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Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal–organic framework

Abstract

Metal–organic frameworks (MOFs)—microporous materials constructed by bridging metal centres with organic ligands—show promise for applications in hydrogen storage, which is a key challenge in the development of the ‘hydrogen economy’. Their adsorption capacities, however, have remained insufficient for practical applications, and thus strategies to enhance hydrogen–MOF interactions are required. Here we describe an anionic MOF material built from In(iii) centres and tetracarboxylic acid ligands (H4L) in which kinetic trapping behaviour—where hydrogen is adsorbed at high pressures but not released immediately on lowering the pressure—is modulated by guest cations. With piperazinium dications in its pores, the framework exhibits hysteretic hydrogen adsorption. On exchange of these dications with lithium cations, no hysteresis is seen, but instead there is an enhanced adsorption capacity coupled to an increase in the isosteric heat of adsorption. This is rationalized by the different locations of the cations within the pores, determined with precision by X-ray crystallography.

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Figure 1: Views of single crystal X-ray structures of triporous units of 1-ppz-solv and 1-Li-solv, and in situ infrared spectra of 1-Li-solv.
Figure 2: Views of framework structures of 1-ppz-solv and 1-Li-solv.
Figure 3: Gas adsorption isotherms of 1-ppz and 1-Li.
Figure 4: H2 adsorption kinetic profiles and Arrhenius plots for H2 uptake in 1-ppz.

References

  1. Schlapbach, L. & Züttel, A. Hydrogen-storage materials for mobile applications. Nature 414, 353–358 (2001).

    Article  CAS  Google Scholar 

  2. Rosi, N. L. et al. Hydrogen storage in microporous metal–organic frameworks. Science 300, 1127–1130 (2003).

    Article  CAS  Google Scholar 

  3. Lin, X., Jia, J., Hubberstey, P., Schröder, M. & Champness, N. R. Hydrogen storage in metal–organic frameworks. CrystEngComm. 9, 438–448 (2007).

    Article  CAS  Google Scholar 

  4. Férey, G. et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 309, 2040–2042 (2005); correction 310, 1119 (2005).

    Article  Google Scholar 

  5. Bhatia, S. K. & Myers, A. L. Optimum conditions for adsorptive storage. Langmuir 22, 1688–1700 (2006).

    Article  CAS  Google Scholar 

  6. Chun, H., Dybtsev, D. N., Kim, H. & Kim, K. Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: Implications for hydrogen storage in porous materials. Chem. Eur. J. 11, 3521–3529 (2005).

    Article  CAS  Google Scholar 

  7. Luo, J. et al. Hydrogen adsorption in a highly stable porous rare-earth metal–organic framework: sorption properties and neutron diffraction studies. J. Am. Chem. Soc. 130, 9626–9297 (2008).

    Article  CAS  Google Scholar 

  8. Lin, X. et al. High H2 adsorption by coordination-framework materials. Angew. Chem. Int. Ed. 45, 7358–7364 (2006).

    Article  CAS  Google Scholar 

  9. Dincă, M. et al. Observation of Cu2+-H2 interactions in a fully desolvated sodalite-type metal–organic framework. Angew. Chem. Int. Ed. 46, 1419–1422 (2007).

    Article  Google Scholar 

  10. Lin, X. et al. High capacity hydrogen adsorption in Cu(ii) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites. J. Am. Chem. Soc. 131, 2159–2171 (2009).

    Article  CAS  Google Scholar 

  11. Zhao, X. et al. Hysteretic adsorption and desorption of hydrogen by nanoporous metal–organic frameworks. Science 306, 1012–1015 (2004).

    Article  CAS  Google Scholar 

  12. Choi, H. J., Dincă, M. & Long, J. R. Broadly hysteretic H2 adsorption in the microporous metal–organic framework Co(1, 4-benzenedipyrazolate). J. Am. Chem. Soc. 130, 7848–7850 (2008).

    Article  CAS  Google Scholar 

  13. Férey, G. et al. Hydrogen adsorption in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+), MIL-53. Chem. Commun. 2976–2977 (2003).

