journal article·2026-05

Versatile heavy metal ion separation via biological ion-channel-inspired membranes

Yongye Zhao, Hongfei Gao, Lei Yu, Qi Li, Chaoxu Li, Lei Jiang, Jun Gao

Nature Nanotechnology· Volume 21· Issue 5
Publisher page

Abstract

Solvent extraction and adsorption methods are predominantly used to extract heavy metal ions by binding them selectively. However, these methods require excessive chemical use and cause environmental problems. The membrane separation method avoids these problems but remains poorly compatible with heavy metal ions. In nature, biological CaV channels allow selectively bound ions (Ca2+) to rapidly and selectively permeate by exploiting the repulsive interactions between single-file ions and the anomalous mole fraction effect. Here, inspired by these channels, we demonstrate a general strategy that can transform adsorptive materials into separation membranes for heavy metal ion separation. The membranes consist of channels that can adsorb target ions in a single file. Using uranium-adsorption channels, uranium separation via the membrane was achieved, demonstrating a uranium/vanadium selectivity of 734 in real seawater and a throughput far exceeding that of previous materials. This strategy is further generalized to the separation of rare earth metals, copper and gold. Moreover, this strategy unifies the adsorption and membrane separation methods, and can also transform separation membranes to adsorbents, showing notably enhanced capacity and selectivity by rejecting the entering of competing ions, reducing the environmental impact of the adsorption method.
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Research context

OpenAlex topics: Extraction and Separation Processes · Chemical Synthesis and Characterization · Adsorption and biosorption for pollutant removal

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (57)

