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Functional carbon nanosheets prepared from hexayne amphiphile monolayers at room temperature

Nature Chemistry volume 6, pages 468–476 (2014)Cite this article

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Abstract

Carbon nanostructures that feature two-dimensional extended nanosheets are important components for technological applications such as high-performance composites, lithium-ion storage, photovoltaics and nanoelectronics. Chemical functionalization would render such structures better processable and more suited for tailored applications, but typically this is precluded by the high temperatures needed to prepare the nanosheets. Here, we report direct access to functional carbon nanosheets of uniform thickness at room temperature. We used amphiphiles that contain hexayne segments as metastable carbon precursors and self-assembled these into ordered monolayers at the air/water interface. Subsequent carbonization by ultraviolet irradiation in ambient conditions resulted in the quantitative carbonization of the hexayne sublayer. Carbon nanosheets prepared in this way retained their surface functionalization and featured an sp2-rich amorphous carbon structure comparable to that usually obtained on annealing above 800 °C. Moreover, they exhibited a molecularly defined thickness of 1.9 nm, were mechanically self-supporting over several micrometres and had macroscopic lateral dimensions on the order of centimetres.

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Figure 1: Well-ordered monolayer of the hexayne amphiphile 1 at the air/water interface.
Figure 2: Fitting of the experimental IRRA spectra for a layer of 1 at the air/water interface.
Figure 3: XR measurements as well as GIXD data for a layer of amphiphile 1.
Figure 4: Carbonization process of a film of 1 monitored by IRRA spectroscopy and characterization of the carbonized films by BAM as well as UV/vis and Raman spectroscopy.
Figure 5: SEM and TEM images of carbon nanosheets obtained by carbonization of 1 at the air/water interface after transfer to a holey carbon TEM grid.

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Acknowledgements

The authors thank I. Berndt for help with the isotherm measurements and E. Bremond for assistance with the IRRA surface plots. Also, F. Stellacci, J. C. Brauer and T. N. Hoheisel are gratefully acknowledged for helpful discussions and comments on the manuscript. Funding from the European Research Council (ERC Grant 239831, ‘OrgElNanoCarbMater’) is gratefully acknowledged, C.S. thanks the Max Planck Society for a stipend, C.Sch. thanks the DFG for funding within FOR 1145 and C.C. acknowledges the Swiss NSF Grant 200021_121577/1. We thank HASYLAB at DESY, Hamburg, Germany, for beam time and excellent support.

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Authors and Affiliations

  1. Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Materials, Laboratory of Macromolecular and Organic Materials, EPFL STI IMX LMOM, MXG 037, Station 12, Lausanne, 1015, Switzerland

    Stephen Schrettl & Holger Frauenrath

  2. Department of Interfaces, Max Planck Institute of Colloids and Interfaces, Potsdam, 14476, Germany

    Cristina Stefaniu & Gerald Brezesinski

  3. Martin Luther Universität Halle-Wittenberg, Institute of Chemistry, Halle (Saale), 06120, Germany

    Christian Schwieger

  4. Ecole Polytechnique Fédérale de Lausanne (EPFL), Interdisciplinary Centre for Electron Microscopy, Lausanne, 1015, Switzerland

    Guillaume Pasche & Emad Oveisi

  5. Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Condensed Matter Physics, Electron Spectrometry and Microscopy Laboratory, 1015 Lausanne, Switzerland

    Emad Oveisi

  6. Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Materials, Laboratory of Semiconductor Materials, Lausanne, 1015, Switzerland

    Yannik Fontana & Anna Fontcuberta i Morral

  7. Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Materials, Supramolecular Nanomaterials and Interfaces Laboratory, Lausanne, 1015, Switzerland

    Javier Reguera

  8. Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, Laboratory for Computational Molecular Design, Lausanne, 1015, Switzerland

    Riccardo Petraglia & Clémence Corminboeuf

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  1. Stephen Schrettl
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  12. Holger Frauenrath
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Contributions

S.S. synthesized all the compounds, performed Langmuir experiments, BAM and IRRA spectroscopy together with C.S., TEM imaging with J.R., SEM imaging with G.P., HR-TEM with E.O. and carried out the carbonization experiments as well as UV/vis spectroscopy. C.S. and G.B contributed the GIXD and specular XR experiments. C.Sch. carried out the simulation, fitting and interpretation of the IRRA spectra. Y.F. performed the Raman spectroscopy supervised by A.FiM. J.R. synthesized the hydrophilic gold nanoparticles. R.P. and C.C. performed the DFT computations. All these authors contributed to writing the manuscript. H.F. had the idea, directed the research and co-wrote the manuscript with S.S.

Corresponding author

Correspondence to Holger Frauenrath.

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Schrettl, S., Stefaniu, C., Schwieger, C. et al. Functional carbon nanosheets prepared from hexayne amphiphile monolayers at room temperature. Nature Chem 6, 468–476 (2014). https://doi.org/10.1038/nchem.1939

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