  14. Yang, C., Wang, X. & Omary, M. A. Fluorous metal–organic frameworks for high-density gas adsorption. J. Am. Chem. Soc., 129, 15454–15455 (2007).

    Article  CAS  Google Scholar 

  15. Mulfort, K. L. & Hupp, J. T. Chemical reduction of metal–organic framework materials as a method to enhance gas uptake and binding. J. Am. Chem. Soc. 129, 9604–9605 (2007).

    Article  CAS  Google Scholar 

  16. Mulfort, K. L. & Hupp, J. T. Alkali metal cation effects on hydrogen uptake and binding in metal–organic frameworks. Inorg. Chem. 47, 7936–7938 (2008).

    Article  CAS  Google Scholar 

  17. Blomqvist, A., Araújo, C. M., Srepusharawoot, P. & Ahuja, R. Li-decorated metal–organic framework 5: a route to achieving a suitable hydrogen storage medium. Proc. Natl Acad. Sci. USA 104, 20173–20176 (2007).

    Article  CAS  Google Scholar 

  18. Han, S. S. & Goddard, W. A. Lithium-doped metal–organic frameworks for reversible H2 storage at ambient temperature. J. Am. Chem. Soc. 129, 8422–8423 (2007).

    Article  CAS  Google Scholar 

  19. Han, S. S. & Goddard, W. A. High H2 storage of hexagonal metal–organic frameworks from first-principles-based grand canonical Monte carlo simulations. J. Phys Chem. C. 112, 13431–13436 (2008).

    Article  CAS  Google Scholar 

  20. Klontzas, E., Mavrandonakis, A., Tylianakis, E. & Froudakis, G. E. Improving hydrogen storage capacity of MOF by functionalization of the organic linker with lithium atoms. Nano Lett. 8, 1572–1576 (2008).

    Article  Google Scholar 

  21. Mavrandonakis, A., Tylianakis, E., Stubos, A. K. & Froudakis, G. E. Why Li doping in MOFs enhances H2 storage capacity? a multi-scale theoretical study. J. Phys. Chem. C. 112, 7290–7294 (2008).

    Article  CAS  Google Scholar 

  22. Dalach, P., Frost, H., Snurr, R. Q. & Ellis, D. E. Enhanced hydrogen uptake and the electronic structure of lithium-doped metal–organic frameworks. J. Phys. Chem. C. 112, 9278–9284 (2008).

    Article  CAS  Google Scholar 

  23. Cao, D., Lan, J., Wang, W. & Smit, B. Lithium-doped 3D covalent organic frameworks: high-capacity hydrogen storage materials. Angew. Chem. Int. Ed. 48, 4730–4733 (2009).

    Article  CAS  Google Scholar 

  24. Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 36, 7–13 (2003).

    Article  CAS  Google Scholar 

  25. Yang, T., Yang, S., Liao, F. & Lin, J. Two isotypic diphosphates LiM2H3(P2O7)2 (M = Ni, Co) containing ferromagnetic zigzag MO6 chains. J. Solid State Chem. 181, 1347–1353 (2006).

    Article  Google Scholar 

  26. Fuentes-Cabrera, M., Nicholson, D. M. & Sumpter, B. G. Electronic structure and properties of isoreticular metal–organic frameworks: the case of M-IRMOF1 (M = Zn, Cd, Be, Mg, and Ca). J. Chem. Phys. 123, 124713–124718 (2005).

    Article  Google Scholar 

  27. Düren, T., Millange, F., Férey, G., Walton K. S. & Snurr R. Q. Calculating geometric surface areas as a characterization tool for metal–organic frameworks. J. Phys. Chem. C. 111, 15350–15356 (2007).

    Article  Google Scholar 

  28. Rappé, A. K., Casewit, C. J., Colwell, K. S., Goddard, W. A. & Skid, W. M. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc. 114, 10024–10035 (1992).

