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Room-temperature metastability of multilayer graphene oxide films

Nature Materials volume 11, pages 544–549 (2012)Cite this article

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Abstract

Graphene oxide potentially has multiple applications. The chemistry of graphene oxide and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This understanding is crucial to enable future applications of this material. Here, a combined experimental and density functional theory study shows that multilayer graphene oxide produced by oxidizing epitaxial graphene through the Hummers method is a metastable material whose structure and chemistry evolve at room temperature with a characteristic relaxation time of about one month. At the quasi-equilibrium, graphene oxide reaches a nearly stable reduced O/C ratio, and exhibits a structure deprived of epoxide groups and enriched in hydroxyl groups. Our calculations show that the structural and chemical changes are driven by the availability of hydrogen in the oxidized graphitic sheets, which favours the reduction of epoxide groups and the formation of water molecules.

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Figure 1: Room-temperature experimental XPS spectra of aged GO films.
Figure 2: Atomistic structures of multilayered GO generated from DFT.
Figure 3: DFT and experimental XPS spectra.
Figure 4: DFT energy diagram for GO reduction.

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Acknowledgements

S.K., S.Z., A.B. and E.R. acknowledge the support of the National Science Foundation (NSF) (CMMI-1100290 and DMR-0820382). Y.H., C.B. and W.d.H. acknowledge the support of NSF grant DMR-0820382. A.B. acknowledges the support of the Samsung Advanced Institute of Technology (SAIT). E.R. acknowledges the support of the NSF grant DMR-0706031 and the Office of Basic Energy Sciences of the US Department of Energy (DE-FG02-06ER46293). Y.J.C. and M.A. acknowledge the support of the Office of Basic Sciences of the US Department of Energy (DE-SC001951). We thank D. Wang, P. Sheehan and A. R. Laracuente of the US Naval Research Laboratory for the 4-point electrical transport measurements.

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Authors and Affiliations

  1. School of Physics, Georgia Institute of Technology, Atlanta 30332-0430 Georgia, USA

    Suenne Kim, Yike Hu, Claire Berger, Walt de Heer & Elisa Riedo

  2. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta 30332-0400 Georgia, USA

    Si Zhou & Angelo Bongiorno

  3. Department of Materials Science and Engineering, The University of Texas at Dallas, Richardson, Texas 75080, USA

    Muge Acik & Yves J. Chabal

  4. Centre National de la Recherche Scientifique—Institut Néel, Grenoble, B.P. 166, 38042, France

    Claire Berger

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Contributions

S.K. performed XPS, AFM and optical experiments. S.Z. carried out DFT calculations. Y.H., C.B. and W.d.H. synthesized the GO samples. M.A. and Y.J.C. performed infrared measurements. A.B. conceived and designed the theory and analysed the data. E.R. conceived and designed the experiment and analysed the data. All authors contributed to writing the article.

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Correspondence to Angelo Bongiorno or Elisa Riedo.

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Kim, S., Zhou, S., Hu, Y. et al. Room-temperature metastability of multilayer graphene oxide films. Nature Mater 11, 544–549 (2012). https://doi.org/10.1038/nmat3316

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