journal article·2024-08Open access

Molecular transport enhancement in pure metallic carbon nanotube porins

Yuhao Li, Zhongwu Li, Rahul Prasanna Misra, Chenxing Liang, Alice J. Gillen, Sidi Zhao, Jobaer Abdullah, Ted Laurence, Jeffrey A. Fagan, Narayana Aluru, Daniel Blankschtein, Aleksandr Noy

Nature Materials· Volume 23· Issue 8

Abstract

Nanofluidic channels impose extreme confinement on water and ions, giving rise to unusual transport phenomena strongly dependent on the interactions at the channel-wall interface. Yet how the electronic properties of the nanofluidic channels influence transport efficiency remains largely unexplored. Here we measure transport through the inner pores of sub-1 nm metallic and semiconducting carbon nanotube porins. We find that water and proton transport are enhanced in metallic nanotubes over semiconducting nanotubes, whereas ion transport is largely insensitive to the nanotube bandgap value. Molecular simulations using polarizable force fields highlight the contributions of the anisotropic polarizability tensor of the carbon nanotubes to the ion-nanotube interactions and the water friction coefficient. We also describe the origin of the proton transport enhancement in metallic nanotubes using deep neural network molecular dynamics simulations. These results emphasize the complex role of the electronic properties of nanofluidic channels in modulating transport under extreme nanoscale confinement.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Nanopore and Nanochannel Transport Studies · Carbon Nanotubes in Composites · Graphene research and applications

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

References (60)