Show source-provided references
1. DuChanois, R. M. et al. Prospects of metal recovery from wastewater and brine. Nat. Water 1, 37–46 (2023).10.1038/s44221-022-00006-z ↗
2. Pell, R. et al. Towards sustainable extraction of technology materials through integrated approaches. Nat. Rev. Earth. Environ. 2, 665–679 (2021).10.1038/s43017-021-00211-6 ↗
3. Wilson, A. M. et al. Solvent extraction: the coordination chemistry behind extractive metallurgy. Chem. Soc. Rev. 43, 123–134 (2014).10.1039/C3CS60275C ↗
4. Vahidi, E. & Zhao, F. Environmental life cycle assessment on the separation of rare earth oxides through solvent extraction. J. Environ. Manage. 203, 255–263 (2017).10.1016/j.jenvman.2017.07.076 ↗
5. Xie, Y. et al. Uranium extraction from seawater: material design, emerging technologies and marine engineering. Chem. Soc. Rev. 52, 97–162 (2023).10.1039/D2CS00595F ↗
6. Mattocks, J. A. et al. Enhanced rare-earth separation with a metal-sensitive lanmodulin dimer. Nature 618, 87–93 (2023).10.1038/s41586-023-05945-5 ↗
7. Uliana, A. A. et al. Ion-capture electrodialysis using multifunctional adsorptive membranes. Science 372, 296–299 (2021).10.1126/science.abf5991 ↗
8. Liang, J. et al. Constructing two-dimensional (2D) heterostructure channels with engineered biomembrane and graphene for precise scandium sieving. Adv. Mater. 36, 2470240 (2024).10.1002/adma.202470240 ↗
9. Qasem, N. A. A., Mohammed, R. H. & Lawal, D. U. Removal of heavy metal ions from wastewater: a comprehensive and critical review. NPJ Clean Water 4, 36 (2021).10.1038/s41545-021-00127-0 ↗
10. Chen, L. et al. An overview on membrane strategies for rare earths extraction and separation. Sep. Purif. Technol. 197, 70–85 (2018).10.1016/j.seppur.2017.12.053 ↗
11. Lair, L. et al. Critical mineral separations: opportunities for membrane materials and processes to advance sustainable economies and secure supplies. Annu. Rev. Chem. Biomol. Eng. 15, 243–266 (2024).10.1146/annurev-chembioeng-100722-114853 ↗
12. Epsztein, R., DuChanois, R. M., Ritt, C. L., Noy, A. & Elimelech, M. Towards single-species selectivity of membranes with subnanometre pores. Nat. Nanotechnol. 15, 426–436 (2020).10.1038/s41565-020-0713-6 ↗
13. Violet, C. et al. Designing membranes with specific binding sites for selective ion separations. Nat. Water 2, 706–718 (2024).10.1038/s44221-024-00279-6 ↗
14. Razmjou, A., Asadnia, M., Hosseini, E., Habibnejad Korayem, A. & Chen, V. Design principles of ion selective nanostructured membranes for the extraction of lithium ions. Nat. Commun. 10, 5793 (2019).10.1038/s41467-019-13648-7 ↗
15. Zhang, H. et al. Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides. Nature 616, 482–487 (2023).10.1038/s41586-023-05840-z ↗
16. DuChanois, R. M. et al. Designing polymeric membranes with coordination chemistry for high-precision ion separations. Sci. Adv. 8, eabm9436 (2022).10.1126/sciadv.abm9436 ↗
17. Sheng, C., Wijeratne, S., Cheng, C., Baker, G. L. & Bruening, M. L. Facilitated ion transport through polyelectrolyte multilayer films containing metal-binding ligands. J. Membr. Sci. 459, 169–176 (2014).10.1016/j.memsci.2014.01.051 ↗
18. Hess, P. & Tsien, R. W. Mechanism of ion permeation through calcium channels. Nature 309, 453–456 (1984).10.1038/309453a0 ↗
19. Tang, L. et al. Structural basis for Ca2+ selectivity of a voltage-gated calcium channel. Nature 505, 56–61 (2014).10.1038/nature12775 ↗
20. Tsien, R. W. Calcium Signals (OP Publishing, 2023).
21. Friel, D. D. & Tsien, R. W. Voltage-gated calcium channels: direct observation of the anomalous mole fraction effect at the single-channel level. Proc. Natl Acad. Sci. USA 86, 5207–5211 (1989).10.1073/pnas.86.13.5207 ↗
22. Hille, B. Ion Channels Of Excitable Membranes Vol. 507 (Sinauer Sunderland, 2001).
23. Côté, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).10.1126/science.1120411 ↗
24. Ding, S.-Y. & Wang, W. Covalent organic frameworks (COFs): from design to applications. Chem. Soc. Rev. 42, 548–568 (2013).10.1039/C2CS35072F ↗
25. Huang, N., Wang, P. & Jiang, D. Covalent organic frameworks: a materials platform for structural and functional designs. Nat. Rev. Mater. 1, 16068 (2016).10.1038/natrevmats.2016.68 ↗
26. Sun, Q. et al. Covalent organic frameworks as a decorating platform for utilization and affinity enhancement of chelating sites for radionuclidesequestration. Adv. Mater. 30, 1705479 (2018).10.1002/adma.201705479 ↗
27. Yang, L. et al. Bioinspired hierarchical porous membrane for efficient uranium extraction from seawater. Nat. Sustain. 5, 71–80 (2022).10.1038/s41893-021-00792-6 ↗
28. Wang, Y. et al. High-Purity, High-yield synthesis of covalent organic framework nanosheets for fast and selective molecular separation. Chem. Mater. 34, 6345–6354 (2022).10.1021/acs.chemmater.2c00834 ↗
