Abstract
Chemical functionalization of graphene is promising for a variety of next-generation technologies. Although graphene oxide (GO) is a versatile material in this direction, its use is limited by the production of metastable, chemically inhomogeneous and spatially disordered GO structures under current synthetic protocols, which results in poor optoelectronic properties. Here, we present a mild thermal annealing procedure, with no chemical treatments involved, to manipulate as-synthesized GO on a large scale to enhance sheet properties with the oxygen content preserved. Using experiments supported by atomistic calculations, we demonstrate that GO structures undergo a phase transformation into prominent oxidized and graphitic domains by temperature-driven oxygen diffusion. Consequently, as-synthesized GO that absorbs mainly in the ultraviolet region becomes strongly absorbing in the visible region, photoluminescence is blue shifted and electronic conductivity increases by up to four orders of magnitude. Our thermal processing method offers a suitable way to tune and enhance the properties of GO, which creates opportunities for various applications.
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References
Eda, G., Fanchini, G. & Chhowalla, M. Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. Nature Nanotechnol. 3, 270–274 (2008).
Eda, G. & Chhowalla, M. Chemically derived graphene oxide: towards large-area thin-film electronics and optoelectronics. Adv. Mater. 22, 2392–2415 (2010).
Loh, K. P., Bao, Q., Eda, G. & Chhowalla, M. Graphene oxide as a chemically tunable platform for optical applications. Nature Chem. 2, 1015–1024 (2010).
Kamat, P. V. Graphene-based nanoassemblies for energy conversion. J. Phys. Chem. Lett. 2, 242–251 (2011).
Yun, J. M. et al. Solution-processable reduced graphene oxide as a novel alternative to PEDOT:PSS hole transport layers for highly efficient and stable polymer solar cells. Adv. Mater. 23, 4923–4928 (2011).
Xu, B. et al. What is the choice for supercapacitors: graphene or graphene oxide? Energy Environ. Sci. 4, 2826–2830 (2011).
Zhu, X., Zhu, Y., Murali, S., Stoller, M. D. & Ruoff, R. S. Nanostructured reduced graphene oxide/Fe2O3 composite as a high-performance anode material for lithium ion batteries. ACS Nano 5, 3333–3338 (2011).
Gao, W., Alemany, L. B., Ci, L., & Ajayan, P. M. New insights into the structure and reduction of graphite oxide. Nature Chem. 1, 403–408 (2009).
Johns, J. E. & Hersam, M. C. Atomic covalent functionalization of graphene. Acc. Chem. Res. 46, 77–86 (2013).
Su, C. et al. Probing the catalytic activity of porous graphene oxide and the origin of this behaviour. Nature Commun. 3, 1298–1306 (2012).
Pyun, J. Graphene oxide as catalyst: application of carbon materials beyond nanotechnology. Angew. Chem. Int. Ed. 50, 46–48 (2011).
Ramanathan, T. et al. Functionalized graphene sheets for polymer nanocomposites. Nature Nanotechnol. 3, 327–331 (2008).
Potts, J. R., Dreyer, D. R., Bielawski, C. W. & Ruoff, R. S. Graphene-based polymer nanocomposites. Polymer 52, 5–25 (2011).
Kamat, P. V. Graphene-based nanoarchitectures. Anchoring semiconductor and metal nanoparticles on a two-dimensional carbon support. J. Phys. Chem. Lett. 1, 520–527 (2010).
Lin, Y. et al. Dramatically enhanced photoresponse of reduced graphene oxide with linker-free anchored CdSe nanoparticles. ACS Nano 4, 3033–3038 (2010).
Hummers, W. S. & Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339 (1958).
Szabo, T. et al. Evolution of surface functional groups in a series of progressively oxidized graphite oxides. Chem. Mater. 18, 2740–2749 (2006).
Hunt, A. et al. Epoxide speciation and functional group distribution in graphene oxide paper-like materials. Adv. Funct. Mater. 22, 3950–3957 (2012).
Hossain, Z. et al. Chemically homogeneous and thermally reversible oxidation of epitaxial graphene. Nature Chem. 4, 305–309 (2012).
Bagri, A. et al. Structural evolution during the reduction of chemically derived graphene oxide. Nature Chem. 2, 581–587 (2010).
Feng, H., Cheng, R., Zhao, X., Duan, X. & Li, J. A low-temperature method to produce highly reduced graphene oxide. Nature Commun. 5, 1539–1545 (2013).
Fan, X. et al. Deoxygenation of exfoliated graphite oxide under alkaline conditions: a green route to graphene preparation. Adv. Mater. 20, 4490–4493 (2008).
