Abstract
Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robust to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size-selective membranes1,2,3,4,5,6,7,8 because of its atomic thickness9, high mechanical strength10, relative inertness and impermeability to all standard gases11,12,13,14. However, pores that can exclude larger molecules but allow smaller molecules to pass through would have to be introduced into the material. Here, we show that ultraviolet-induced oxidative etching15,16 can create pores in micrometre-sized graphene membranes, and the resulting membranes can be used as molecular sieves. A pressurized blister test and mechanical resonance are used to measure the transport of a range of gases (H2, CO2, Ar, N2, CH4 and SF6) through the pores. The experimentally measured leak rate, separation factors and Raman spectrum agree well with models based on effusion through a small number of ångstrom-sized pores.
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References
Jiang, D., Cooper, V. R. & Dai, S. Porous graphene as the ultimate membrane for gas separation. Nano Lett. 9, 4019–4024 (2009).
Du, H. et al. Separation of hydrogen and nitrogen gases with porous graphene membrane. J. Phys. Chem. C 115, 23261–23266 (2011).
Schrier, J. Helium separation using porous graphene membranes. J. Phys. Chem. Lett. 1, 2284–2287 (2010).
Hauser, A. W. & Schwerdtfeger, P. Nanoporous graphene membranes for efficient 3He/4He separation. J. Phys. Chem. Lett. 3, 209–213 (2012).
Blankenburg, S. et al. Porous graphene as an atmospheric nanofilter. Small 6, 2266–2271 (2010).
Suk, M. E. & Aluru, N. R. Water transport through ultrathin graphene. J. Phys. Chem. Lett. 1, 1590–1594 (2010).
Schrier, J. & McClain, J. Thermally-driven isotope separation across nanoporous graphene. Chem. Phys. Lett. 521, 118–124 (2012).
Li, Y., Zhou, Z., Shen, P. & Chen, Z. Two-dimensional polyphenylene: experimentally available porous graphene as a hydrogen purification membrane. Chem. Commun. 46, 3672–3674 (2010).
Meyer, J. C. et al. The structure of suspended graphene sheets. Nature 446, 60–63 (2007).
Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).
Bunch, J. S. et al. Impermeable atomic membranes from graphene sheets. Nano Lett. 8, 2458–2462 (2008).
Nair, R. R., Wu, H. A., Jayaram, P. N., Grigorieva, I. V. & Geim, A. K. Unimpeded permeation of water through helium-leak-tight graphene-based membranes. Science 335, 442–444 (2012).
Leenaerts, O., Partoens, B. & Peeters, F. M. Graphene: a perfect nanoballoon. Appl. Phys. Lett. 93, 193107 (2008).
Chen, S. et al. Oxidation resistance of graphene-coated Cu and Cu/Ni alloy. ACS Nano 5, 1321–1327 (2011).
Ozeki, S., Ito, T., Uozumi, K. & Nishio, I. Scanning tunneling microscopy of UV-induced gasification reaction on highly oriented pyrolytic graphite. Jpn. J. Appl. Phys. 35, 3772–3774 (1996).
Huh, S. et al. UV/ozone-oxidized large-scale graphene platform with large chemical enhancement in surface-enhanced Raman scattering. ACS Nano 5, 9799–9806 (2011).
Novoselov, K. S. et al. Two-dimensional atomic crystals. Proc. Natl Acad. Sci. USA 102, 10451–10453 (2005).
Koenig, S. P., Boddeti, N. G., Dunn, M. L. & Bunch, J. S. Ultrastrong adhesion of graphene membranes. Nature Nanotech. 6, 543–546 (2011).
Liu, L. et al. Graphene oxidation: thickness-dependent etching and strong chemical doping. Nano Lett. 8, 1965–1970 (2008).
Chang, H. & Bard, A. J. Scanning tunneling microscopy studies of carbon–oxygen reactions on highly oriented pyrolytic graphite. J. Am. Chem. Soc. 113, 5588–5596 (1991).
Bieri, M. et al. Porous graphenes: two-dimensional polymer synthesis with atomic precision. Chem. Commun. 6919–6921 (2009).
Girit, C. O. et al. Graphene at the edge: stability and dynamics. Science 323, 1705–1708 (2009).
Schrier, J. Fluorinated and nanoporous graphene materials as sorbents for gas separations. ACS Appl. Mater. Interf. 3, 4451–4458 (2011).
Bai, J., Zhong, X., Jiang, S., Huang, Y. & Duan, X. Graphene nanomesh. Nature Nanotech. 5, 190–194 (2010).
Sint, K., Wang, B. & Král, P. Selective ion passage through functionalized graphene nanopores. J. Am. Chem. Soc. 130, 16448–16449 (2008).
Fan, Z. et al. Easy synthesis of porous graphene nanosheets and their use in supercapacitors. Carbon 50, 1699–1703 (2012).
Fox, D. et al. Nitrogen assisted etching of graphene layers in a scanning electron microscope. Appl. Phys. Lett. 98, 243117 (2011).
Breck, D. W. in Zeolites Molecular Sieves: Structure, Chemistry, and Use 593–724 (Wiley, 1973).
Bunch, J. S. et al. Electromechanical resonators from graphene sheets. Science 315, 490–493 (2007).
Hencky, H. Uber den spannungzustand in kreisrunden platten mit verschwindender biegungssteiflgeit. Z. fur Mathematik und Physik 63, 311–317 (1915).
Blakslee, O. L., Proctor, D. G., Seldin, E. J., Spence, G. B. & Weng, T. Elastic constants of compression-annealed pyrolytic graphite. J. Appl. Phys. 41, 3373–3382 (1970).
Acknowledgements
The authors thank D. McSweeney and M. Tanksalvala for help with the resonance measurements and R. Raj for use of the Raman microscope. This work was supported by National Science Foundation (NSF) grants 0900832 (CMMI: Graphene Nanomechanics: The Role of van der Waals Forces) and 1054406 (CMMI: CAREER: Atomic Scale Defect Engineering in Graphene Membranes), the DARPA Center on Nanoscale Science and Technology for Integrated Micro/Nano-Electromechanical Transducers (iMINT), the NSF Industry/University Cooperative Research Center for Membrane Science, Engineering and Technology (MAST), and the National Nanotechnology Infrastructure Network (NNIN) and NSF (grant no. ECS-0335765).
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S.P.K. and L.W. performed the experiments. S.P.K. and J.S.B. conceived and designed the experiments. All authors interpreted the results and co-wrote the manuscripts.
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Koenig, S., Wang, L., Pellegrino, J. et al. Selective molecular sieving through porous graphene. Nature Nanotech 7, 728–732 (2012). https://doi.org/10.1038/nnano.2012.162
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DOI: https://doi.org/10.1038/nnano.2012.162
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