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High-capacity methane storage in flexible alkane-linked porous aromatic network polymers

Nature Energy volume 4, pages 604–611 (2019)Cite this article

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Abstract

Adsorbed natural gas (ANG) technology is a viable alternative to conventional liquefied or compressed natural-gas storage. Many different porous materials have been considered for adsorptive, reversible methane storage, but fall short of the US Department of Energy targets (0.5 g g−1, 263 l l−1). Here, we prepare a flexible porous polymer, made from benzene and 1,2-dichloroethane in kilogram batches, that has a high methane working capacity of 0.625 g g−1 and 294 l l−1 when cycled between 5 and 100 bar pressure. We suggest that the flexibility provides rapid desorption and thermal management, while the hydrophobicity and the nature of the covalently bonded framework allow the material to tolerate harsh conditions. The polymer also shows an adsorbate memory effect, where a less adsorptive gas (N2) follows the isotherm profile of a high-capacity adsorbate (CO2), which is attributed to the thermal expansion caused by the adsorption enthalpy. The high methane capacity and memory effect make flexible porous polymers promising candidates for ANG technology.

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Fig. 1: Design and synthesis of flexible porous polymers.
Fig. 2: Reversible methane uptake by flexible porous polymers.
Fig. 3: Adsorbate memory effect.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author on reasonable request.

References

  1. Kumar, K. V., Preuss, K., Titirici, M.-M. & Rodríguez-Reinoso, F. Nanoporous materials for the onboard storage of natural gas. Chem. Rev. 117, 1796–1825 (2017).

    Article  Google Scholar 

  2. Mason, J. A. et al. Methane storage in flexible metal–organic frameworks with intrinsic thermal management. Nature 527, 357–361 (2015).

    Article  Google Scholar 

  3. Peng, Y. et al. Methane storage in metal–organic frameworks: current records, surprise findings, and challenges. J. Am. Chem. Soc. 135, 11887–11894 (2013).

    Article  Google Scholar 

  4. Li, B., Wen, H.-M., Zhou, W., Xu, J. Q. & Chen, B. Porous metal-organic frameworks: promising materials for methane storage. Chem 1, 557–580 (2016).

    Article  Google Scholar 

  5. Deria, P. et al. Beyond post-synthesis modification: evolution of metal-organic frameworks via building block replacement. Chem. Soc. Rev. 43, 5896–5912 (2014).

    Article  Google Scholar 

  6. Guillerm, V. et al. A supermolecular building approach for the design and construction of metal-organic frameworks. Chem. Soc. Rev. 43, 6141–6172 (2014).

    Article  Google Scholar 

  7. Li, M., Li, D., O’Keeffe, M. & Yaghi, O. M. Topological analysis of metal–organic frameworks with polytopic linkers and/or multiple building units and the minimal transitivity principle. Chem. Rev. 114, 1343–1370 (2014).

    Article  Google Scholar 

  8. Krause, S. et al. A pressure-amplifying framework material with negative gas adsorption transitions. Nature 532, 348–352 (2016).

    Article  Google Scholar 

  9. Jung, J. Y. et al. Limitations and high pressure behavior of MOF-5 for CO2 capture. Phys. Chem. Chem. Phys. 15, 14319–14327 (2013).

    Article  Google Scholar 

  10. Byun, J., Patel, H. A., Thirion, D. & Yavuz, C. T. Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks. Nat. Commun. 7, 13377 (2016).

    Article  Google Scholar 

  11. Patel, H. A. et al. High capacity carbon dioxide adsorption by inexpensive covalent organic polymers. J. Mater. Chem. 22, 8431–8437 (2012).

    Article  Google Scholar 

  12. Tian, T. et al. A sol–gel monolithic metal–organic framework with enhanced methane uptake. Nat. Mater. 17, 174–179 (2018).

    Article  Google Scholar 

  13. Chang, G. et al. A microporous metal-organic framework with polarized trifluoromethyl groups for high methane storage. Chem. Commun. 51, 14789–14792 (2015).

    Article  Google Scholar 

  14. Li, B. et al. A porous metal–organic framework with dynamic pyrimidine groups exhibiting record high methane storage working capacity. J. Am. Chem. Soc. 136, 6207–6210 (2014).

    Article  Google Scholar 

  15. Ma, S. et al. Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake. J. Am. Chem. Soc. 130, 1012–1016 (2008).

    Article  Google Scholar 

  16. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).

    Article  Google Scholar 

  17. Olah, G. A., Reddy, V. P. & Prakash, G. K. S. in Kirk-Othmer Encyclopedia of Chemical Technology 159–199 (Wiley, 2000).

  18. Martin, C. F. et al. Hypercrosslinked organic polymer networks as potential adsorbents for pre-combustion CO2 capture. J. Mater. Chem. 21, 5475–5483 (2011).

    Article  Google Scholar 

  19. Tan, L. et al. Hypercrosslinked porous polymer materials: design, synthesis, and applications. Chem. Soc. Rev. 46, 3322–3356 (2017).

    Article  Google Scholar 

  20. Li, B. et al. A new strategy to microporous polymers: knitting rigid aromatic building blocks by external cross-linker. Macromolecules 44, 2410–2414 (2011).

