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On-water surface synthesis of crystalline, few-layer two-dimensional polymers assisted by surfactant monolayers

Nature Chemistry volume 11, pages 994–1000 (2019)Cite this article

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Abstract

Despite rapid progress in recent years, it has remained challenging to prepare crystalline two-dimensional polymers. Here, we report the controlled synthesis of few-layer two-dimensional polyimide crystals on the surface of water through reaction between amine and anhydride monomers, assisted by surfactant monolayers. We obtained polymers with high crystallinity, thickness of ~2 nm and an average crystal domain size of ~3.5 μm2. The molecular structure of the materials, their grain boundaries and their edge structures were characterized using X-ray scattering and transmission electron microscopy techniques. These characterizations were supported by computations. The formation of crystalline polymers is attributed to the pre-organization of monomers at the water–surfactant interface. The surfactant, depending on its polar head, promoted the arrangement of the monomers—and in turn their polymerization—either horizontally or vertically with respect to the water surface. The latter was observed with a surfactant bearing a carboxylic acid group, which anchored amine monomers vertically through a condensation reaction. In both instances, micrometre-sized, few-layer two-dimensional polyamide crystals were grown.

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Fig. 1: Synthesis protocol of 2D polymers.
Fig. 2: Structural characterization of 2DPI.
Fig. 3: GIWAXS analysis of the transition from pre-H to 2DPI.
Fig. 4: Structural characterization of 2DPA.
Fig. 5: GIWAXS analysis of the transition from pre-V to v2DPA.

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Data availability

The data supporting the findings of this study are available within the Article and its Supplementary Information or from the corresponding author upon reasonable request.

References

  1. Rodenas, T. et al. Metal–organic framework nanosheets in polymer composite materials for gas separation. Nat. Mater. 14, 48–55 (2015).

    Article  CAS  Google Scholar 

  2. Tessler, N., Denton, G. J. & Friend, R. H. Lasing from conjugated-polymer microcavities. Nature 382, 695–697 (1996).

    Article  CAS  Google Scholar 

  3. Yu, Y., Nakano, M. & Ikeda, T. Photomechanics: directed bending of a polymer film by light. Nature 425, 145 (2003).

    Article  CAS  Google Scholar 

  4. Staudinger, H. Über polymerisation. Ber. Dtsch Chem. Ges. 53, 1073–1085 (1920).

    Article  Google Scholar 

  5. Gee, G. Reactions in monolayers of drying oils. II. Polymerization of the oxidized forms of the maleic anhydride compound of beta elaeostearin. Proc. R. Soc. A 153, 129–141 (1935).

    Article  CAS  Google Scholar 

  6. Blumstein, A., Herz, J., Sinn, V. & Sadron, C. Sur un procede de polymerisation en couche adsorbee. Comptes Rendus Acad. Sci. 246, 1856–1858 (1958).

    CAS  Google Scholar 

  7. Stupp, S., Son, S., Lin, H. & Li, L. Synthesis of two-dimensional polymers. Science 259, 59–63 (1993).

    Article  CAS  Google Scholar 

  8. Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).

    Article  CAS  Google Scholar 

  9. Sakamoto, J., van Heijst, J., Lukin, O. & Schlüter, A. D. Two-dimensional polymers: just a dream of synthetic chemists? Angew. Chem. Int. Ed. 48, 1030–1069 (2009).

    Article  CAS  Google Scholar 

  10. Chen, L., Hernandez, Y., Feng, X. & Mullen, K. From nanographene and graphene nanoribbons to graphene sheets: chemical synthesis. Angew. Chem. Int. Ed. 51, 7640–7654 (2012).

    Article  CAS  Google Scholar 

  11. Grill, L. et al. Nano-architectures by covalent assembly of molecular building blocks. Nat. Nanotechnol. 2, 687–691 (2007).

    Article  CAS  Google Scholar 

  12. Bieri, M. et al. Porous graphenes: two-dimensional polymer synthesis with atomic precision. Chem. Commun. 2009, 6919–6921 (2009).

    Article  Google Scholar 

  13. Lafferentz, L. et al. Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nat. Chem. 4, 215–220 (2012).

    Article  CAS  Google Scholar 

  14. Gutzler, R. & Perepichka, D. π-Electron conjugation in two dimensions. J. Am. Chem. Soc. 135, 16585–16594 (2013).

    Article  CAS  Google Scholar 

  15. Cardenas, L. et al. Synthesis and electronic structure of a two dimensional-conjugated polythiophene. Chem. Sci. 4, 3263–3268 (2013).