29. Qian, C. et al. Imine and imine-derived linkages in two-dimensional covalent organic frameworks. Nat. Rev. Chem. 6, 881–898 (2022).10.1038/s41570-022-00437-y ↗
30. Zhang, W. et al. Reconstructed covalent organic frameworks. Nature 604, 72–79 (2022).10.1038/s41586-022-04443-4 ↗
31. Liang, Y. et al. Polyamide nanofiltration membrane with highly uniform sub-nanometre pores for sub-1 Å precision separation. Nat. Commun. 11, 2015 (2020).10.1038/s41467-020-15771-2 ↗
32. Wang, A. et al. Selective ion transport through hydrated micropores in polymer membranes. Nature 635, 353–358 (2024).10.1038/s41586-024-08140-2 ↗
33. Yang, D. et al. Solution-processable polymer membranes with hydrophilic subnanometre pores for sustainable lithium extraction. Nat. Water 3, 319–333 (2025).10.1038/s44221-025-00398-8 ↗
34. Gui, Y. et al. High-performance membrane for rapid and selective extraction of uranium from simulated seawater: a novel polyacrylonitrile-poly(amidoxime) hydrogel membrane material. J. Water Process Eng. 69, 106732 (2025).10.1016/j.jwpe.2024.106732 ↗
35. Ahmad, Z. et al. A membrane-supported bifunctional poly(amidoxime-ethyleneimine) network for enhanced uranium extraction from seawater and wastewater. J. Hazard. Mater. 427, 127995 (2021).
36. Corry, B., Allen, T. W., Kuyucak, S. & Chung, S. H. Mechanisms of permeation and selectivity in calcium channels. Biophys. J. 80, 195–214 (2001).10.1016/S0006-3495(01)76007-9 ↗
37. Xie, F., Zhang, T. A., Dreisinger, D. & Doyle, F. A critical review on solvent extraction of rare earths from aqueous solutions. Miner. Eng. 56, 10–28 (2014).10.1016/j.mineng.2013.10.021 ↗
38. Avdibegović, D., Regadío, M. & Binnemans, K. Recovery of scandium(III) from diluted aqueous solutions by a supported ionic liquid phase (SILP). RSC Adv. 7, 49664–49674 (2017).10.1039/C7RA07957E ↗
39. Yuan, Y. et al. Selective scandium ion capture through coordination templating in a covalent organic framework. Nat. Chem. 15, 1599–1606 (2023).10.1038/s41557-023-01273-3 ↗
40. Free, M. L. Hydrometallurgy: Fundamentals And Applications (Springer Nature, 2021).
41. Kaes, C., Katz, A. & Hosseini, M. W. Bipyridine: the most widely used ligand. A review of molecules comprising at least two 2,2’-bipyridine units. Chem. Rev. 100, 3553–3590 (2000).10.1021/cr990376z ↗
42. Harper, M. J. et al. Oxidative sddition, transmetalation, and reductive elimination at a 2,2′-bipyridyl-ligated gold center. J. Am. Chem. Soc. 140, 4440–4445 (2018).10.1021/jacs.8b01411 ↗
43. Cocco, F. et al. Intramolecular C(sp2)–H bond activation in 6,6′-dimethoxy-2,2′-bipyridine with gold(III). Crystal and molecular structure of the first N′,C(3) ‘rollover’ cycloaurated derivative. Organometallics 29, 1064–1066 (2010).10.1021/om1000474 ↗
44. Li, Q. et al. Covalent organic framework interlayer spacings as perfectly selective artificial proton channels. Angew. Chem. Int. Ed. 63, e202402094 (2024).10.1002/anie.202402094 ↗
45. Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
46. Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
47. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).10.1103/PhysRevB.59.1758 ↗
48. Perdew, J. P. & Zunger, A. Self-interaction correction to density-functional approximations for many-electron systems. Phys. Rev. B 23, 5048–5079 (1981).10.1103/PhysRevB.23.5048 ↗
49. Liechtenstein, A. I., Anisimov, V. V. & Zaanen, J. Density-functional theory and strong interactions: orbital ordering in Mott–Hubbard insulators. Phys. Rev. B 52, R5467–R5470 (1995).10.1103/PhysRevB.52.R5467 ↗
50. Dudarev, S. L., Manh, D. N. & Sutton, A. P. Effect of Mott–Hubbard correlations on the electronic structure and structural stability of uranium dioxide. Philos. Mag. B 75, 613–628 (1997).10.1080/13642819708202343 ↗
51. Liebsch, A., Ishida, H. & Bihlmayer, G. Coulomb correlations and orbital polarization in the metal-insulator transition of VO2. Phys. Rev. B 71, 085109 (2005).10.1103/PhysRevB.71.085109 ↗
52. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).10.1103/PhysRevB.13.5188 ↗
53. Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).10.1063/1.4865107 ↗
54. He, X., Zhu, Y. & Mo, Y. Origin of fast ion diffusion in super-ionic conductors. Nat. Commun. 8, 15893 (2017).10.1038/ncomms15893 ↗
55. Humphrey, W., Dalke, A. & Schulten, K. VMD: visual molecular dynamics. J. Mol. Graph. 14, 33–38 (1996).10.1016/0263-7855(96)00018-5 ↗
56. Plimpton, S. Fast parallel algorithms for short-range molecular-dynamics. J. Comput. Phys. 117, 1–19 (1995).10.1006/jcph.1995.1039 ↗
57. Jorgensen, W. L., Maxwell, D. S. & TiradoRives, J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).10.1021/ja9621760 ↗