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Molecular valves for controlling gas phase transport made from discrete ångström-sized pores in graphene

Abstract

An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale three-dimensional printing, catalysis and sensor design1,2,3,4. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores5,6,7,8,9,10,11,12,13,14,15,16,17,18. Here, we show that gas flux through discrete ångström-sized pores in monolayer graphene can be detected and then controlled using nanometre-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid-state nanopores19.

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Figure 1: Fabrication of molecular valves in suspended graphene.
Figure 2: Controlling the leak rate by laser-induced heating.
Figure 3: Leak rates of gases through porous monolayer suspended graphene without gold nanoparticles.
Figure 4: Stochastic switching of the leak rate through porous monolayer graphene without gold nanoparticles.

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Acknowledgements

The authors thank X. Yin for useful discussions and A. Swan, B. Goldberg and J. Christopher for assistance with Raman spectroscopy. This work was supported by the National Science Foundation (NSF), grant no. 1054406 (CMMI: CAREER, Atomic Scale Defect Engineering in Graphene Membranes), the NSF Industry/University Cooperative Research Center for Membrane Science, Engineering and Technology (MAST), in part by the National Nanotechnology Infrastructure Network (NNIN) and the NSF under grant no. ECS-0335765 and the NSF Graduate Research Fellowship under grant no. DGE-1247312. The theory and modelling part was supported (in part) by the US Army Research Office under contract no. W911NF-13-D-0001.

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L.W., L.C. and S.P.K. performed the experiments. L.W. and J.S.B. conceived and designed the experiments. L.W.D. and M.S.S. developed the theory and modelling. L.W., L.C., S.P.K. and X.L. prepared and fabricated the samples. L.W., L.W.D., J.P., M.S.S. and J.S.B. interpreted the results and co-wrote the manuscript.

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Correspondence to J. Scott Bunch.

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Wang, L., Drahushuk, L., Cantley, L. et al. Molecular valves for controlling gas phase transport made from discrete ångström-sized pores in graphene. Nature Nanotech 10, 785–790 (2015). https://doi.org/10.1038/nnano.2015.158

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