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The effect of hydration number on the interfacial transport of sodium ions

A Publisher Correction to this article was published on 22 August 2018

This article has been updated

Abstract

Ion hydration and transport at interfaces are relevant to a wide range of applied fields and natural processes1,2,3,4,5. Interfacial effects are particularly profound in confined geometries such as nanometre-sized channels6,7,8, where the mechanisms of ion transport in bulk solutions may not apply9,10. To correlate atomic structure with the transport properties of hydrated ions, both the interfacial inhomogeneity and the complex competing interactions among ions, water and surfaces require detailed molecular-level characterization. Here we constructed individual sodium ion (Na+) hydrates on a NaCl(001) surface by progressively attaching single water molecules (one to five) to the Na+ ion using a combined scanning tunnelling microscopy and noncontact atomic force microscopy system. We found that the Na+ ion hydrated with three water molecules diffuses orders of magnitude more quickly than other ion hydrates. Ab initio calculations revealed that such high ion mobility arises from the existence of a metastable state, in which the three water molecules around the Na+ ion can rotate collectively with a rather small energy barrier. This scenario would apply even at room temperature according to our classical molecular dynamics simulations. Our work suggests that anomalously high diffusion rates for specific hydration numbers of ions are generally determined by the degree of symmetry match between the hydrates and the surface lattice.

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Fig. 1: Geometries and high-resolution STM/AFM images of Na+ hydrates.
Fig. 2: Tip-induced diffusion dynamics of Na+ hydrates.
Fig. 3: Calculated diffusion barrier of Na+ hydrates by DFT.
Fig. 4: Molecular dynamics simulations of the diffusion of Na+ hydrates at high temperatures.

Change history

  • 22 August 2018

    In this Letter, the links to Supplementary Videos 5, 7, 9 and 10 were incorrect, and there were some formatting errors in the Supplementary Video legends. These errors have been corrected online.

References

  1. 1.

    Sipilä, M. et al. Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3. Nature 537, 532–534 (2016).

    ADS  Article  PubMed  PubMed Central  CAS  Google Scholar 

  2. 2.

    Klimeš, J., Bowler, D. R. & Michaelides, A. Understanding the role of ions and water molecules in the NaCl dissolution process. J. Chem. Phys. 139, 234702 (2013).

    ADS  Article  PubMed  CAS  Google Scholar 

  3. 3.

    Cohen-Tanugi, D. & Grossman, J. C. Water desalination across nanoporous graphene. Nano Lett. 12, 3602–3608 (2012).

    ADS  Article  PubMed  CAS  Google Scholar 

  4. 4.

    Payandeh, J., Scheuer, T., Zheng, N. & Catterall, W. A. The crystal structure of a voltage-gated sodium channel. Nature 475, 353–358 (2011).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  5. 5.

    Gouaux, E. & MacKinnon, R. Principles of selective ion transport in channels and pumps. Science 310, 1461–1465 (2005).

    ADS  Article  PubMed  CAS  Google Scholar 

  6. 6.

    Schoch, R. B., Han, J. & Renaud, P. Transport phenomena in nanofluidics. Rev. Mod. Phys. 80, 839–883 (2008).

    ADS  Article  CAS  Google Scholar 

  7. 7.

    Guo, W., Tian, Y. & Jiang, L. Asymmetric ion transport through ion-channel-mimetic solid-state nanopores. Acc. Chem. Res. 46, 2834–2846 (2013).

    Article  PubMed  CAS  Google Scholar 

  8. 8.

    Whitby, M. & Quirke, N. Fluid flow in carbon nanotubes and nanopipes. Nat. Nanotechnol. 2, 87–94 (2007).

    ADS  Article  PubMed  CAS  Google Scholar 

  9. 9.

    Stein, D., Kruithof, M. & Dekker, C. Surface-charge-governed ion transport in nanofluidic channels. Phys. Rev. Lett. 93, 035901 (2004).

    ADS  Article  PubMed  CAS  Google Scholar 

  10. 10.

    Duan, C. & Majumdar, A. Anomalous ion transport in 2-nm hydrophilic nanochannels. Nat. Nanotechnol. 5, 848–852 (2010).

    ADS  Article  PubMed  CAS  Google Scholar 

  11. 11.

    Omta, A. W., Kropman, M. F., Woutersen, S. & Bakker, H. J. Negligible effect of ions on the hydrogen-bond structure in liquid water. Science 301, 347–349 (2003).

    ADS  Article  PubMed  CAS  Google Scholar 

  12. 12.

