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Title: Phase transitions of ordered ice in graphene nanocapillaries and carbon nanotubes

New phase diagrams for water confined in graphene nanocapillaries and single-walled carbon nanotubes (CNTs) are proposed, identifying ice structures, their melting points and revealing the presence of a solid-liquid critical point. For quasi-2D water in nanocapillaries, we show through molecular-dynamics simulations that AA stacking in multilayer quasi-2D ice arises from interlayer hydrogen-bonding and is stable up to three layers, thereby explaining recent experimental observations. Detailed structural and energetic analyses show that quasi-2D water can freeze discontinuously through a first-order phase transition or continuously with a critical point. The first-order transition line extends to a continuous transition line, defined by a sharp transition in diffusivity between solid-like and liquid-like regimes. For quasi-1D water, confined in CNTs, we observe the existence of a similar critical point at intermediate densities. In addition, an end point is identified on the continuous-transition line, above which the solid and liquid phases deform continuously. The solid-liquid phase transition temperatures in CNTs are shown to be substantially higher than 273 K, confirming recent Raman spectroscopy measurements. In conclusion, we observe ultrafast proton and hydroxyl transport in quasi-1D and -2D ice at 300 K, exceeding those of bulk water up to a factor of five, thereby providing possible applicationsmore » to fuel-cells and electrolyzers.« less
Authors:
ORCiD logo [1] ;  [2] ;  [1]
  1. Stanford Univ., Stanford, CA (United States)
  2. The Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING
OSTI Identifier:
1480603

Raju, Muralikrishna, van Duin, Adri C. T., and Ihme, Matthias. Phase transitions of ordered ice in graphene nanocapillaries and carbon nanotubes. United States: N. p., Web. doi:10.1038/s41598-018-22201-3.
Raju, Muralikrishna, van Duin, Adri C. T., & Ihme, Matthias. Phase transitions of ordered ice in graphene nanocapillaries and carbon nanotubes. United States. doi:10.1038/s41598-018-22201-3.
Raju, Muralikrishna, van Duin, Adri C. T., and Ihme, Matthias. 2018. "Phase transitions of ordered ice in graphene nanocapillaries and carbon nanotubes". United States. doi:10.1038/s41598-018-22201-3. https://www.osti.gov/servlets/purl/1480603.
@article{osti_1480603,
title = {Phase transitions of ordered ice in graphene nanocapillaries and carbon nanotubes},
author = {Raju, Muralikrishna and van Duin, Adri C. T. and Ihme, Matthias},
abstractNote = {New phase diagrams for water confined in graphene nanocapillaries and single-walled carbon nanotubes (CNTs) are proposed, identifying ice structures, their melting points and revealing the presence of a solid-liquid critical point. For quasi-2D water in nanocapillaries, we show through molecular-dynamics simulations that AA stacking in multilayer quasi-2D ice arises from interlayer hydrogen-bonding and is stable up to three layers, thereby explaining recent experimental observations. Detailed structural and energetic analyses show that quasi-2D water can freeze discontinuously through a first-order phase transition or continuously with a critical point. The first-order transition line extends to a continuous transition line, defined by a sharp transition in diffusivity between solid-like and liquid-like regimes. For quasi-1D water, confined in CNTs, we observe the existence of a similar critical point at intermediate densities. In addition, an end point is identified on the continuous-transition line, above which the solid and liquid phases deform continuously. The solid-liquid phase transition temperatures in CNTs are shown to be substantially higher than 273 K, confirming recent Raman spectroscopy measurements. In conclusion, we observe ultrafast proton and hydroxyl transport in quasi-1D and -2D ice at 300 K, exceeding those of bulk water up to a factor of five, thereby providing possible applications to fuel-cells and electrolyzers.},
doi = {10.1038/s41598-018-22201-3},
journal = {Scientific Reports},
number = 1,
volume = 8,
place = {United States},
year = {2018},
month = {3}
}

Works referenced in this record:

Unimpeded Permeation of Water Through Helium-Leak-Tight Graphene-Based Membranes
journal, January 2012

Osmotic water transport through carbon nanotube membranes
journal, July 2003
  • Kalra, A.; Garde, S.; Hummer, G.
  • Proceedings of the National Academy of Sciences, Vol. 100, Issue 18, p. 10175-10180
  • DOI: 10.1073/pnas.1633354100