Show source-provided references
1. Werber, J. R., Osuji, C. O. & Elimelech, M. Materials for next-generation desalination and water purification membranes. Nat. Rev. Mater. 1, 16018 (2016).10.1038/natrevmats.2016.18 ↗
2. Cheisson, T. & Schelter, E. J. Rare earth elements: Mendeleev’s bane, modern marvels. Science 363, 489–493 (2019).10.1126/science.aau7628 ↗
3. Lively, R. P. & Sholl, D. S. From water to organics in membrane separations. Nat. Mater. 16, 276–279 (2017).10.1038/nmat4860 ↗
4. Lalia, B. S., Kochkodan, V., Hashaikeh, R. & Hilal, N. A review on membrane fabrication: structure, properties and performance relationship. Desalination 326, 77–95 (2013).10.1016/j.desal.2013.06.016 ↗
5. 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 ↗
6. Aidley, D. J. & Stanfield, P. R. Ion Channels: Molecules in Action (Cambridge Univ. Press, 1996).
7. Fyles, T. M. Synthetic ion channels in bilayer membranes. Chem. Soc. Rev. 36, 335–347 (2007).10.1039/B603256G ↗
8. Faucher, S. et al. Critical knowledge gaps in mass transport through single-digit nanopores: a review and perspective. J. Phys. Chem. C 123, 21309–21326 (2019).10.1021/acs.jpcc.9b02178 ↗
9. Tunuguntla, R. H. et al. Enhanced water permeability and tunable ion selectivity in sub-nanometer carbon nanotube porins. Science 357, 792–796 (2017).10.1126/science.aan2438 ↗
10. Noy, A. et al. Nanofluidics in carbon nanotubes. Nano Today 2, 22–29 (2007).10.1016/S1748-0132(07)70170-6 ↗
11. Corry, B. Designing carbon nanotube membranes for efficient water desalination. J. Phys. Chem. B 112, 1427–1434 (2008).10.1021/jp709845u ↗
12. Peter, C. & Hummer, G. Ion transport through membrane-spanning nanopores studied by molecular dynamics simulations and continuum electrostatics calculations. Biophys. J. 89, 2222–2234 (2005).10.1529/biophysj.105.065946 ↗
13. Misra, R. P. & Blankschtein, D. Insights on the role of many-body polarization effects in the wetting of graphitic surfaces by water. J. Phys. Chem. C 121, 28166–28179 (2017).10.1021/acs.jpcc.7b08891 ↗
14. Li, Z. et al. Breakdown of the Nernst–Einstein relation in carbon nanotube porins. Nat. Nanotechnol. 18, 177–183 (2023).10.1038/s41565-022-01276-0 ↗
15. Kavokine, N., Bocquet, M.-L. & Bocquet, L. Fluctuation-induced quantum friction in nanoscale water flows. Nature 602, 84–90 (2022).10.1038/s41586-021-04284-7 ↗
16. Won, C. Y., Joseph, S. & Aluru, N. R. Effect of quantum partial charges on the structure and dynamics of water in single-walled carbon nanotubes. J. Chem. Phys. 125, 114701 (2006).10.1063/1.2338305 ↗
17. Sam, A., Prasad, V. & Sathian, S. P. Water flow in carbon nanotubes: the role of tube chirality. Phys. Chem. Chem. Phys. 21, 6566–6573 (2019).10.1039/C9CP00429G ↗
18. Panahi, A., Sadeghi, P., Akhlaghi, A. & Sabour, M. H. Investigating the effect of single-walled carbon nanotubes chirality on the electrokinetics transport of water and ions: a molecular dynamics study. Diam. Relat. Mater. 110, 108105 (2020).10.1016/j.diamond.2020.108105 ↗
19. Velioğlu, S. et al. Metallicity-dependent ultrafast water transport in carbon nanotubes. Small 16, 1907575 (2020).10.1002/smll.201907575 ↗
20. Liu, H. et al. Translocation of single-stranded DNA through single-walled carbon nanotubes. Science 327, 64–67 (2010).10.1126/science.1181799 ↗
21. Liu, L., Yang, C., Zhao, K., Li, J. & Wu, H.-C. Ultrashort single-walled carbon nanotubes in a lipid bilayer as a new nanopore sensor. Nat. Commun. 4, 2989 (2013).
22. Choi, W. et al. Diameter-dependent ion transport through the interior of isolated single-walled carbon nanotubes. Nat. Commun. 4, 2397 (2013).
23. Fagan, J. A. et al. Isolation of specific small diameter single wall carbon nanotube species via aqueous two phase extraction. Adv. Mater. 26, 2800–2804 (2014).10.1002/adma.201304873 ↗
24. Tunuguntla, R. H., Escalada, A., Frolov, V. A. & Noy, A. Synthesis, lipid membrane incorporation and ion permeability testing of carbon nanotube porins. Nat. Protoc. 11, 2029–2047 (2016).10.1038/nprot.2016.119 ↗
25. Leptihn, S. et al. Constructing droplet interface bilayers from the contact of aqueous droplets in oil. Nat. Protoc. 8, 1048–1057 (2013).10.1038/nprot.2013.061 ↗
26. Hwang, W. L., Chen, M., Cronin, B., Holden, M. A. & Bayley, H. Asymmetric droplet interface bilayers. J. Am. Chem. Soc. 130, 5878–5879 (2008).10.1021/ja802089s ↗
27. Misra, R. P. & Blankschtein, D. Uncovering a universal molecular mechanism of salt ion adsorption at solid/water interfaces. Langmuir 37, 722–733 (2021).10.1021/acs.langmuir.0c02829 ↗
28. Kozinsky, B. & Marzari, N. Static dielectric properties of carbon nanotubes from first principles. Phys. Rev. Lett. 96, 166801 (2006).10.1103/PhysRevLett.96.166801 ↗
29. Lu, W., Wang, D. & Chen, L. Near-static dielectric polarization of individual carbon nanotubes. Nano Lett. 7, 2729–2733 (2007).10.1021/nl071208m ↗
30. Brothers, E. N., Scuseria, G. E. & Kudin, K. N. Longitudinal polarizability of carbon nanotubes. J. Phys. Chem. B 110, 12860–12864 (2006).10.1021/jp0603839 ↗
31. Siepmann, J. I. & Sprik, M. Influence of surface topology and electrostatic potential on water/electrode systems. J. Chem. Phys. 102, 511–524 (1995).10.1063/1.469429 ↗
