Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Probing the critical nucleus size for ice formation with graphene oxide nanosheets

Nature volume 576, pages 437–441 (2019)Cite this article

Subjects

Abstract

Water freezing is ubiquitous and affects areas as diverse as climate, the chemical industry, cryobiology and materials science. Ice nucleation is the controlling step in water freezing1,2,3,4,5 and has, for nearly a century, been assumed to require the formation of a critical ice nucleus6,7,8,9,10. But there has been no direct experimental evidence for the existence of such a nucleus, owing to its transient and nanoscale nature6,7. Here we report ice nucleation in water droplets containing graphene oxide nanosheets of controlled sizes and show that they have a notable impact on ice nucleation only above a certain size that varies with the degree of supercooling of the droplets. We infer from our experimental data and theoretical calculations that the critical size of the graphene oxide reflects the size of the critical ice nucleus, which in the case of sufficiently large graphene oxides sits on their surface and gives rise to ice formation behaviour consistent with classical nucleation theory. By contrast, when the graphene oxide size is smaller than that of the critical ice nucleus, pinning at the periphery of the graphene oxide deforms the ice nucleus as it grows. This gives rise to a much higher free-energy barrier for nucleation and suppresses the promoting effect of the graphene oxide11. The results provide experimental information on the existence and temperature-dependent size of the critical ice nucleus, which has previously only been explored theoretically and through simulations12,13,14,15,16. As pinning of a pre-critical nucleus at a nanoparticle edge is not specific to the ice nucleus on graphene oxides, we expect that our approach could be extended to probe the critical nuclei in other nucleation processes.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: GOs of controlled sizes.
Fig. 2: Ice nucleation activities of GOs with different sizes and oxidation degrees.
Fig. 3: Transitions in the ice nucleation activity of nanosheets.
Fig. 4: Abrupt change in the free-energy barrier of ice nucleation on GO nanosheets.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Sosso, G. C. et al. Crystal nucleation in liquids: open questions and future challenges in molecular dynamics simulations. Chem. Rev. 116, 7078–7116 (2016).

    Article  CAS  Google Scholar 

  2. Gallo, P. et al. Water: a tale of two liquids. Chem. Rev. 116, 7463–7500 (2016).

    Article  CAS  Google Scholar 

  3. Zhang, Z. & Liu, X. Y. Control of ice nucleation: freezing and antifreeze strategies. Chem. Soc. Rev. 47, 7116–7139 (2018).

    Article  CAS  Google Scholar 

  4. Kiselev, A. et al. Active sites in heterogeneous ice nucleation—the example of K-rich feldspars. Science 355, 367–371 (2017).

    Article  CAS  ADS  Google Scholar 

  5. He, Z., Liu, K. & Wang, J. Bioinspired materials for controlling ice nucleation, growth, and recrystallization. Acc. Chem. Res. 51, 1082–1091 (2018).

    Article  CAS  Google Scholar 

  6. Moore, E. B. & Molinero, V. Structural transformation in supercooled water controls the crystallization rate of ice. Nature 479, 506–508 (2011).

    Article  CAS  ADS  Google Scholar 

  7. Matsumoto, M., Saito, S. & Ohmine, I. Molecular dynamics simulation of the ice nucleation and growth process leading to water freezing. Nature 416, 409–413 (2002).

    Article  CAS  ADS  Google Scholar 

  8. Fitzner, M., Sosso, G. C., Pietrucci, F., Pipolo, S. & Michaelides, A. Pre-critical fluctuations and what they disclose about heterogeneous crystal nucleation. Nat. Commun. 8, 2257 (2017).

    Article  ADS  Google Scholar 

  9. Pereyra, R. G., Szleifer, I. & Carignano, M. A. Temperature dependence of ice critical nucleus size. J. Chem. Phys. 135, 034508 (2011).

    Article  ADS  Google Scholar 

  10. Pradzynski, C. C., Forck, R. M., Zeuch, T., Slavicek, P. & Buck, U. A fully size-resolved perspective on the crystallization of water clusters. Science 337, 1529–1532 (2012).

    Article  CAS  ADS  Google Scholar 

  11. Xiao, Q. et al. What experiments on pinned nanobubbles can tell about the critical nucleus for bubble nucleation. Eur. Phys. J. E 40, 114 (2017).

    Article  Google Scholar 

  12. Lupi, L., Peters, B. & Molinero, V. Pre-ordering of interfacial water in the pathway of heterogeneous ice nucleation does not lead to a two-step crystallization mechanism. J. Chem. Phys. 145, 211910 (2016).

    Article  ADS  Google Scholar 

  13. Cabriolu, R. & Li, T. Ice nucleation on carbon surface supports the classical theory for heterogeneous nucleation. Phys. Rev. E 91, 052402 (2015).