Rourke, J. P. et al. The real graphene oxide revealed: stripping the oxidative debris from the graphene-like sheets. Angew. Chem. Int. Ed. 50, 3173–3177 (2011).
Liao, K. H. et al. Aqueous only route toward graphene from graphite oxide. ACS Nano 5, 1253–1258 (2011).
Wei, Z. et al. Nanoscale tunable reduction of graphene oxide for graphene electronics. Science 328, 1373–1376 (2010).
Mattson, E. C. et al. Evidence of nanocrystalline semiconducting graphene monoxide during thermal reduction of graphene oxide in vacuum. ACS Nano 5, 9710–9717 (2011).
Kim, S. et al. Room-temperature metastability of multilayer graphene oxide films. Nature Mater. 11, 544–549 (2012).
Suarez, A. M., Radovic, L. R., Bar-Ziv, E. & Sofo, J. O. Gate-voltage control of oxygen diffusion on graphene. Phys. Rev. Lett. 106, 146802 (2011).
Solenov, D. & Velizhanin, K. A. Adsorbate transport on graphene by electromigration. Phys. Rev. Lett. 109, 095504 (2012).
Eda, G. et al. Blue photoluminescence from chemically derived graphene oxide. Adv. Mater. 22, 505–509 (2010).
Jung, I., Dikin, D. A., Piner, R. D. & Ruoff, R. S. Tunable electrical conductivity of individual graphene oxide sheets reduced at low temperatures. Nano Lett. 8, 4283–4287 (2008).
Chien, C. T. et al. Tunable photoluminescence from graphene oxide. Angew. Chem. Int. Ed. 51, 6662–6666 (2012).
Van Duin, A. C. T., Dasgupta, S., Lorant, F. & Goddard, W. A. ReaxFF: A reactive force field for hydrocarbons. J. Phys. Chem. A 105, 9396–9409 (2001).
Wang, L. et al. Stability of graphene oxide phases from first-principles calculations. Phys. Rev. B 82, 2–5 (2010).
Nguyen, M. T., Erni, R. & Passerone, D. Two-dimensional nucleation and growth mechanism explaining graphene oxide structures. Phys. Rev. B 86, 115406 (2012).
Topsakal, M. & Ciraci, S. Domain formation on oxidized graphene. Phys. Rev. B 86, 205402 (2012).
Huang, B., Xiang, H., Xu, Q. & Wei, S. H. Overcoming the phase inhomogeneity in chemically functionalized graphene: the case of graphene oxides. Phys. Rev. Lett. 110, 085501 (2013).
Ci, L. et al. Atomic layers of hybridized boron nitride and graphene domains. Nature Mater. 9, 430–435 (2010).
Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).
Paci, J. T., Belytschko, T. & Schatz, G. C. Computational studies of the structure, behavior upon heating, and mechanical properties of graphite oxide. J. Phys. Chem. B 111, 18099–18111 (2007).
Kumar, P. V., Bernardi, M. & Grossman, J. C. The impact of functionalization on the stability, work function, and photoluminescence of reduced graphene oxide. ACS Nano 7, 1638–1645 (2013).
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab-initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758 (1999).
Perdew, J., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Acknowledgements
The authors dedicate this paper to the memory of S. Collier for his caring service to the Massachusetts Institute of Technology (MIT) community and for his sacrifice in defending the MIT campus in the line of duty. P.V.K. is grateful to Eni for financial support via the Solar Frontiers Program at MIT. P.V.K. and J.C.G. thank the Texas Advanced Computer Sector Stampede system for computational resources. This study was supported in part by the Institute for Collaborative Biotechnologies through grant W911NF-09-0001 from the US Army Research Office. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. N.M.B. and P.V.K. are grateful for the use of the Materials Analysis Shared Experimental Facilities at the Center for Materials Science and Engineering at MIT, and thank T. McClure, E. Shaw, T. Kucharski, J. Qi, G. Zhang, J. Ohmura and A. Maurano for assistance with experiments.
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P.V.K., N.M.B., A.M.B. and J.C.G. conceived and designed the experiments, P.V.K. and N.M.B. performed the experiments, calculations and co-wrote the manuscript with input from J.C.G. and A.M.B., and S.T. and J.W. performed AES, and contributed to Raman and PL mapping.
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Kumar, P., Bardhan, N., Tongay, S. et al. Scalable enhancement of graphene oxide properties by thermally driven phase transformation. Nature Chem 6, 151–158 (2014). https://doi.org/10.1038/nchem.1820
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DOI: https://doi.org/10.1038/nchem.1820
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