    Article  Google Scholar 

  21. Wang, S. et al. Layered microporous polymers by solvent knitting method. Sci. Adv. 3, e1602610 (2017).

    Article  Google Scholar 

  22. Li, L., Cai, K., Wang, P., Ren, H. & Zhu, G. Construction of sole benzene ring porous aromatic frameworks and their high adsorption properties. ACS Appl. Mater. Interfaces 7, 201–208 (2015).

    Article  Google Scholar 

  23. Msayib, K. J. & McKeown, N. B. Inexpensive polyphenylene network polymers with enhanced microporosity. J. Mater. Chem. A 4, 10110–10113 (2016).

    Article  Google Scholar 

  24. Jiang, J. et al. High methane storage working capacity in metal–organic frameworks with acrylate links. J. Am. Chem. Soc. 138, 10244–10251 (2016).

    Article  Google Scholar 

  25. Ullah, R. et al. Investigation of ester- and amide-linker-based porous organic polymers for carbon dioxide capture and separation at wide temperatures and pressures. ACS Appl. Mater. Interfaces 8, 20772–20785 (2016).

    Article  Google Scholar 

  26. Mason, J. A., Veenstra, M. & Long, J. R. Evaluating metal-organic frameworks for natural gas storage. Chem. Sci. 5, 32–51 (2014).

    Article  Google Scholar 

  27. Yuan, D., Lu, W., Zhao, D. & Zhou, H.-C. Highly stable porous polymer networks with exceptionally high gas-uptake capacities. Adv. Mater. 23, 3723–3725 (2011).

    Article  Google Scholar 

  28. Casco, M. E. et al. High-pressure methane storage in porous materials: are carbon materials in the pole position? Chem. Mater. 27, 959–964 (2015).

    Article  Google Scholar 

  29. Patel, H. A., Byun, J. & Yavuz, C. T. Carbon dioxide capture adsorbents: chemistry and methods. ChemSusChem 10, 1303–1317 (2017).

    Article  Google Scholar 

  30. Wu, K. et al. Methane storage in nanoporous material at supercritical temperature over a wide range of pressures. Sci. Rep. 6, 33461 (2016).

    Article  Google Scholar 

  31. Alezi, D. et al. MOF crystal chemistry paving the way to gas storage needs: aluminum-based soc-MOF for CH4, O2, and CO2 storage. J. Am. Chem. Soc. 137, 13308–13318 (2015).

    Article  Google Scholar 

  32. Kong, G. Q. et al. Expanded organic building units for the construction of highly porous metal–organic frameworks. Chem. Eur. J. 19, 14886–14894 (2013).

    Article  Google Scholar 

  33. He, Y., Zhou, W., Yildirim, T. & Chen, B. A series of metal–organic frameworks with high methane uptake and an empirical equation for predicting methane storage capacity. Energy Environ. Sci. 6, 2735–2744 (2013).

    Article  Google Scholar 

  34. DeSantis, D. et al. Techno-economic analysis of metal–organic frameworks for hydrogen and natural gas storage. Energy Fuels 31, 2024–2032 (2017).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by National Research Foundation of Korea (NRF) grants funded by the Korean government (Ministry of Science, ICT and Future Planning) (nos NRF-2016R1A2B4011027, NRF-2017M3A7B4042140 and NRF-2017M3A7B4042235).

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Authors and Affiliations

  1. Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Korea

    Vepa Rozyyev, Damien Thirion, Joosung Lee & Cafer T. Yavuz

  2. National Institute for Materials Science (NIMS), Tsukuba, Japan

    Ruh Ullah

  3. Department of Energy Engineering, Gyeongnam National University of Science and Technology (GNTECH), Jinju, Korea

    Minji Jung & Hyunchul Oh

  4. Department of Chemical Engineering, Texas A&M University at Qatar, Doha, Qatar

    Mert Atilhan

  5. Gas and Fuels Research Center, Texas A&M University, College Station, TX, USA

    Mert Atilhan

  6. Department of Chemical and Biomolecular Engineering, KAIST, Daejeon, Korea

    Cafer T. Yavuz

  7. Department of Chemistry, KAIST, Daejeon, Korea

    Cafer T. Yavuz

Authors
  1. Vepa Rozyyev
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  2. Damien Thirion
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  4. Joosung Lee
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  5. Minji Jung
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  7. Mert Atilhan
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  8. Cafer T. Yavuz
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Contributions

V.R. synthesized and characterized all the sorbents. D.T. helped in syntheses and analyses. R.U. and M.A. carried out high-pressure pure-gas uptake studies. V.R. and J.L. tested COP-150 in an actual cylinder. M.J. and H.O. collected cryogenic (111K) CH4 isotherms. M.A. explained the high-pressure behaviour of the sorbents. C.T.Y. conceived the project and wrote the manuscript with contributions from all authors.

Corresponding authors

Correspondence to Mert Atilhan or Cafer T. Yavuz.

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Competing interests

KAIST has filed a provisional patent application (10-2019-0058296) related to the new flexible porous polymers reported in this manuscript.

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Supplementary Information

Supplementary Methods, Supplementary Notes 1–3, Supplementary Figs. 1–35, Supplementary Tables 1–10 and Supplementary refs.

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Rozyyev, V., Thirion, D., Ullah, R. et al. High-capacity methane storage in flexible alkane-linked porous aromatic network polymers. Nat Energy 4, 604–611 (2019). https://doi.org/10.1038/s41560-019-0427-x

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