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Low-voltage electrostatic modulation of ion diffusion through layered graphene-based nanoporous membranes


Ion transport in nanoconfinement differs from that in bulk and has been extensively researched across scientific and engineering disciplines1,2,3,4. For many energy and water applications of nanoporous materials, concentration-driven ion diffusion is simultaneously subjected to a local electric field arising from surface charge or an externally applied potential. Due to the uniquely crowded intermolecular forces under severe nanoconfinement (<2 nm), the transport behaviours of ions can be influenced by the interfacial electrical double layer (EDL) induced by a surface potential, with complex implications, engendering unusual ion dynamics5,6,7. However, it remains an experimental challenge to investigate how such a surface potential and its coupling with nanoconfinement manipulate ion diffusion. Here, we exploit the tunable nanoconfinement in layered graphene-based nanoporous membranes to show that sub-2 nm confined ion diffusion can be strongly modulated by the surface potential-induced EDL. Depending on the potential sign, the combination and concentration of ion pairs, diffusion rates can be reversibly modulated and anomalously enhanced by 4~7 times within 0.5 volts, across a salt concentration gradient up to seawater salinity. Modelling suggests that this anomalously enhanced diffusion is related to the strong ion–ion correlations under severe nanoconfinement, and cannot be explained by conventional theoretical predictions.

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Fig. 1: Ion diffusion through nanoconfined EDLs in charged layered graphene-based nanoporous membranes.
Fig. 2: Normalized membrane flux dependence on Vg under various levels of nanoconfinement and concentration gradient.
Fig. 3: Ion-specific electrostatically modulated ion diffusion through layered graphene-based nanoporous membranes (d= 2 nm).
Fig. 4: Role of ion–ion correlations in altering channel counter- and co-ion concentrations, membrane potential and membrane flux against varied channel height.


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We would like to acknowledge financial support from the Australian Research Council. This work made use of the facilities at the Monash Centre for Electron Microscopy (MCEM).

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C.C. conceived, designed and carried out the experiments under the guidance of D.L. and G.P.S. D.L. and C.C. formulated the concept of using a nano-confined electrical double layer for ion modulation. G.J. designed and carried out the theoretical modelling under the guidance of J.Z.L. All authors discussed and interpreted the results. C.C. and G.J. wrote the manuscript with contributions from all the other authors.

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Correspondence to Jefferson Zhe Liu or Dan Li.

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Cheng, C., Jiang, G., Simon, G.P. et al. Low-voltage electrostatic modulation of ion diffusion through layered graphene-based nanoporous membranes. Nature Nanotech 13, 685–690 (2018).

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