    Article  ADS  Google Scholar 

  14. Lupi, L. et al. Role of stacking disorder in ice nucleation. Nature 551, 218–222 (2017).

    Article  CAS  ADS  Google Scholar 

  15. Russo, J., Romano, F. & Tanaka, H. New metastable form of ice and its role in the homogeneous crystallization of water. Nat. Mater. 13, 733–739 (2014).

    Article  CAS  ADS  Google Scholar 

  16. Palmer, J. C. et al. Metastable liquid−liquid transition in a molecular model of water. Nature 510, 385–388 (2014).

    Article  CAS  ADS  Google Scholar 

  17. Fletcher, N. H. Size effect in heterogeneous nucleation. J. Chem. Phys. 29, 572–576 (1958).

    Article  CAS  ADS  Google Scholar 

  18. Welti, A., Lüönd, F., Stetzer, O. & Lohmann, U. Influence of particle size on the ice nucleating ability of mineral dusts. Atmos. Chem. Phys. 9, 6705–6715 (2009).

    Article  CAS  ADS  Google Scholar 

  19. Liou, Y. C., Tocilj, A., Davies, P. L. & Jia, Z. C. Mimicry of ice structure by surface hydroxyls and water of a beta-helix antifreeze protein. Nature 406, 322–324 (2000).

    Article  CAS  ADS  Google Scholar 

  20. Garnham, C. P., Campbell, R. L., Walker, V. K. & Davies, P. L. Novel dimeric beta-helical model of an ice nucleation protein with bridged active sites. BMC Struct. Biol. 11, (2011).

  21. Liu, K. et al. Janus effect of antifreeze proteins on ice nucleation. Proc. Natl Acad. Sci. USA 113, 14739–14744 (2016).

    Article  CAS  Google Scholar 

  22. Whale, T. F., Rosillo-Lopez, M., Murray, B. J. & Salzmann, C. G. Ice nucleation properties of oxidized carbon nanomaterials. J. Phys. Chem. Lett. 6, 3012–3016 (2015).

    Article  CAS  Google Scholar 

  23. Häusler, T. et al. Ice nucleation activity of graphene and graphene oxides. J. Phys. Chem. C 122, 8182–8190 (2018).

    Article  Google Scholar 

  24. Lupi, L., Hudait, A. & Molinero, V. Heterogeneous nucleation of ice on carbon surfaces. J. Am. Chem. Soc. 136, 3156–3164 (2014).

    Article  CAS  Google Scholar 

  25. Zheng, Y., Su, C., Lu, J. & Loh, K. P. Room-temperature ice growth on graphite seeded by nano-graphene oxide. Angew. Chem. 52, 8708–8712 (2013).

    Article  CAS  Google Scholar 

  26. Roscoe, R. B. How does a rain drop grow? Science 129, 123–129 (1959).

    Article  Google Scholar 

  27. Koop, T., Luo, B. P., Tsias, A. & Peter, T. Water activity as the determinant for homogeneous ice nucleation in aqueous solutions. Nature 406, 611–614 (2000).

    Article  CAS  ADS  Google Scholar 

  28. Li, T. S., Donadio, D., Russo, G. & Galli, G. Homogeneous ice nucleation from supercooled water. Phys. Chem. Chem. Phys. 13, 19807–19813 (2011).

    Article  CAS  Google Scholar 

  29. Němec, T. Estimation of ice–water interfacial energy based on pressure-dependent formulation of classical nucleation theory. Chem. Phys. Lett. 583, 64–68 (2013).

    Article  ADS  Google Scholar 

  30. Eberle, P., Tiwari, M. K., Maitra, T. & Poulikakos, D. Rational nanostructuring of surfaces for extraordinary icephobicity. Nanoscale 6, 4874–4881 (2014).

    Article  CAS  ADS  Google Scholar 

  31. Tu, Y. et al. Destructive extraction of phospholipids from Escherichia coli membranes by graphene nanosheets. Nat. Nanotechnol. 8, 594–601 (2013).

    Article  CAS  ADS  Google Scholar 

  32. Geng, H. et al. Graphene oxide restricts growth and recrystallization of ice crystals. Angew. Chem. 56, 997–1001 (2017).

    Article  CAS  Google Scholar 

  33. Rourke, J. P. et al. The real graphene oxide revealed: stripping the oxidative debris from the graphene-like sheets. Angew. Chem. 50, 3173–3177 (2011).

    Article  CAS  Google Scholar 

  34. Fan, X. et al. Deoxygenation of exfoliated graphite oxide under alkaline conditions: a green route to graphene preparation. Adv. Mater. 20, 4490–4493 (2008).

