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Advancing osmotic power generation by covalent organic framework monolayer

Nature Nanotechnology volume 17, pages 622–628 (2022)Cite this article

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Abstract

Osmotic power, also known as ‘blue energy’, is produced by mixing solutions of different salt concentrations, and represents a vast, sustainable and clean energy source. The efficiency of harvesting osmotic power is primarily determined by the transmembrane performance, which is in turn dependent on ion conductivity and selectivity towards positive or negative ions. Atomically or molecularly thin membranes with a uniform pore environment and high pore density are expected to possess an outstanding ion permeability and selectivity, but remain unexplored. Here we demonstrate that covalent organic framework monolayer membranes that feature a well-ordered pore arrangement can achieve an extremely low membrane resistivity and ultrahigh ion conductivity. When used as osmotic power generators, these membranes produce an unprecedented output power density over 200 W m−2 on mixing the artificial seawater and river water. This work opens up the application of porous monolayer membranes with an atomically precise structure in osmotic power generation.

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Fig. 1: Shape and structure characterization of a COF monolayer membrane.
Fig. 2: Transmembrane ion current and voltage.
Fig. 3: Osmotic power generation in NaCl solution.
Fig. 4: Enhanced osmotic power generation in multivalent ion electrolytes.

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Data availability

All the 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

We acknowledge financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB36000000, Z.T.), National Key Basic Research Program of China (2016YFA0200700, Z.T.), National Natural Science Foundation of China (21922504 and 52073069, L.L., and 92056204, 21890381 and 21721002, Z.T.), Frontier Science Key Project of the Chinese Academy of Sciences (QYZDJ-SSW-SLH038, Z.T.), Youth Innovation Promotion Association CAS (2018046, L.L.), China National Postdoctoral Program for Innovative Talents (BX20200102, J.Y.) and China Postdoctoral Science Foundation (2019M660583, J.Y.). K. Peng is acknowledged for focused ion beam (FIB) technical help.

Author information

Author notes

  1. These authors contributed equally: Jinlei Yang, Bin Tu.

Authors and Affiliations

  1. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, P. R. China

    Jinlei Yang, Bin Tu, Guangjie Zhang, Pengchao Liu, Kui Hu, Jiarong Wang, Zhuang Yan, Zhiwei Huang, Munan Fang, Junjun Hou, Qiaojun Fang, Xiaohui Qiu, Lianshan Li & Zhiyong Tang

  2. University of Chinese Academy of Sciences, Beijing, P. R. China

    Bin Tu, Guangjie Zhang, Kui Hu, Jiarong Wang, Zhuang Yan, Zhiwei Huang, Munan Fang, Junjun Hou, Qiaojun Fang, Xiaohui Qiu, Lianshan Li & Zhiyong Tang

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Contributions

L.L., J.Y. and Z.T. conceived the research idea, designed all the experiments and wrote the manuscript. J.Y., P.L. and M.F. carried out the experimental measurements and data analysis with help from K.H., J.W. and Z.Y. B.T. performed the simulations and interpreted the simulation results. G.Z., Z.H., J.H., Q.F. and X.Q. joined the discussion of the data and gave useful suggestions. All the authors commented on the manuscript.

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Correspondence to Lianshan Li or Zhiyong Tang.

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Nature Nanotechnology thanks Soryong Chae 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 Electrochemical measurement.

a, Scheme of the experimental setup. ZnTPP-COF monolayer membrane suspending on the SiNx/Si chip containing a 2 μm aperture is mounted on a Teflon disk, with both sides of the membrane in contact with aqueous solution. Ag/AgCl electrodes are applied to characterize the current-voltage response, where agarose salt bridges are used to eliminate the imbalanced redox potential at the electrode|electrolyte interface. b, Photograph of the disassembled electrochemical device. c, An empty SiNx aperture and a ZnTPP-COF monolayer membrane covered SiNx aperture.