    Article  CAS  Google Scholar 

  16. Bunck, D. N. & Dichtel, W. R. Bulk synthesis of exfoliated two-dimensional polymers using hydrazone-linked covalent organic frameworks. J. Am. Chem. Soc. 135, 14952–14955 (2013).

    Article  CAS  Google Scholar 

  17. Kissel, P. et al. A two-dimensional polymer prepared by organic synthesis. Nat. Chem. 4, 287–291 (2012).

    Article  CAS  Google Scholar 

  18. Kissel, P., Murray, D. J., Wulftange, W. J., Catalano, V. J. & King, B. T. A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization. Nat. Chem. 6, 774–778 (2014).

    Article  CAS  Google Scholar 

  19. Liu, W. et al. A two-dimensional conjugated aromatic polymer via C–C coupling reaction. Nat. Chem. 9, 563–570 (2017).

    Article  CAS  Google Scholar 

  20. Payamyar, P. et al. Synthesis of a covalent monolayer sheet by photochemical anthracene dimerization at the air/water interface and its mechanical characterization by AFM indentation. Adv. Mater. 26, 2052–2058 (2014).

    Article  CAS  Google Scholar 

  21. Murray, D. J. et al. Large area synthesis of a nanoporous two-dimensional polymer at the air/water interface. J. Am. Chem. Soc. 137, 3450–3453 (2015).

    Article  CAS  Google Scholar 

  22. Müller, V. et al. A two-dimensional polymer synthesized at the air/water interface. Angew. Chem. Int. Ed. 57, 10584–10588 (2018).

    Article  Google Scholar 

  23. Sahabudeen, H. et al. Wafer-sized multifunctional polyimine-based two-dimensional conjugated polymers with high mechanical stiffness. Nat. Commun. 7, 13461 (2016).

    Article  Google Scholar 

  24. Dey, K. et al. Selective molecular separation by interfacially crystallized covalent organic framework thin films. J. Am. Chem. Soc. 139, 13083–13091 (2017).

    Article  CAS  Google Scholar 

  25. Matsumoto, M. et al. Lewis-acid-catalyzed interfacial polymerization of covalent organic framework films. Chem 4, 308–317 (2018).

    Article  CAS  Google Scholar 

  26. Son, H.-J. et al. Light-harvesting and ultrafast energy migration in porphyrin-based metal–organic frameworks. J. Am. Chem. Soc. 135, 862–869 (2013).

    Article  CAS  Google Scholar 

  27. Huang, P. Y. et al. Grains and grain boundaries in single-layer graphene atomic patchwork quilts. Nature 469, 389–392 (2011).

    Article  CAS  Google Scholar 

  28. Robertson, A. W. et al. Atomic structure of interconnected few-layer graphene domains. ACS Nano 5, 6610–6618 (2011).

    Article  CAS  Google Scholar 

  29. Kurasch, S. et al. Atom-by-atom observation of grain boundary migration in graphene. Nano Lett. 12, 3168–3173 (2012).

    Article  CAS  Google Scholar 

  30. Najmaei, S. et al. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers. Nat. Mater. 12, 754–759 (2013).

    Article  CAS  Google Scholar 

  31. Van Der Zande, A. M. et al. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nat. Mater. 12, 554–561 (2013).

    Article  Google Scholar 

  32. Baumgartner, B., Puchberger, M. & Unterlass, M. M. Towards a general understanding of hydrothermal polymerization of polyimides. Polym. Chem. 6, 5773–5781 (2015).

    Article  CAS  Google Scholar 

  33. Fang, Q. et al. Designed synthesis of large-pore crystalline polyimide covalent organic frameworks. Nat. Commun. 5, 4503 (2014).

    Article  Google Scholar 

  34. Jung, Y. & Marcus, R. A. On the nature of organic catalysis ‘on water’. J. Am. Chem. Soc. 129, 5492–5502 (2007).

    Article  CAS  Google Scholar 

  35. Narayan, S. et al. ‘On water’: unique reactivity of organic compounds in aqueous suspension. Angew. Chem. Int. Ed. 44, 3275–3279 (2005).

    Article  CAS  Google Scholar 

  36. Butler, R. N. & Coyne, A. G. Water: nature’s reaction enforcer-comparative effects for organic synthesis ‘in-water’ and ‘on-water’. Chem. Rev. 110, 6302–6337 (2010).