    Article  CAS  Google Scholar 

  35. Bai, G. et al. Self-assembly of ceria/graphene oxide composite films with ultra-long antiwear lifetime under a high applied load. Carbon 84, 197–206 (2015).

    Article  CAS  Google Scholar 

  36. Du, N., Liu, X. Y. & Hew, C. L. Ice nucleation inhibition—mechanism of antifreeze by antifreeze protein. J. Biol. Chem. 278, 36000–36004 (2003).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The work is supported by the National Natural Science Foundation of China through grant nos 21733010, 11574310 and 21534007, the National Key R&D Program of China 2018YFA0208502, and the Strategic Priority Research Program of Chinese Academy of Sciences, grant no. XDB28000000. We thank B. Guan and Y. Liu for help in cryo-TEM experiments.

Author information

Authors and Affiliations

  1. Key Laboratory for Green Printing, Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Guoying Bai, Zhang Liu & Jianjun Wang

  2. Research Institute for Energy Equipment Materials, School of Materials Science and Engineering, Hebei University of Technology, Tianjin, China

    Guoying Bai

  3. Key Laboratory of Hebei Province for Molecular Biophysics Institute of Biophysics, Hebei University of Technology, Tianjin, China

    Dong Gao

  4. School of Physical Sciences and CAS Center for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing, China

    Xin Zhou

  5. Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou, China

    Xin Zhou

  6. Songshan Lake Materials Laboratory, Dongguan, Guangdong, China

    Xin Zhou & Jianjun Wang

  7. School of Future Technology, University of Chinese Academy of Sciences, Beijing, China

    Jianjun Wang

Authors
  1. Guoying Bai
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dong Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xin Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jianjun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

G.B., X.Z. and J.W. conceived the project and designed the experiments. G.B., D.G. and Z.L. performed the experiments. G.B., D.G., Z.L., X.Z. and J.W. analysed the data. G.B., D.G., X.Z. and J.W. prepared the manuscript.

Corresponding authors

Correspondence to Xin Zhou or Jianjun Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature thanks Niall English, Christoph Salzmann and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data figures and tables

Extended Data Fig. 1 Characterizations of GOs of controlled sizes.

a, AFM images of GOs of five controlled sizes and the corresponding height profiles along the lines marked. b, Cryo-TEM images of GOs of various sizes before size fractionation, showing the shape of the GOs in water. The upper image is the original; the lower panel is the image with enhanced contrast by colouring the GO domains to help the visibility. Scale bar, 10 nm. c, Photographs of 0.04 mg ml−1 GO aqueous dispersions. From left to right, the average lateral sizes of GO are <1 kDa, 3 nm, 8 nm, 11 nm, 21 nm and 50 nm, respectively. All the GO aqueous dispersions are clear and transparent, indicating the good dispersibility of various-sized GOs in water.

Extended Data Fig. 2 Influence of the substrate on the ice nucleation measurement.

a, Optical microscopic images of frozen water droplets on glass coverslip coated with a thin layer of silicone oil (left) and without silicone oil (right) during the ice nucleation assays. The other experimental conditions for these two images are identical (see Methods). The frozen water droplets on a glass coverslip coated with a thin oil film are independent. In contrast, on the glass coverslip without a thin oil film, the freezing events of the water droplets are not independent. b, Ice nucleation temperatures of water droplets on glass coated with silicone oil, glass without oil, silicon wafer and highly oriented pyrolytic graphite (HOPG). Data are means ±s.e.m. For each mean, the total number of the measurements is not less than 50. The volume of the water droplet is 0.2 µl. Cooling rate, 5 °C min−1. TIN of water droplets on different substrates shows different values, suggesting that the ice nucleation is initiated at the water/substrate interface.

Extended Data Fig. 3 Ice nucleation probability distribution of water droplets containing GOs of controlled sizes at three different concentrations.

The distributions are fitted by Gaussian functions. For each distribution, the total number of ice nucleation measurements is about 150. The results show that the change in concentration (from 0.52 to 13 μmol l−1) of GOs with sizes smaller than 8 nm does not affect the TIN of water droplets; however, TIN increases with the concentration of GOs when the GO size is above 11 nm.

Extended Data Fig. 4 Ice nucleation temperatures of droplets of GO aqueous dispersions at cooling rates ranging from 1 °C min−1 to 15 °C min−1.

a, Cooling rate dependence of TIN of water droplets containing GO samples of controlled sizes. Data are means ±s.e.m. For each mean, the total number of measurements is about 150. b, Ice nucleation probability distribution of the blank control (water droplets) at various cooling rates with Gaussian fitting. c, Ice nucleation probability distribution (Gaussian fitting) of water droplets containing GOs with a series of average lateral sizes at various cooling rates. For each distribution, the total number of measurements is about 150. The concentration of GO aqueous dispersion is 5.2 µmol l−1. All the volumes of water droplets are 0.2 µl.

