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Nanoporous organic polymer networks

Nanoporous organic polymer networks. Reporter: Meng Wei Wang Advising Prof: Ru Jong Jeng. Adams, D. J., et al, Prog. Polym. Sci., 2012, 37, 530. Outline. Introduction Synthesis of nanoporous organic polmers Covalent organic frameworks (COFs) Hypercrosslinked polymers (HCPs)

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Nanoporous organic polymer networks

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  1. Nanoporous organic polymer networks Reporter: Meng Wei Wang Advising Prof: Ru Jong Jeng Adams, D. J.,et al, Prog. Polym. Sci., 2012, 37, 530.

  2. Outline • Introduction • Synthesis of nanoporous organic polmers • Covalent organic frameworks (COFs) • Hypercrosslinked polymers (HCPs) • Conjugated microporous polymers (CMPs) • Polymers of intrinsic microporosity (PIMs) • Summary

  3. Nanoporous polymer networks • Gas storage, separations, catalysis • Pore size: • Macroporous (> 50 nm) • Mesoporous (2-50 nm) • Microporous (< 2 nm) • Surface area in polymer networks: • Langmuir • Brunauer-Emmett-Teller (BET) How to create a pore structure?

  4. Covalent organic frameworks (COFs) 711 m2/g COF-5 1590 m2/g COF-1 Yaghi, O. M.,et al, Science, 2005, 310, 1166.

  5. COFs synthesized by the Yaghi group COF-6: 980 m2/g COF-8: 1400 m2/g COF-10: 2080 m2/g COF-102: 3472 m2/g COF-103: 4210 m2/g Yaghi, O. M.,et al, J. Am. Chem. Soc., 2007, 129, 12914. Yaghi, O. M.,et al, Science, 2007, 316, 268.

  6. Tailoring the microporosity Reduction in BET surface area from 1263 m2/g (COF-18A) to 105 m2/g (COF-11A) This chemical tuning of the pore size could be useful for selective gas separations. (pore size↓, N2↓, H2↑) Lavigne, J. J.,et al, Chem. Mater., 2006, 18, 5296. Lavigne, J. J.,et al, Adv. Mater., 2008, 20, 2741.

  7. Imine formation COF-300 Yaghi, O. M.,et al, J. Am. Chem. Soc., 2009, 131, 4570. Cooper, A. I.,et al, Angew. Chem. Int. Ed., 2011, 50, 749.

  8. Hypercrosslinked polymers (HCPs) • These materials hadapparent BET surface areas of up to 1900 m2/g and were generally more porous when BCMBP was included. • Themaximum apparent BET surface area for DCX networks was∼1400 m2/g. • The surface areas were found to increase with increasing amounts of Lewis acid. Cooper, A. I.,et al, Chem. Commun., 2006, 2670. Svec, F.,et al, Chem. Mater., 2006, 18, 4430. Cooper, A. I.,et al, Chem. Mater., 2007, 19, 2034.

  9. Polysilanes • Thermally stable and hydrophobic. • BET surface areas：780 m2/g (EOF-1) 1046 m2/g (EOF- 2). The BET surface areas for these networks were 445 (Sn), 423 (Sb) and 261 m2/g(Bi), which is lower than the Si EOFs but might in part be explained by the increased mass of the tetrahedral metal nodes. Kaskel, S.,et al, Chem. Commun., 2008, 2462. Kaskel, S.,et al, Materials, 2010, 3, 2447.

  10. A variety of other reactions Ullman Reaction Buchwald Reaction Frechet, J. M. J.,et al, Chem. Mater., 2008, 20, 7069. Svec, F.,et al, J. Mater. Chem., 2007, 17, 4989.

  11. Conjugated microporous polymers (CMPs) Cooper, A. I.,et al, J. Am. Chem. Soc., 2008, 130, 7710.

  12. Triazine-Based Frameworks Thomas, A.,et al, Angew. Chem. Int. Ed., 2008, 47, 3450.

  13. Suzuki reactions Thomas, A.,et al, J. Am. Chem. Soc., 2008, 130, 6334. Weber, J.,et al, Polym. Chem., 2011, 2, 1950. Han, B.-H.,et al, Macromolecules, 2011, 44, 5573.

  14. Yamamoto reactions Thomas, A.,et al, Macromolecules, 2009, 42, 4426.

  15. Click reactions Cooper, A.I.,et al, Macromolecules, 2010, 43, 8531. Nguyen, S. T.,et al, J. Mater. Chem., 2010, 21, 1700.

  16. Polymers of intrinsic microporosity (PIMs) McKeown, N. B.,et al, Chem. Commun, 2004, 230.

  17. Polymers of intrinsic microporosity (PIMs) McKeown, N. B.,et al, Chem. Eur. J., 2005, 11, 2610.

  18. Towards Chiral Microporous Soluble Polymers Weber, J.,et al, Macromol. Rapid. Commun., 2011, 32, 438. Weber, J., et al, Macromolecules, 2011, 44, 2025.

  19. Summary HCPs COFs PIMs CMPs

  20. Thanks for your attention.

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