    Heisler, I. A. & Meech, S. R. Low-frequency modes of aqueous alkali halide solutions: glimpsing the hydrogen bonding vibration. Science 327, 857–860 (2010).

    ADS  Article  PubMed  CAS  Google Scholar 

  13. 13.

    Tielrooij, K. J., Garcia-Araez, N., Bonn, M. & Bakker, H. J. Cooperativity in ion hydration. Science 328, 1006–1009 (2010).

    ADS  Article  PubMed  CAS  Google Scholar 

  14. 14.

    Carrillo-Tripp, M., Saint-Martin, H. & Ortega-Blake, I. A comparative study of the hydration of Na+ and K+ with refined polarizable model potentials. J. Chem. Phys. 118, 7062 (2003).

    ADS  Article  CAS  Google Scholar 

  15. 15.

    Jungwirth, P. & Tobias, D. J. Specific ion effects at the air/water interface. Chem. Rev. 106, 1259–1281 (2006).

    Article  PubMed  CAS  Google Scholar 

  16. 16.

    Kumagai, T. et al. H-atom relay reactions in real space. Nat. Mater. 11, 167–172 (2012).

    ADS  Article  CAS  Google Scholar 

  17. 17.

    Carrasco, J., Hodgson, A. & Michaelides, A. A molecular perspective of water at metal interfaces. Nat. Mater. 11, 667–674 (2012).

    ADS  Article  PubMed  CAS  Google Scholar 

  18. 18.

    Guo, J. et al. Real-space imaging of interfacial water with submolecular resolution. Nat. Mater. 13, 184–189 (2014).

    ADS  Article  PubMed  CAS  Google Scholar 

  19. 19.

    Maier, S. & Salmeron, M. How does water wet a surface? Acc. Chem. Res. 48, 2783–2790 (2015).

    Article  PubMed  CAS  Google Scholar 

  20. 20.

    Shiotari, A. & Sugimoto, Y. Ultrahigh-resolution imaging of water networks by atomic force microscopy. Nat. Commun. 8, 14313 (2017).

    ADS  Article  PubMed  PubMed Central  CAS  Google Scholar 

  21. 21.

    Peng, J. et al. Weakly perturbative imaging of interfacial water with submolecular resolution by atomic force microscopy. Nat. Commun. 9, 122 (2018).

    ADS  Article  PubMed  PubMed Central  CAS  Google Scholar 

  22. 22.

    Meng, X. et al. Direct visualization of concerted proton tunnelling in a water nanocluster. Nat. Phys. 11, 235–239 (2015).

    Article  CAS  Google Scholar 

  23. 23.

    Fukuma, T., Ueda, Y., Yoshioka, S. & Asakawa, H. Atomic-scale distribution of water molecules at the mica–water interface visualized by three-dimensional scanning force microscopy. Phys. Rev. Lett. 104, 016101 (2010).

    ADS  Article  PubMed  CAS  Google Scholar 

  24. 24.

    Ricci, M., Spijker, P. & Voitchovsky, K. Water-induced correlation between single ions imaged at the solid–liquid interface. Nat. Commun. 5, 4400 (2014).

    ADS  Article  PubMed  CAS  Google Scholar 

  25. 25.

    Giessibl, F. J. Advances in atomic force microscopy. Rev. Mod. Phys. 75, 949–983 (2003).

    ADS  Article  CAS  Google Scholar 

  26. 26.

    Peng, J. et al. Atomic-scale imaging of the dissolution of NaCl islands by water at low temperature. J. Phys. Condens. Matter 29, 104001 (2017).

    ADS  Article  PubMed  Google Scholar 

  27. 27.

    Gross, L. et al. The chemical structure of a molecule resolved by atomic force microscopy. Science 325, 1110–1114 (2009).

    ADS  Article  PubMed  CAS  Google Scholar 

  28. 28.

    Gawronski, H., Carrasco, J., Michaelides, A. & Morgenstern, K. Manipulation and control of hydrogen bond dynamics in absorbed ice nanoclusters. Phys. Rev. Lett. 101, 136102 (2008).

    ADS  Article  PubMed  CAS  Google Scholar 

  29. 29.

    Stipe, B. C., Rezaei, M. A. & Ho, W. Single-molecule vibrational spectroscopy and microscopy. Science 280, 1732–1735 (1998).

    ADS  Article  PubMed  CAS  Google Scholar 

  30. 30.

    Fuentes-Azcatl, R. & Barbosa, M. C. Sodium chloride, NaCl/ε: new force field. J. Phys. Chem. B 120, 2460–2470 (2016).

    Article  PubMed  CAS  Google Scholar 

  31. 31.