Extended Data Fig. 2 Ion selectivity simulation.

a, The simulated 2D domain for PNP model. The pore length and diameter of each pore is 0.6 nm and 2 nm, respectively. In all the simulations, the concentration and potential of the central pore are used to calculate the current. b, c, Calculated steady-state concentration distribution of K+ (b) and Cl− (c) near ZnTPP-COF monolayer membrane with a surface charge density of 4.1 mC m-2 under a salt gradient of 10 mM/0.1 mM, respectively. The higher concentration of Cl− (counter-ions) compared with that of K+ (co-ions) in the whole pore region suggests the anion selectivity of the membrane. d, An electrostatic potential under salt gradient of 10 mM/0.1 mM builds up along the salinity gradient direction, owing to the selective transport of anions across the membrane.

Extended Data Fig. 3 Investigation on the pore-pore coupling effect.

a, Electrostatic potential showing different pore-pore coupling between the central pore and the 1-1, 2-2, 3-3, and 4-4 pores. b, Ion selectivity of the central pore upon coupling with the 1-1, 2-2, 3-3, and 4-4 pores. c, Osmotic current of the central pore upon coupling with the 1-1, 2-2, 3-3, and 4-4 pores. Surface charge density is set to be 4.1 mC m−2 under a salt gradient of 10 mM KCl/0.1 mM KCl.

Extended Data Fig. 4 Effect of interpore distance on the pore-pore coupling effect.

a, Electrostatic potential built under varied pore distance of 2.5 nm to 8.5 nm. b, Ion selectivity of the central pore when the interpore distance increases from 2.5 nm to 8.5 nm. c, Osmotic current of the central pore when the interpore distance increases from 2.5 nm to 8.5 nm. Surface charge density is set to be 4.1 mC m−2 under a salt gradient of 10 mM KCl/0.1 mM KCl. In the range of the interpore distance larger than 4.5 nm, small change in ion selectivity but obvious drop in osmotic current are discerned with the interpore distance decreasing (in other words, the pore density increasing), which reflects the effect of enhanced concentration polarization or ion transport resistance. On the contrary, in the range of the interpore distance smaller than 4.5 nm, a positive gain of pore-pore coupling effect comes to play a dominant role, namely, large increase in ion selectivity. This result reveals big enhancement of ion selectivity due to the strong pore-pore coupling. Meanwhile, the enhancement of osmotic current caused by the pore-pore coupling effect greatly compensates the decrease of osmotic current caused by concentration polarization or ion transport resistance, as the interpore distance decreases to below 4.5 nm (Extended Data Fig. 4c).

Extended Data Fig. 5 Atomic charge distribution of ZnTPP-COF (a), NiTPP-COF (b) and CuTPP-COF (c) from DFT calculation.

The metal centers show positive charge intensity in the order of ZnTPP-COF > NiTPP-COF > CuTPP-COF, which is consistent with the experimental trend on the positive surface charge density of these membranes. (orange: Zn, teal: Ni, green: Cu, blue: N, red: O, grey: C, white: H).

Extended Data Fig. 6 Osmotic power generation by NiTPP-COF and CuTPP-COF monolayer membranes.

Current-voltage curves (a, d) as well as current density and output power density on the external load resistance (b, e) of NiTPP-COF (a, b) and CuTPP-COF (d, e) monolayer membranes in the artificial seawater/artificial river water gradient system. Ios and Vos are the osmotic current and voltage, respectively. The current density-time curves of NiTPP-COF (c) and CuTPP-COF (f) monolayer membranes with electrolyte replenishing every 50 min operated under the condition of the maximum output power density.

Extended Data Table 1 Ionic species and their bulk diffusion coefficient
Full size table
Extended Data Table 2 Ion composition in the artificial seawater46
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–23, discussion and Tables 1–5.

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Yang, J., Tu, B., Zhang, G. et al. Advancing osmotic power generation by covalent organic framework monolayer. Nat. Nanotechnol. 17, 622–628 (2022). https://doi.org/10.1038/s41565-022-01110-7

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