Extended Data Fig. 5 The transitions of the ice nucleation activity of GOs.

a, The mean ice nucleation (supercooling) temperature −ΔT ≡ TIN − Tm versus the number of GOs in the water droplet, n = CV (for concentration, C and volume, V), for three degrees of oxidation of GOs with the same lateral size of 11 nm. Here the cooling rate is always 5 °C min−1. Data are means ±s.e.m. For each mean, the total number of the measurements is about 50. b, The scaled delay time of ice nucleation of water droplets containing GOs, τ = ntD(T; n), versus ΔT. The three curves for each GO size come from different n (the same as Fig. 3b in the main text) and collapse into the same curve. Data are means; error bars are standard deviation estimated by the jackknife resampling technique. For each mean, the total number of measurements varies from 20 to 150 to ensure that the nucleation event number m is typically not less than 10 (see Methods).

Extended Data Fig. 6 Characterization and ice nucleation activity of laponite.

a, AFM characterization of the prepared laponite. The insets show the lateral size distribution, the thickness and the hydrodynamic diameter of laponite. The size distribution is obtained by averaging the lateral sizes of more than 100 laponite nanosheets imaged by AFM. The hydrodynamic diameter of laponite nanosheets is measured by a Malvern Zetasizer. b, The ice nucleation (supercooling) temperature −ΔT ≡ TIN − Tm versus the number of laponites contained in the water droplet (for concentration, C and volume, V). Here the cooling rate is always 5 °C min−1. Data are means ±s.e.m. For each mean, the total number of the measurements is about 50.

Extended Data Fig. 7 Characterization and ice nucleation temperature investigations of GOs anchored on silicon water surface.

a, Schematic illustration showing the preparation process of the anchored GOs on Si wafer surfaces. b, AFM characterizations of the prepared surfaces without GOs and with GOs of controlled sizes. c, The ice nucleation (supercooling) temperature −ΔT ≡ TIN − Tm versus the contact area between the water droplets and the surface to which the GOs are anchored. The contact area, measured by optical microscopy, is proportional to the number of nucleation active sites (see Methods). Here the cooling rate is always 5 °C min−1. Data are means ±s.e.m. For each mean, the total number of measurements is about 50.

Extended Data Fig. 8 Theoretical analysis of ice nucleation on finite-sized nanosheet.

a, Free-energy barrier of ice nucleation on a thin-disk GO versus the normalized size of GOs. The inset shows the schematic illustration of thin-disk-shaped GOs with a smooth hemispherical edge. Its major diameter (lateral size) is L, and the thickness is H. b, Schematic diagram showing three typical shapes of ice nucleus on GO when L ≈ 2Rc. The first and the third are the critical ice nuclei corresponding to two different free-energy barriers (see Methods). c, The calculated dimensionless free energy, radius of ice nucleus (in units of Rc) and the apparent contact angle ψ versus the volume of ice nucleus (in units of (4π/3)Rc3) on the thin-disk GO nanosheet when L ≈ 2Rc . Here the dimensionless thickness of GO disk h = H/2Rc = 0.1, and θ (=30°) is the intrinsic contact angle between ice nucleus and the GO. The obtained results are not sensitive to these details of GO and the applied parameters (see Methods and Supplementary Section PS6).

Extended Data Table 1 Summary of characterization of GOs of controlled sizes
Full size table
Extended Data Table 2 Ice nucleation temperatures of water droplets containing GOs of controlled sizes and decreasing degrees of oxidation
Full size table

Supplementary information

Supplementary Information

This file contains parts PS1−PS7 with 20 Supplementary Figures and one Supplementary Table showing characterizations of GOs, TIN data about GOs, the size effect of Au nanoparticles on ice nucleation, theoretical analysis of ice nucleation on nanoparticles and Supplementary References.

Video 1

Freezing process of a water droplet containing GOs with an average lateral size of 8 nm. Volume of the water droplet, 0.2 µl. Cooling rate, 5 °C min−1. The concentration of GOs in the water droplet, 13 µmol l−1. The video shows that the freezing of the droplet occurs at the temperature of −27.6 °C.

Video 2

Freezing process of a water droplet containing GOs with an average lateral size of 11 nm. Volume of the water droplet, 0.2 µl. Cooling rate, 5 °C min−1. The concentration of GOs in the water droplet, 13 µmol l−1. The video shows that the freezing of the droplet occurs at the temperature of −17.7 °C.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bai, G., Gao, D., Liu, Z. et al. Probing the critical nucleus size for ice formation with graphene oxide nanosheets. Nature 576, 437–441 (2019). https://doi.org/10.1038/s41586-019-1827-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-019-1827-6

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing