, respectively. The authors thank the user support group at ISIS (C. Goodway and M. Kibble) for technical help at ISIS beamline TOSCA, M. Fray for help with TEM measurements, and K. Refson for discussions on DFT modelling. J.S. acknowledges support from the Swedish Research Council (VR).

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Authors and Affiliations

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

    Sihai Yang, Daniel P. Anderson, Ruth Newby, Alexander J. Blake & Martin Schröder

  2. College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Junliang Sun

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

    Anibal J. Ramirez-Cuesta, Samantha K. Callear & William I. F. David

  4. Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR, UK

    William I. F. David

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

    Julia E. Parker & Chiu C. Tang

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Contributions

S.Y., D.P.A. and R.N. carried out syntheses of the MOF samples. J.S. and W.I.F.D. contributed to solution and refinement of the structures from PXRD data. S.Y. characterized the MOF samples and carried out measurements and analysis of adsorption isotherms. S.Y., A.J.B., C.C.T. and J.E.P. collected and analysed the synchrotron X-ray powder diffraction data. S.Y., S.K.C. and A.J.R.C. collected and analysed the neutron scattering data and carried out DFT modelling of the neutron scattering data. M.S. and S.Y. were responsible for the overall direction and design of the project and preparation of the manuscript, with contributions from all authors.

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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 5020 kb)

Supplementary information

Fractional coordinates for compound NOTT-300-solvated (CIF 1 kb)

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Fractional coordinates for compound NOTT-300-3.2CO2 (CIF 1 kb)

Supplementary information

Fractional coordinates for compound NOTT-300-4SO2 (CIF 2 kb)

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Yang, S., Sun, J., Ramirez-Cuesta, A. et al. Selectivity and direct visualization of carbon dioxide and sulfur dioxide in a decorated porous host. Nature Chem 4, 887–894 (2012). https://doi.org/10.1038/nchem.1457

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