Power generation by reverse electrodialysis in a single-layer nanoporous membrane made from core–rim polycyclic aromatic hydrocarbons

Abstract

Nanoporous graphene and related atomically thin layered materials are promising candidates in reverse electrodialysis research owing to their remarkable ionic conductivity and high permselectivity. The synthesis of atomically thin nanoporous membranes with a narrow pore size distribution, however, remains challenging. Here, we report the fabrication of nanoporous carbon membranes via the thermal crosslinking of core–rim structured monomers, that is, polycyclic aromatic hydrocarbons. The mechanically robust, centimetre-sized membrane has a pore size of 3.6 ± 1.8 nm and a thickness of 2.0 ± 0.5 nm. When applied to reverse electrodialysis, the nanoporous carbon membrane offers a high short-circuit current with an output power density of 67 W m−2, which is about two orders of magnitude beyond that of the classic ion-exchange membranes and current prototype nanoporous membranes reported in the literature. Crosslinked and atomically thin porous polycyclic aromatic hydrocarbon membranes therefore represent new scaffolds that will revolutionize the rapidly developing fields of sustainable energy and membrane technology.

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Fig. 1: The preparation of atomically thin nanoporous carbon membranes.
Fig. 2: Characterization of the membrane prepared at 10 mN m−1.
Fig. 3: Pore density and transmembrane ionic current measurements.
Fig. 4: Reverse electrodialysis performance of the membrane prepared at 10 mN m–1.

Data availability

Source data for Figs. 14 and Extended Data Fig. 1 are provided with the paper. All other data that support the plots within this paper and other findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

This work is supported by the Netherlands Organization for Scientific Research (Vidi 723.013.007), the European Research Council (ERC) Proof of Concept NANOPORE (no. 780004). We acknowledge Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) Exact and Natural Sciences for the use of the supercomputer facilities at SURFsara. H.Q. and U.K. gratefully acknowledge the financial support by the German Research Foundation (DFG) and the Ministry of Science, Research and the Arts (MWK) of Baden-Wuerttemberg in the framework of the “SALVE” (Sub-Angstrom Low-Voltage Electron Microscopy) project (DFG KA 1295/21-1). S. G. Lemay is acknowledged for the general discussion about nanofluidics. W. Fu and X. Zhang are acknowledged for the discussions about ionic conductance. J. van Gerwen and C. van Helvoirt are acknowledged for the XPS measurements.

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Contributions

G.F.S. supervised the project. X.L. performed the monomer synthesis and characterization. X.L. and M.H. performed the membrane synthesis, characterization and ionic conductance measurements. H.Q. and U.K. conducted HRTEM and HAADF-STEM measurements. D.C., G.J.A.S. and F.B. performed the MD simulations. K.B.S.S.G., D.C., G.J.A.S., F.B. and H.d.G. performed the solid-state NMR studies. All authors contributed to discussions. X.L. wrote the manuscript with help from all authors.

Corresponding author

Correspondence to Grégory F. Schneider.

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Peer review information Nature Nanotechnology thanks Yongsheng Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 MD simulations analysis of HPAHBC molecules on water surface.

ac, Schematic visualization of starting conformations for the HPAHBC molecules at the beginning of the MD simulation, vertical (a), stacked (b), planar (c); carbon atoms are shown in grey and nitrogen atoms in blue balls (hydrogens are omitted). d, Illustration of the tilt angle Φ (red arc) between the plane of the HBC ring defined by three specific carbon atom on the edge (yellow balls) and the x–y plane; carbon atoms in grey, nitrogen atoms in blue (hydrogens are omitted). The cpptraj module of AmberTools are used for the calculation of the HBC plane. e, Distribution of tilt angle (Φ) per each molecule from MD simulations with the increasing amount of HPAHBC molecules, from 1 to 6, and different starting point conformation, vertical (red), stacked (blue), planar (green). With the red circle at 90° and the concentric blue-green circle at 0°, we underline the starting point for the tilt angle at the beginning of the pre-equilibration simulations, for vertical and stacked-planar conformation, respectively. f, Distribution of number of hydrogen bonds (H-bonds) per HPAHBC molecule from MD simulations with increasing amount of the HPAHBC molecules, from 1 to 6, and different starting point conformation, vertical (red), stacked (blue), planar (green). Gromacs Tool (gmx hbond) is used for the calculation of the number of hydrogen bonds determined based on cutoffs for the angle Hydrogen–OH–N 125º and the distance OH–N 3.5 Å. OH is regarded as the donor, N as the acceptor. The distribution curves were obtained via Gaussian broadening with default standard deviation. Source data

Extended Data Fig. 2 Solid-state NMR spectra of HPAHBC powder annealed at different temperatures.

As the temperature increases from 400 degrees to 550 degrees, the peaks marked with blue dots gradually vanish, which is attributed to decomposition of the dipyridylamino rim.

Supplementary information

Supplementary Information

Supplementary Figs. 1–26, Tables 1–5 and refs. 1–13.

Source data

Source Data Fig. 1

Numerical data.

Source Data Fig. 2

Numerical data.

Source Data Fig. 3

Numerical data.

Source Data Fig. 4

Numerical data.

Source Data Extended Data Fig. 1

Numerical data.

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Liu, X., He, M., Calvani, D. et al. Power generation by reverse electrodialysis in a single-layer nanoporous membrane made from core–rim polycyclic aromatic hydrocarbons. Nat. Nanotechnol. 15, 307–312 (2020). https://doi.org/10.1038/s41565-020-0641-5

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