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Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes

Nature Nanotechnology volume 12, pages 267–273 (2017)Cite this article

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Abstract

Fluid phase transitions inside single, isolated carbon nanotubes are predicted to deviate substantially from classical thermodynamics. This behaviour enables the study of ice nanotubes and the exploration of their potential applications. Here we report measurements of the phase boundaries of water confined within six isolated carbon nanotubes of different diameters (1.05, 1.06, 1.15, 1.24, 1.44 and 1.52 nm) using Raman spectroscopy. The results reveal an exquisite sensitivity to diameter and substantially larger temperature elevations of the freezing transition (by as much as 100 °C) than have been theoretically predicted. Dynamic water filling and reversible freezing transitions were marked by 2–5 cm−1 shifts in the radial breathing mode frequency, revealing reversible melting bracketed to 105–151 °C and 87–117 °C for 1.05 and 1.06 nm single-walled carbon nanotubes, respectively. Near-ambient phase changes were observed for 1.44 and 1.52 nm nanotubes, bracketed between 15–49 °C and 3–30 °C, respectively, whereas the depression of the freezing point was observed for the 1.15 nm nanotube between −35 and 10 °C. We also find that the interior aqueous phase reversibly decreases the axial thermal conductivity of the nanotube by as much as 500%, allowing digital control of the heat flux.

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Figure 1: Evidence of filling and phase transition of water inside CNTs.
Figure 2: Diameter-dependent vapour–liquid and liquid–solid phase transitions of confined water inside CNTs.
Figure 3: Reversibility of the water phases inside the CNT on heating and cooling, and agreement in the phase transition data obtained by the two heating methods.
Figure 4: Comparison of the diameter-dependent phase transition temperatures and reduction in the axial conductivity of the CNTs on water filling.

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Acknowledgements

This work was supported in part by the U. S. Army Research Laboratory and the U. S. Army Research Office through the Institute for Soldier Nanotechnologies, under contract number W911NF-13-D-0001. We acknowledge support from the Shell-MIT-EI Energy Research Fund as well. We also acknowledge support from the National Science Foundation under Grant Number 1306529.

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  1. Kumar Varoon Agrawal and Steven Shimizu: These authors contributed equally to this work

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  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Kumar Varoon Agrawal, Steven Shimizu, Lee W. Drahushuk, Daniel Kilcoyne & Michael S. Strano

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Contributions

K.V.A, S.S. and M.S.S. conceived and designed the experiments. K.V.A., S.S., L.W.D. and D.K. performed the experiments, analyzed the data, and contributed materials/analysis tools. K.V.A. and M.S.S. wrote the paper. All authors commented on the manuscript.

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Correspondence to Michael S. Strano.

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Agrawal, K., Shimizu, S., Drahushuk, L. et al. Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes. Nature Nanotech 12, 267–273 (2017). https://doi.org/10.1038/nnano.2016.254

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