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High-rate nanofluidic energy absorption in porous zeolitic frameworks

Abstract

Optimal mechanical impact absorbers are reusable and exhibit high specific energy absorption. The forced intrusion of liquid water in hydrophobic nanoporous materials, such as zeolitic imidazolate frameworks (ZIFs), presents an attractive pathway to engineer such systems. However, to harness their full potential, it is crucial to understand the underlying water intrusion and extrusion mechanisms under realistic, high-rate deformation conditions. Here, we report a critical increase of the energy absorption capacity of confined water-ZIF systems at elevated strain rates. Starting from ZIF-8 as proof-of-concept, we demonstrate that this attractive rate dependence is generally applicable to cage-type ZIFs but disappears for channel-containing zeolites. Molecular simulations reveal that this phenomenon originates from the intrinsic nanosecond timescale needed for critical-sized water clusters to nucleate inside the nanocages, expediting water transport through the framework. Harnessing this fundamental understanding, design rules are formulated to construct effective, tailorable and reusable impact energy absorbers for challenging new applications.

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Fig. 1: Experimental setup.
Fig. 2: Water intrusion and extrusion of ZIF-8 at low-rate, medium-rate and high-rate loading conditions.
Fig. 3: Simulated water distribution in ZIF-8 and its effect on gate opening.
Fig. 4: Determining the intrinsic timescale for water mobility in the ZIF-8 nanocages by non-equilibrium MD simulations.
Fig. 5: Generalization of the design rules.
Fig. 6: Water intrusion and extrusion of channel-containing zeolites at different conditions.

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Data availability

Source data for the main paper figures are provided with this paper. Additional experimental data generated during the current study are available from the authors upon request. Relevant configurations for the optimizations and MD simulations are available through Zenodo77. Additional computational data supporting the results of this work are available from the online GitHub repository at https://github.com/SvenRogge/supporting-info or upon request from the authors.

Code availability

The Yaff software used to perform the MD simulations in this paper is freely accessible via https://molmod.ugent.be/software/yaff. Representative input and processing scripts are available at https://github.com/SvenRogge/supporting-info.

References

  1. Lu, G. & Yu, T. Energy Absorption of Structures and Materials (Woodhead, 2003). .

  2. Gibson, L. J. & Ashby, M. F. Cellular Solids: Structure and Properties 2nd edn (Cambridge Univ. Press, 1997).

    Book  Google Scholar 

  3. Clough, E. C. et al. Elastomeric microlattice impact attenuators. Matter 1, 1519–1531 (2019).

    Article  Google Scholar 

  4. Fraux, G., Coudert, F. X., Boutin, A. & Fuchs, A. H. Forced intrusion of water and aqueous solutions in microporous materials: from fundamental thermodynamics to energy storage devices. Chem. Soc. Rev. 46, 7421–7437 (2017).

    Article  CAS  Google Scholar 

  5. Eroshenko, V., Regis, R.-C., Soulard, M. & Patarin, J. Energetics: a new field of applications for hydrophobic zeolites. J. Am. Chem. Soc. 123, 8129–8130 (2001).

    Article  CAS  Google Scholar 

  6. Tinti, A., Giacomello, A., Grosu, Y. & Casciola, C. M. Intrusion and extrusion of water in hydrophobic nanopores. Proc. Natl Acad. Sci. USA 114, E10266–E10273 (2017).

    Article  CAS  Google Scholar 

  7. Furukawa, H., Cordova, K. E., O'Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013).

    Article  Google Scholar 

  8. Moghadam, P. Z. et al. Development of a Cambridge Structural Database subset: a collection of metal–organic frameworks for past, present, and future. Chem. Mater. 29, 2618–2625 (2017).

    Article  CAS  Google Scholar 

  9. Ortiz, G., Nouali, H., Marichal, C., Chaplais, G. & Patarin, J. Energetic performances of the metal–organic framework ZIF-8 obtained using high pressure water intrusion–extrusion experiments. Phys. Chem. Chem. Phys. 15, 4888–4891 (2013).

    Article  CAS  Google Scholar 

  10. Grosu, Y. et al. Stability of zeolitic imidazolate frameworks: effect of forced water intrusion and framework flexibility dynamics. RSC Adv. 5, 89498–89502 (2015).

    Article  CAS  Google Scholar 

  11. Ortiz, G., Nouali, H., Marichal, C., Chaplais, G. & Patarin, J. L. Energetic performances of ‘ZIF-71-aqueous solution’ systems: a perfect shock-absorber with water. J. Phys. Chem. C. 118, 21316–21322 (2014).

    Article  CAS  Google Scholar 

  12. Sun, Y., Li, Y. & Tan, J. C. Liquid intrusion into zeolitic imidazolate framework-7 nanocrystals: exposing the roles of phase transition and gate opening to enable energy absorption applications. ACS Appl. Mater. Interfaces 10, 41831–41838 (2018).

    Article  CAS  Google Scholar 

  13. Grosu, Y. et al. A highly stable nonhysteretic {Cu2(tebpz) MOF + water} molecular spring. Chem. Phys. Chem. 17, 3359–3364 (2016).

  14. Park, K. S. et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl Acad. Sci. USA 103, 10186–10191 (2006).

  15. Banerjee, R. et al. High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture. Science 319, 939–943 (2008).

  16. Ortiz, A. U., Freitas, A. P., Boutin, A., Fuchs, A. H. & Coudert, F.-X. What makes zeolitic imidazolate frameworks hydrophobic or hydrophilic? The impact of geometry and functionalization on water adsorption. Phys. Chem. Chem. Phys. 16, 9940–9949 (2014).

    Article  CAS  Google Scholar 

  17. Khay, I. et al. Assessment of the energetic performances of various ZIFs with SOD or RHO topology using high pressure water intrusion-extrusion experiments. Dalton Trans. 45, 4392–4400 (2016).

    Article  CAS  Google Scholar 

  18. Sun, Y., Li, Y. & Tan, J. C. Framework flexibility of ZIF-8 under liquid intrusion: discovering time-dependent mechanical response and structural relaxation. Phys. Chem. Chem. Phys. 20, 10108–10113 (2018).

    Article  CAS  Google Scholar 

  19. Lowe, A. et al. Effect of flexibility and nanotriboelectrification on the dynamic reversibility of water intrusion into nanopores: pressure-transmitting fluid with frequency-dependent dissipation capability. ACS Appl. Mater. Interfaces 11, 40842–40849 (2019).

    Article  CAS  Google Scholar 

  20. Bocquet, L. Nanofluidics coming of age. Nat. Mater. 19, 254–256 (2020).

    Article  CAS  Google Scholar 

  21. Huang, X. C., Lin, Y. Y., Zhang, J. P. & Chen, X. M. Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. Angew. Chem. Int. Ed. 45, 1557–1559 (2006).

    Article  CAS  Google Scholar 

  22. Khay, I., Chaplais, G., Nouali, H., Marichal, C. & Patarin, J. Water intrusion–extrusion experiments in ZIF-8: impacts of the shape and particle size on the energetic performances. RSC Adv. 5, 31514–31518 (2015).

    Article  CAS  Google Scholar 

  23. Fraux, G., Boutin, A., Fuchs, A. H. & Coudert, F.-X. Structure, dynamics, and thermodynamics of intruded electrolytes in ZIF-8. J. Phys. Chem. C. 123, 15589–15598 (2019).

    Article  CAS  Google Scholar 

  24. Sakata, Y. et al. Shape-memory nanopores induced in coordination frameworks by crystal downsizing. Science 339, 193–196 (2013).

    Article  CAS  Google Scholar 

  25. Krause, S. et al. The effect of crystallite size on pressure amplification in switchable porous solids. Nat. Commun. 9, 1573 (2018).