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    ADS  Article  CAS  Google Scholar 

  32. 32.

    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).

    ADS  Article  CAS  Google Scholar 

  33. 33.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    ADS  Article  CAS  Google Scholar 

  34. 34.

    Klimeš, J., Bowler, D. R. & Michaelides, A. Chemical accuracy for the van der Waals density functional. J. Phys. Condens. Matter 22, 022201 (2010).

    ADS  Article  PubMed  CAS  Google Scholar 

  35. 35.

    Klimeš, J., Bowler, D. R. & Michaelides, A. Van der Waals density functionals applied to solids. Phys. Rev. B 83, 195131 (2011).

    ADS  Article  CAS  Google Scholar 

  36. 36.

    Neugebauer, J. & Scheffler, M. Adsorbate-substrate and adsorbate–adsorbate interactions of Na and K adlayers on Al(111). Phys. Rev. B 46, 16067–16080 (1992).

    ADS  Article  CAS  Google Scholar 

  37. 37.

    Makov, G. & Payne, M. C. Periodic boundary conditions in ab initio calculations. Phys. Rev. B 51, 4014–4022 (1995).

    ADS  Article  CAS  Google Scholar 

  38. 38.

    Henkelman, G., Arnaldsson, A. & Jonsson, H. A fast and robust algorithm for Bader decomposition of charge density. Comput. Mater. Sci. 36, 354–360 (2006).

    Article  Google Scholar 

  39. 39.

    Henkelman, G. & Jonsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).

    ADS  Article  CAS  Google Scholar 

  40. 40.

    Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

    ADS  Article  CAS  Google Scholar 

  41. 41.

    Hapala, P., Temirov, R., Tautz, F. S. & Jelinek, P. Origin of high-resolution IETS-STM images of organic molecules with functionalized tips. Phys. Rev. Lett. 113, 226101 (2014).

    ADS  Article  PubMed  Google Scholar 

  42. 42.

    Hapala, P. et al. Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys. Rev. B 90, 085421 (2014).

    ADS  Article  CAS  Google Scholar 

  43. 43.

    Ellner, M. et al. The electric field of CO tips and its relevance for atomic force microscopy. Nano Lett. 16, 1974–1980 (2016).

    ADS  Article  PubMed  CAS  Google Scholar 

  44. 44.

    Leontyev, I. V. & Stuchebrukhov, A. A. Polarizable molecular interactions in condensed phase and their equivalent nonpolarizable models. J. Chem. Phys. 141, 014103 (2014).

    ADS  Article  PubMed  PubMed Central  CAS  Google Scholar 

  45. 45.

    Hansen, J. P. & McDonald, I. R. Theory of Simple Liquids 3rd edn (Academic Press, 2006).

  46. 46.

    Berendsen, H. J. C., Grigera, J. R. & Straatsma, T. P. The missing term in effective pair potentials. J. Phys. Chem. 91, 6269–6271 (1987).

    Article  CAS  Google Scholar 

  47. 47.

    Joung, I. S. & Cheatham, T. E. Molecular dynamics simulations of the dynamic and energetic properties of alkali and halide ions using water-model-specific ion parameters. J. Phys. Chem. B 113, 13279–13290 (2009).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  48. 48.

    Case, D. A. et al. AMBER version 14. http://ambermd.org (University of California, San Francisco, 2014).

    Google Scholar 

  49. 49.

    Ryckaert, J. P., Ciccotti, G. & Berendsen, H. J. C. Numerical integration of the Cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes. J. Comput. Phys. 23, 327–341 (1977).

    ADS  Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Key R&D Program under grant numbers 2016YFA0300901, 2017YFA0205003, 2016YFA0300903 and 2015CB856801; the National Natural Science Foundation of China under grant numbers 11634001, 11525520, 21573006 and 11290162/A040106; and the Key Research Program of the Chinese Academy of Sciences under grant numbers XDPB08-1 and XDPB08-4. Y.J. acknowledges support by the National Science Fund for Distinguished Young Scholars (grant number 21725302) and the Cheung Kong Young Scholar Program. P.H. and P.J. acknowledge support from the Czech Academy of Sciences project number MSM100101705 and Premium Academiae and GACR project number 18-09914S. J.G. acknowledges support from the National Postdoctoral Program for Innovative Talents. J.P. acknowledges support from the Weng Hongwu Original Research Foundation under grant number WHW201502. We are grateful for the computational resources provided by the TianHe-1A, TianHe II supercomputer, and the High-performance Computing Platform of Peking University. This work is supported in part by Songshan Lake Laboratory for Material Sciences.

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Nature thanks P. Asinari and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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Authors

Contributions

Y.J. and E.-G.W. designed and supervised the project. J.P. performed the STM/AFM measurements (with J.G. and R.M.). D.C., J.C., X.-Z.L. and L.-M.X. performed ab initio DFT calculations. Z.H., W.J.X. and Y.Q.G. carried out the classical molecular dynamics simulations. P.H. and P.J. carried out the theoretical simulations of the AFM images (in collaboration with D.C. and B.C.). J.P., D.C., Z.H., J.G., W.J.X., X.-Z.L., Y.Q.G., L.-M.X., E.-G.W. and Y.J. analysed the data. Y.J. wrote the manuscript with input from all other authors. The manuscript reflects the contributions of all authors.

Corresponding authors

Correspondence to Li-Mei Xu, Yi Qin Gao, En-Ge Wang or Ying Jiang.

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Supplementary information

Supplementary Information

This file contains Supplementary Text 1–13 (see contents page for more details), Supplementary Figures S1–S13, Supplementary Tables S1–S3 and references.

Video 1: Diffusion trajectory of Na+H2O on NaCl(001) surface during a period of 10 ns.

The video was generated by molecular dynamics simulations at 275 K. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Overall diffusion dynamics can be seen clearly in the video.

Video 2: Diffusion trajectory of Na+2H2O on NaCl(001) surface during a period of 10 ns.

The video was generated by molecular dynamics simulations at 275 K. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Overall diffusion dynamics can be seen clearly in the video.

Video 3: Diffusion trajectory of Na+3H2O on NaCl(001) surface during a period of 10 ns.

The video was generated by molecular dynamics simulations at 275 K. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Overall diffusion dynamics can be seen clearly in the video. The mobility of Na+·3H2O is more than one order of magnitude larger than that of other clusters.

Video 4: Diffusion trajectory of Na+4H2O on NaCl(001) surface during a period of 10 ns.

The video was generated by molecular dynamics simulations at 275 K. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Overall diffusion dynamics can be seen clearly in the video.

Video 5: Diffusion trajectory of Na+5H2O on NaCl(001) surface during a period of 10 ns.

The video was generated by molecular dynamics simulations at 275 K. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Overall diffusion dynamics can be seen clearly in the video.

Video 6: Diffusion trajectory of Na+H2O during a period of 20 ps.

The video was generated by molecular dynamics simulations at 300 K and played with a 2,000-times higher frame rate than Supplementary Video 1. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. The intermediate transitions during the diffusion can be seen clearly in the video. Na·H2O hops between the bridge sites, accompanied with the rotation of water around the Na+.

Video 7: Diffusion trajectory of Na+2H2O during a period of 20 ps.

The video was generated by molecular dynamics simulations at 300 K and played with a 2,000-times higher frame rate than Supplementary Video 2. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Na+·2H2O hops between the bridge sites, accompanied with the rotation of two water molecules around the Na+.

Video 8: Diffusion trajectory of Na+3H2O during a period of 20 ps.

The video was generated by molecular dynamics simulations at 300 K and played with a 2,000-times higher frame rate than Supplementary Video 3. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. The diffusion of Na+·3H2O is facilitated by a metastable state (Fig. 4f), where the Na+ is located at the top Cl− site of NaCl in contrast to the bridge site in the most stable state (Fig. 4e). See Fig. 4 for detailed discussions.

Video 9: Diffusion trajectory of Na+4H2O during a period of 20 ps.

The video was generated by molecular dynamics simulations at 300 K and played with a 2,000-times higher frame rate than Supplementary Video 4. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Na+·4H2O hops between the top Cl− sites. The diffusion of Na+·4H2O is usually accompanied with the flipping of water molecules, that is, one water molecule climbs onto the top of the Na+ ion, leaving the rest three in contact with the surface. Such a configuration resembles that of Na+·3H2O, leading to the stabilization at the bridge site. See Supplementary Figure 11 for detailed discussions.

Video 10: Diffusion trajectory of Na+5H2O during a period of 20 ps.

The video was generated by molecular dynamics simulations at 300 K and played with a 2,000-times higher frame rate than Supplementary Video 5. H, O, Cl, Na atoms are denoted as white, red, green and purple spheres, respectively. Na+·5H2O hops between the top Cl− sites and shows a similar flipping-assisted diffusion behaviour to Na+·4H2O. See Supplementary Figure 11 for detailed discussions.

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Peng, J., Cao, D., He, Z. et al. The effect of hydration number on the interfacial transport of sodium ions. Nature 557, 701–705 (2018). https://doi.org/10.1038/s41586-018-0122-2

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