32. Ojaghlou, N., Bratko, D., Salanne, M., Shafiei, M. & Luzar, A. Solvent–solvent correlations across graphene: the effect of image charges. ACS Nano 14, 7987–7998 (2020).10.1021/acsnano.9b09321 ↗
33. Schlaich, A., Jin, D., Bocquet, L. & Coasne, B. Electronic screening using a virtual Thomas–Fermi fluid for predicting wetting and phase transitions of ionic liquids at metal surfaces. Nat. Mater. 21, 237–245 (2022).10.1038/s41563-021-01121-0 ↗
34. Li, Y. et al. Water-ion permselectivity of narrow-diameter carbon nanotubes. Sci. Adv. 6, eaba9966 (2020).10.1126/sciadv.aba9966 ↗
35. Lamoureux, G., Harder, E., Vorobyov, I. V., Roux, B. & MacKerell, A. D. A polarizable model of water for molecular dynamics simulations of biomolecules. Chem. Phys. Lett. 418, 245–249 (2006).10.1016/j.cplett.2005.10.135 ↗
36. Berendsen, H.-J.-C., Grigera, J.-R. & Straatsma, T. P. The missing term in effective pair potentials. J. Phys. Chem. 91, 6269–6271 (1987).10.1021/j100308a038 ↗
37. Secchi, E. et al. Massive radius-dependent flow slippage in carbon nanotubes. Nature 537, 210–213 (2016).10.1038/nature19315 ↗
38. Aluru, N. R. et al. Fluids and electrolytes under confinement in single-digit nanopores. Chem. Rev. 123, 2737–2831 (2023).10.1021/acs.chemrev.2c00155 ↗
39. Walther, J. H., Ritos, K., Cruz-Chu, E. R., Megaridis, C. M. & Koumoutsakos, P. Barriers to superfast water transport in carbon nanotube membranes. Nano Lett. 13, 1910–1914 (2013).10.1021/nl304000k ↗
40. Dellago, C., Naor, M. M. & Hummer, G. Proton transport through water-filled carbon nanotubes. Phys. Rev. Lett. 90, 105902 (2003).10.1103/PhysRevLett.90.105902 ↗
41. Tunuguntla, R. H., Allen, F. I., Kim, K., Belliveau, A. & Noy, A. Ultrafast proton transport in sub-1-nm diameter carbon nanotube porins. Nat. Nanotechnol. 11, 639–644 (2016).10.1038/nnano.2016.43 ↗
42. Wang, H., Zhang, L., Han, J. & Weinan, E. DeePMD-kit: a deep learning package for many-body potential energy representation and molecular dynamics. Comp. Phys. Comm. 228, 178–184 (2018).10.1016/j.cpc.2018.03.016 ↗
43. Pichler, T. et al. Localized and delocalized electronic states in single-wall carbon nanotubes. Phys. Rev. Lett. 80, 4729–4732 (1998).10.1103/PhysRevLett.80.4729 ↗
44. Khripin, C. Y., Fagan, J. A. & Zheng, M. Spontaneous partition of carbon nanotubes in polymer-modified aqueous phases. J. Am. Chem. Soc. 135, 6822–6825 (2013).10.1021/ja402762e ↗
45. Fagan, J. A. Aqueous two-polymer phase extraction of single-wall carbon nanotubes using surfactants. Nanoscale Adv. 1, 3307–3324 (2019).10.1039/C9NA00280D ↗
46. Hicks, J. M. et al. Electric field induced biomimetic transmembrane electron transport using carbon nanotube porins. Small 17, 2102517 (2021).10.1002/smll.202102517 ↗
47. Wachlmayr, J. et al. Biophysical quantification of unitary solute and solvent permeabilities to enable translation to membrane science. J. Membr. Sci. 675, 121308 (2022).10.1016/j.memsci.2022.121308 ↗
48. Lamoureux, G. & Roux, B. Modeling induced polarization with classical Drude oscillators: theory and molecular dynamics simulation algorithm. J. Chem. Phys. 119, 3025–3039 (2003).10.1063/1.1589749 ↗
49. Thole, B. T. Molecular polarizabilities calculated with a modified dipole interaction. Chem. Phys. 59, 341–350 (1981).10.1016/0301-0104(81)85176-2 ↗
50. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comp. Phys. 117, 1–19 (1995).10.1006/jcph.1995.1039 ↗
51. Dequidt, A., Devémy, J. & Pádua, A. A. H. Thermalized Drude oscillators with the LAMMPS molecular dynamics simulator. J. Chem. Inform. Model. 56, 260–268 (2016).10.1021/acs.jcim.5b00612 ↗
52. Bocquet, L. & Barrat, J.-L. Flow boundary conditions from nano- to micro-scales. Soft Matter 3, 685–693 (2007).10.1039/b616490k ↗
53. Falk, K., Sedlmeier, F., Joly, L., Netz, R. R. & Bocquet, L. Molecular origin of fast water transport in carbon nanotube membranes: superlubricity versus curvature dependent friction. Nano Lett. 10, 4067–4073 (2010).10.1021/nl1021046 ↗
54. Thompson, A. P. et al. LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso and continuum scales. Comp. Phys. Comm. 271, 108171 (2022).10.1016/j.cpc.2021.108171 ↗
55. Wu, Y. & Aluru, N. R. Graphitic carbon–water nonbonded interaction parameters. J. Phys. Chem. B 117, 8802–8813 (2013).10.1021/jp402051t ↗
56. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).10.1103/PhysRev.140.A1133 ↗
57. Chen, J., Li, X.-Z., Zhang, Q., Michaelides, A. & Wang, E. Nature of proton transport in a water-filled carbon nanotube and in liquid water. Phys. Chem. Chem. Phys. 15, 6344–6349 (2013).10.1039/c3cp50218j ↗
58. Blickle, V., Speck, T., Lutz, C., Seifert, U. & Bechinger, C. Einstein relation generalized to nonequilibrium. Phys. Rev. Lett. 98, 210601 (2007).10.1103/PhysRevLett.98.210601 ↗
59. Zhang, L. et al. End-to-end symmetry preserving inter-atomic potential energy model for finite and extended systems. In Advances in Neural Information Processing Systems (NeurIPS 2018), 31 (eds Bengio, S. et al.) (2018).
60. Noy, A. et al. Molecular transport enhancement in pure metallic carbon nanotube porins. figshare https://doi.org/10.6084/m9.figshare.23205650 (2024).10.6084/m9.figshare.23205650 ↗