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Selective molecular sieving through porous graphene

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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Figure 1: Measuring leak rates in porous graphene membranes.
Figure 2: Comparison of leak rates of pristine and porous graphene membranes.
Figure 3: Measuring leak rates in a porous graphene membrane using mechanical resonance.
Figure 4: Compilation of measured leak rates.

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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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Correspondence to J. Scott Bunch.

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The authors declare no competing financial interests.

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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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