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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Piner, R. D., Zhu, J., Xu, F., Hong, S. H. & Mirkin, C. A. ‘Dip-pen’ nanolithography. Science 283, 661–663 (1999).
Albrecht, P. M., Barraza-Lopez, S. & Lyding, J. W. Preferential orientation of a chiral semiconducting carbon nanotube on the locally depassivated Si(100)–2×1:H surface identified by scanning tunneling microscopy. Small 3, 1402–1406 (2007).
Chen, P. et al. Spatiotemporal catalytic dynamics within single nanocatalysts revealed by single-molecule microscopy. Chem. Soc. Rev. 43, 1107–1117 (2014).
Imboden, M. et al. Building a fab on a chip. Nanoscale 6, 5049–5062 (2014).
Park, H. B. et al. Polymers with cavities tuned for fast selective transport of small molecules and ions. Science 318, 254–258 (2007).
Strathmann, H. Membrane separation processes: current relevance and future opportunities. AIChE J. 47, 1077–1087 (2001).
Lai, Z. P. et al. Microstructural optimization of a zeolite membrane for organic vapor separation. Science 300, 456–460 (2003).
Shiflett, M. B. & Foley, H. C. Ultrasonic deposition of high-selectivity nanoporous carbon membranes. Science 285, 1902–1905 (1999).
Hinds, B. J. et al. Aligned multiwalled carbon nanotube membranes. Science 303, 62–65 (2004).
Ahn, J. Y., Chung, W. J., Pinnau, I. & Guiver, M. D. Poly sulfone/silica nanoparticle mixed-matrix membranes for gas separation. J. Membrane Sci. 314, 123–133 (2008).
de Vos, R. M. & Verweij, H. High-selectivity, high-flux silica membranes for gas separation. Science 279, 1710–1711 (1998).
Jiang, D. E., Cooper, V. R. & Dai, S. Porous graphene as the ultimate membrane for gas separation. Nano Lett. 9, 4019–4024 (2009).
Kim, H. W. et al. Selective gas transport through few-layered graphene and graphene oxide membranes. Science 342, 91–95 (2013).
Li, H. et al. Ultrathin, molecular-sieving graphene oxide membranes for selective hydrogen separation. Science 342, 95–98 (2013).
Boutilier, M. S. H. et al. Implications of permeation through intrinsic defects in graphene on the design of defect-tolerant membranes for gas separation. ACS Nano 8, 841–849 (2014).
Joshi, R. K. et al. Precise and ultrafast molecular sieving through graphene oxide membranes. Science 343, 752–754 (2014).
Drahushuk, L. W. & Strano, M. S. Mechanisms of gas permeation through single layer graphene membranes. Langmuir 28, 16671–16678 (2012).
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).
Dekker, C. Solid-state nanopores. Nature Nanotech. 2, 209–215 (2007).
Bunch, J. S. et al. Impermeable atomic membranes from graphene sheets. Nano Lett. 8, 2458–2462 (2008).
Hu, S. et al. Proton transport through one-atom-thick crystals. Nature 516, 227–230 (2014).
Park, J. Y., Yaish, Y., Brink, M., Rosenblatt, S. & McEuen, P. L. Electrical cutting and nicking of carbon nanotubes using an atomic force microscope. Appl. Phys. Lett. 80, 4446–4448 (2002).
Koenig, S. P., Wang, L. D., Pellegrino, J. & Bunch, J. S. Selective molecular sieving through porous graphene. Nature Nanotech. 7, 728–732 (2012).
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).
Sun, C. et al. Mechanisms of molecular permeation through nanoporous graphene membranes. Langmuir 30, 675–682 (2013).
Reif, F. Fundamentals of Statistical and Thermal Physics (McGraw-Hill, 1965).
Koenig, S. P., Boddeti, N. G., Dunn, M. L. & Bunch, J. S. Ultrastrong adhesion of graphene membranes. Nature Nanotech. 6, 543–546 (2011).
Liu, H., Dai, S. & Jiang, D.-E. Insights into CO2/N2 separation through nanoporous graphene from molecular dynamics. Nanoscale 5, 9984–9987 (2013).
Shan, M. et al. Influence of chemical functionalization on the CO2/N2 separation performance of porous graphene membranes. Nanoscale 4, 5477–5482 (2012).
Jin, H., Heller, D. A., Kim, J. H. & Strano, M. S. Stochastic analysis of stepwise fluorescence quenching reactions on single-walled carbon nanotubes: single molecule sensors. Nano Lett. 8, 4299–4304 (2008).
McKinney, S. A., Joo, C. & Ha, T. Analysis of single-molecule FRET trajectories using hidden Markov modeling. Biophys. J. 91, 1941–1951 (2006).
Cembran, A., Bernardi, F., Garavelli, M., Gagliardi, L. & Orlandi, G. On the mechanism of the cis–trans isomerization in the lowest electronic states of azobenzene: S0, S1, and T1 . J. Am. Chem. Soc. 126, 3234–3243 (2004).
Wang, L. D. et al. Ultrathin oxide films by atomic layer deposition on graphene. Nano Lett. 12, 3706–3710 (2012).
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.
The authors declare no competing financial interests.
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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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