    Article  Google Scholar 

  26. Bennett, T. D. & Cheetham, A. K. Amorphous metal-organic frameworks. Acc. Chem. Res. 47, 1555–1562 (2014).

    Article  CAS  Google Scholar 

  27. Gonzalez, M. A. & Abascal, J. L. A flexible model for water based on TIP4P/2005. J. Chem. Phys. 135, 224516 (2011).

    Article  Google Scholar 

  28. Ghosh, P., Kim, K. C. & Snurr, R. Q. Modeling water and ammonia adsorption in hydrophobic metal-organic frameworks: single components and mixtures. J. Phys. Chem. C. 118, 1102–1110 (2014).

    Article  CAS  Google Scholar 

  29. Zhang, H. & Snurr, R. Q. Computational study of water adsorption in the hydrophobic metal-organic framework ZIF-8: adsorption mechanism and acceleration of the simulations. J. Phys. Chem. C 121, 24000–24010 (2017).

    Article  CAS  Google Scholar 

  30. Hobday, C. L. et al. Understanding the adsorption process in ZIF-8 using high pressure crystallography and computational modelling. Nat. Commun. 9, 1429 (2018).

    Article  Google Scholar 

  31. Durholt, J. P., Fraux, G., Coudert, F. X. & Schmid, R. Ab initio derived force fields for zeolitic imidazolate frameworks: MOF-FF for ZIFs. J. Chem. Theory Comput. 15, 2420–2432 (2019).

    Article  Google Scholar 

  32. Phan, A. et al. Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks. Acc. Chem. Res. 43, 58–67 (2010).

    Article  CAS  Google Scholar 

  33. Majumder, M., Chopra, N., Andrews, R. & Hinds, B. J. Enhanced flow in carbon nanotubes. Nature 438, 44 (2005).

    Article  CAS  Google Scholar 

  34. Holt, J. K. et al. Fast mass transport through sub-2-nanometer carbon nanotubes. Science 312, 1034–1037 (2006).

    Article  CAS  Google Scholar 

  35. Secchi, E. et al. Massive radius-dependent flow slippage in carbon nanotubes. Nature 537, 210–213 (2016).

    Article  CAS  Google Scholar 

  36. Radha, B. et al. Molecular transport through capillaries made with atomic-scale precision. Nature 538, 222–225 (2016).

    Article  CAS  Google Scholar 

  37. Tunuguntla, R. H. et al. Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins. Science 357, 792–796 (2017).

    Article  CAS  Google Scholar 

  38. Keerthi, A. et al. Ballistic molecular transport through two-dimensional channels. Nature 558, 420–424 (2018).

    Article  CAS  Google Scholar 

  39. Moggach, S. A., Bennett, T. D. & Cheetham, A. K. The effect of pressure on ZIF-8: increasing pore size with pressure and the formation of a high-pressure phase at 1.47 GPa. Angew. Chem. Int. Ed. 48, 7087–7089 (2009).

    Article  CAS  Google Scholar 

  40. Cnudde, P. et al. Light olefin diffusion during the MTO process on H-SAPO-34: a complex interplay of molecular factors. J. Am. Chem. Soc. 142, 6007–6017 (2020).

    Article  CAS  Google Scholar 

  41. Sun, Y. et al. Experimental study on energy dissipation characteristics of ZSM‐5 zeolite/water system. Adv. Eng. Mater. 15, 740–746 (2013).

    Article  CAS  Google Scholar 

  42. Sun, Y. et al. A candidate of mechanical energy mitigation system: dynamic and quasi-static behaviors and mechanisms of zeolite β/water system. Mater. Des. 66, 545–551 (2015).

    Article  CAS  Google Scholar 

  43. Gray, G. T. III Classic split Hopkinson pressure bar testing. ASM Handb. 8, 462–476 (2000).

    Google Scholar 

  44. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  CAS  Google Scholar 

  45. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B. 59, 1758–1775 (1999).

    Article  CAS  Google Scholar 

  46. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  CAS  Google Scholar 

  47. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    Article  Google Scholar 

  48. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).

    Article  CAS  Google Scholar 

  49. Vanpoucke, D. E. P., Lejaeghere, K., Van Speybroeck, V., Waroquier, M. & Ghysels, A. Mechanical properties from periodic plane wave quantum mechanical codes: the challenge of the flexible nanoporous MIL-47(V) framework. J. Phys. Chem. C 119, 23752–23766 (2015).