    Article  Google Scholar 

  29. Hirschfelder, J. O., Curtiss, C. F. & Bird, R. B. Molecular Theory of Gases and Liquids 2nd edn (Wiley, 1964).

    Google Scholar 

  30. Fletcher, A. J., Cussen, E. J., Bradshaw, D., Rosseinsky, M. J. & Thomas, K. M. Adsorption of gases and vapors on nanoporous Ni2(4,4′-Bipyridine)3(NO3)4 metal–organic framework materials templated with methanol and ethanol: structural effects in adsorption kinetics. J. Am. Chem. Soc. 126, 9750–9759 (2004).

    Article  CAS  Google Scholar 

  31. Chen, B. et al. Surface interactions and quantum kinetic molecular sieving for H2 and D2 adsorption on a mixed metal–organic framework material. J. Am. Chem. Soc. 130, 6411–6423 (2008).

    Article  CAS  Google Scholar 

  32. Jhi, S. H. A theoretical study of nanoporous organic molecules for hydrogen storage. Microporous Mesoporous Mater. 89, 138–142 (2006).

    Article  CAS  Google Scholar 

  33. Anil Kumar, A. V., Jobic, H. & Bhatia, S. K. Quantum effect induced kinetic molecular sieving of hydrogen and deuterium in microporous materials. Adsorption 13, 501–508 (2007).

    Article  CAS  Google Scholar 

  34. CRC Handbook of Chemistry and Physics 74th edn (CRC, 1993).

  35. Yang, S. et al. Enhancement of H2 adsorption in Li+-exchanged coordination framework materials. Chem. Commun. 6108–6110 (2008).

  36. Hafizovic, J. et al. The inconsistency in adsorption properties and powder XRD data of MOF-5 is rationalized by framework interpenetration and the presence of organic and inorganic species in the nanocavities. J. Am. Chem. Soc. 129, 3612–3620 (2007).

    Article  CAS  Google Scholar 

  37. Cole, J. H. et al. Thermodynamics of high temperature adsorption of some permanent gases by porous carbons. J. Chem. Soc. Faraday Trans. 70, 2154–2169 (1974).

    Article  CAS  Google Scholar 

  38. Nouar, F, Eckert, J., Eubank, J. F., Forster, P. & Eddaoudi, M. Zeolite-like metal–organic frameworks (ZMOFs) as hydrogen storage platform: lithium and magnesium ion-exchange and H2-(rho-ZMOF) interaction studies. J. Am. Chem. Soc. 131, 2864–2870 (2009).

    Article  CAS  Google Scholar 

  39. Himsl, D., Wallacher, D. & Hartmann, M. Improving the hydrogen-adsorption properties of a hydroxy-modified MIL-53(Al) structural analogue by lithium doping. Angew. Chem. Int. Ed. 48, 4639–4642 (2009).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank the EPSRC and the University of Nottingham for support and funding, and the EPSRC-funded National Crystallography Services at the University of Southampton for data collection. We thank J. Burley for PXRD data collection, T. Liu for the help on ICPMAS measurements, and T. Price for infrared spectra. We also thank T. Düren for the assistance and advice on simulation of BET surface areas. M.S. acknowledges receipt of a Royal Society Wolfson Merit Award and an ERC Advanced Grant, and S.Y. thanks Shell-EPSRC for a DHPA scholarship.

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Authors and Affiliations

Authors

Contributions

S.Y. carried out syntheses, characterization, measurements and analysis of adsorption isotherms. X.L. and G.S.W. performed IR measurements and analysis of adsorption results. A.J.B. performed X-ray structural data analysis. P.H., N.R.C. and M.S. were responsible for overall design, direction and supervision of project. All authors co-wrote the paper.

Corresponding authors

Correspondence to Neil R. Champness or Martin Schröder.

Supplementary information

Supplementary information

Supplementary information (PDF 1662 kb)

Supplementary information

Crystallographic information for framework containing piperazinium ions (called 1-ppz-solv) (CIF 18 kb)

Supplementary information

Crystallographic information for framework containing lithium ions (called 1-Li-solv) (CIF 19 kb)

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Yang, S., Lin, X., Blake, A. et al. Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal–organic framework. Nature Chem 1, 487–493 (2009). https://doi.org/10.1038/nchem.333

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