    Article  CAS  Google Scholar 

  37. Maeda, S. et al. Implementation and performance of the artificial force induced reaction method in the GRRM17 program. J. Comput. Chem. 39, 233–251 (2018).

    Article  CAS  Google Scholar 

  38. Maeda, S., Ohno, K. & Morokuma, K. Systematic exploration of the mechanism of chemical reactions: the global reaction route mapping (GRRM) strategy using the ADDF and AFIR methods. Phys. Chem. Chem. Phys. 15, 3683–3701 (2013).

    Article  CAS  Google Scholar 

  39. Habas, S. E., Lee, H., Radmilovic, V., Somorjai, G. A. & Yang, P. Shaping binary metal nanocrystals through epitaxial seeded growth. Nat. Mater. 6, 692–697 (2007).

    Article  CAS  Google Scholar 

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Acknowledgements

We acknowledge financial support from the ERC Grant on T2DCP and the EU Graphene Flagship, COORNET (SPP 1928), CONJUGATION-706082 as well as the German Science Council, Centre of Advancing Electronics Dresden, EXC1056 (Center for Advancing Electronics Dresden) and OR 349/1. H.Q. and U.K. acknowledge financial support from the DFG in the framework of the ‘SALVE’ (Sub-Angstrom Low-voltage Electron Microscopy) project as well the Ministry of Science, Research and the Arts (MWK) of Baden-Wuerttemberg in the framework of the SALVE project. K.L. acknowledges the China Scholarship Council (CSC) for financial support. We acknowledge P. Formánek for assistance with TEM, M. Löffler for scanning electron microscopy and J. Michl for helpful discussions. GIWAXS was carried out at DESY, a member of the Helmholtz Association (HGF), and at Helmholtz-Zentrum Berlin (HZB). We thank M. Schwartzkopf for assistance at the P03-MINAXS beamline and D. Többens at the KMC-2 beamline. We thank HGF and HZB for the allocation of neutron/synchrotron radiation beam time.

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Author notes

  1. These authors contributed equally: Kejun Liu, Haoyuan Qi, Renhao Dong.

Authors and Affiliations

  1. Center for Advancing Electronics Dresden & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Kejun Liu, Renhao Dong, Rishi Shivhare, Tao Zhang, Hafeesudeen Sahabudeen, Thomas Heine, Stefan Mannsfeld & Xinliang Feng

  2. Central Facility of Electron Microscopy, Electron Microscopy Group of Materials Science, Universität Ulm, Ulm, Germany

    Haoyuan Qi & Ute Kaiser

  3. School of Science and Technology, Nottingham Trent University, Nottingham, UK

    Matthew Addicoat

  4. Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Universität Leipzig, Leipzig, Germany

    Thomas Heine

  5. Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Guangdong Engineering Technology Research Center for High-performance Organic and Polymer Photoelectric Functional Films, School of Chemistry, Sun Yat-sen University, Guangzhou, China

    Zhikun Zheng

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Contributions

X.F. conceived and designed the experiments. K.L. and R.D. contributed to the synthesis of 2D polymers and model compounds. H.Q. and U.K. performed AC-HRTEM imaging, SAED and the corresponding analysis. R.S., K.L. and H.S. conducted GIWAXS. K.L., H.Q., R.D., R.S., M.A. and S.M. analysed the diffraction data and proposed the crystal structures. T.Z. performed AFM imaging. K.L. performed optical microscopy, scanning electron microscopy, FTIR and UV–vis measurements. M.A., R.D. and T.H. contributed to the theory calculations and analysis. K.L., R.D. and X.F. proposed the reaction mechanism. K.L., H.Q., R.D., Z.Z. and X.F. co-wrote the manuscript, with contributions from all authors.

Corresponding authors

Correspondence to Ute Kaiser, Zhikun Zheng or Xinliang Feng.

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Supplementary Information

Supplementary Information

Materials, synthetic procedures, UV–vis and FTIR spectra, further discussion about crystal defects using HRTEM, SAED and GIWAXS and calculation about reaction barriers and reaction kinetics.

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Liu, K., Qi, H., Dong, R. et al. On-water surface synthesis of crystalline, few-layer two-dimensional polymers assisted by surfactant monolayers. Nat. Chem. 11, 994–1000 (2019). https://doi.org/10.1038/s41557-019-0327-5

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