    Article  CAS  Google Scholar 

  50. Rogge, S. M. J. et al. A comparison of barostats for the mechanical characterization of metal-organic frameworks. J. Chem. Theory Comput. 11, 5583–5597 (2015).

    Article  CAS  Google Scholar 

  51. VandeVondele, J. et al. Quickstep: fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput. Phys. Commun. 167, 103–128 (2005).

    Article  CAS  Google Scholar 

  52. Hutter, J., Iannuzzi, M., Schiffmann, F. & VandeVondele, J. CP2K: atomistic simulations of condensed matter systems. Wiley Interdiscip. Rev. Comput. Mol. Sci. 4, 15–25 (2014).

    Article  CAS  Google Scholar 

  53. VandeVondele, J. & Hutter, J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J. Chem. Phys. 127, 114105 (2007).

    Article  Google Scholar 

  54. Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).

    Article  CAS  Google Scholar 

  55. Nosé, S. A molecular dynamics method for simulations in the canonical ensemble. Mol. Phys. 52, 255–268 (1984).

    Article  Google Scholar 

  56. Nosé, S. A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 81, 511–519 (1984).

    Article  Google Scholar 

  57. Hoover, W. G. Canonical dynamics: equilibrium phase-space distributions. Phys. Rev. A 31, 1695–1697 (1985).

    Article  CAS  Google Scholar 

  58. Martyna, G. J., Klein, M. L. & Tuckerman, M. Nosé–Hoover chains: the canonical ensemble via continuous dynamics. J. Chem. Phys. 97, 2635–2643 (1992).

    Article  Google Scholar 

  59. Martyna, G. J., Tobias, D. J. & Klein, M. L. Constant pressure molecular dynamics algorithms. J. Chem. Phys. 101, 4177–4189 (1994).

    Article  CAS  Google Scholar 

  60. Martyna, G. J., Tuckerman, M. E., Tobias, D. J. & Klein, M. L. Explicit reversible integrators for extended systems dynamics. Mol. Phys. 87, 1117–1157 (1996).

    Article  CAS  Google Scholar 

  61. Vanduyfhuys, L. et al. Extension of the QuickFF force field protocol for an improved accuracy of structural, vibrational, mechanical and thermal properties of metal-organic frameworks. J. Comput. Chem. 39, 999–1011 (2018).

    Article  CAS  Google Scholar 

  62. Vanduyfhuys, L. et al. QuickFF: a program for a quick and easy derivation of force fields for metal-organic frameworks from ab initio input. J. Comput. Chem. 36, 1015–1027 (2015).

    Article  CAS  Google Scholar 

  63. Mayo, S. L., Olafson, B. D. & Goddard, W. A. DREIDING: a generic force field for molecular simulations. J. Phys. Chem. 94, 8897–8909 (1990).

    Article  CAS  Google Scholar 

  64. Chen, J. & Martínez, T. J. QTPIE: charge transfer with polarization current equalization. A fluctuating charge model with correct asymptotics. Chem. Phys. Lett. 438, 315–320 (2007).

    Article  CAS  Google Scholar 

  65. Verstraelen, T. et al. Minimal basis iterative stockholder: atoms in molecules for force-field development. J. Chem. Theory Comput. 12, 3894–3912 (2016).

    Article  CAS  Google Scholar 

  66. Chen, J. L., Xue, B., Mahesh, K. & Siepmann, J. I. Molecular simulations probing the thermophysical properties of homogeneously stretched and bubbly water systems. J. Chem. Eng. Data 64, 3755–3771 (2019).

    Article  CAS  Google Scholar 

  67. Dubbeldam, D., Calero, S., Ellis, D. E. & Snurr, R. Q. RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials. Mol. Simul. 42, 81–101 (2015).

    Article  Google Scholar 

  68. Peng, D.-Y. & Robinson, D. B. A new two-constant equation of state. Ind. Eng. Chem. Fundam. 15, 59–64 (1976).

    Article  CAS  Google Scholar 

  69. Ewald, P. P. Die Berechnung optischer und elektrostatischer Gitterpotentiale. Ann. der Phys. 369, 253–287 (1921).

    Article  Google Scholar 

  70. Yaff, Yet Another Force Field, v.1.4.2 (Center for Molecular Modeling, 2019); http://molmod.github.io/yaff/index.html

  71. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).

    Article  CAS  Google Scholar 

  72. Humphrey, W., Dalke, A. & Schulten, K. VMD: visual molecular dynamics. J. Mol. Graph. 14, 33–38 (1996).

    Article  CAS  Google Scholar 

  73. Willems, T. F., Rycroft, C. H., Kazi, M., Meza, J. C. & Haranczyk, M. Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials. Micropor. Mesopor. Mat. 149, 134–141 (2012).

    Article  CAS  Google Scholar 

  74. Torrie, G. M. & Valleau, J. P. Nonphysical sampling distributions in Monte Carlo free-energy estimation: umbrella sampling. J. Comput. Phys. 23, 187–199 (1977).

    Article  Google Scholar 

  75. Kumar, S., Rosenberg, J. M., Bouzida, D., Swendsen, R. H. & Kollman, P. A. The weighted histogram analysis method for free‐energy calculations on biomolecules. I. The method. J. Comput. Chem. 13, 1011–1021 (1992).

    Article  CAS  Google Scholar 

  76. Souaille, M. & Roux, B. Extension to the weighted histogram analysis method: combining umbrella sampling with free energy calculations. Comput. Phys. Commun. 135, 40–57 (2001).

    Article  CAS  Google Scholar 

  77. Rogge, S. M. J. Supporting molecular data for high rate nanofluidic energy absorption in porous zeolitic frameworks. Zenodo https://doi.org/10.5281/zenodo.4534252 (2021).

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Acknowledgements

Y.S. and J.-C.T. thank the K.C. Wong Fellowship (Y.S.) and the European Research Council (ERC) Consolidator grant (under the grant agreement no. 771575 PROMOFS (J.-C.T.)) for funding the research. Y.S. also thanks the University of Birmingham for startup funds. S.M.J.R., A.L., S.V. and J.W. thank the Fund for Scientific Research Flanders (FWO, grant nos. 12T3519N (S.M.J.R.), 11D2220N (A.L.), 11U1914N (S.V.) and 1103618 N (J.W.)) and the Research Board of Ghent University (BOF). Funding was also received from the European Union’s Horizon 2020 Research and Innovation Programme (ERC Consolidator grant agreement no. 647755—DYNPOR (2015–2020) (V.V.S.)). We thank the Research Complex at Harwell for access to the materials characterization facilities and T. Johnson at Johnson–Matthey Technology Centre for providing the chabazite material. The computational resources (Stevin Supercomputer Infrastructure) and services used in this work were provided by the VSC (Flemish Supercomputer Centre), funded by Ghent University, the FWO and the Flemish Government—department EWI.

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Contributions

Y.S. conceived and performed all experiments, with guidance from C.R.S. and J.-C.T. S.M.J.R. performed the force-field-based MD simulations. A.L. performed the ab initio and umbrella sampling MD simulations. S.V. performed the GCMC and canonical Monte Carlo simulations. J.W. derived the ZIF-8 covalent force field, all under the guidance of V.V.S. Y.S., S.M.J.R., J.-C.T. and V.V.S wrote the paper with contributions from all authors.

Corresponding authors

Correspondence to Yueting Sun, Sven M. J. Rogge, Veronique Van Speybroeck or Jin-Chong Tan.

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Peer review information Nature Materials thanks Len Barbour, Joern Ilja Siepmann and Dan Zhao for their contribution to the peer review of this work.

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Supplementary Discussion, Figs. 1–93, Tables 1–8 and References 1–97.

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Sun, Y., Rogge, S.M.J., Lamaire, A. et al. High-rate nanofluidic energy absorption in porous zeolitic frameworks. Nat. Mater. 20, 1015–1023 (2021). https://doi.org/10.1038/s41563-021-00977-6

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