An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram

Yuan Liu, Yingying Huang, Chongqin Zhu, Hui Li, Jijun Zhao, Lu Wang, Lars Ojamäe, Joseph S. Francisco, Xiao Cheng Zeng

Research output: Contribution to journalArticle

Abstract

The recent back-to-back findings of low-density porous ice XVI and XVII have rekindled the century-old field of the solid-state physics and chemistry of water. Experimentally, both ice XVI and XVII crystals can be produced by extracting guest atoms or molecules enclosed in the cavities of preformed ice clathrate hydrates. Herein, we examine more than 200 hypothetical low-density porous ices whose structures were generated according to a database of zeolite structures. Hitherto unreported porous EMT ice, named according to zeolite nomenclature, is identified to have an extremely low density of 0.5 g/cm3 and the largest internal cavity (7.88 Å in average radius). The EMT ice can be viewed as dumbbell-shaped motifs in a hexagonal close-packed structure. Our first-principles computations and molecular dynamics simulations confirm that the EMT ice is stable under negative pressures and exhibits higher thermal stability than other ultralow-density ices. If all cavities are fully occupied by hydrogen molecules, the EMT ice hydrate can easily outperform the record hydrogen storage capacity of 5.3 wt % achieved with sII hydrogen hydrate. Most importantly, in the reconstructed temperature–pressure (T-P) phase diagram of water, the EMT ice is located at deeply negative pressure regions below ice XVI and at higher temperature regions next to FAU. Last, the phonon spectra of empty-sII, FAU, EMT, and other zeolite-like ice structures are computed by using the dispersion corrected vdW-DF2 functional. Compared with those of ice XI (0.93 g/cm3), both the bending and stretching vibrational modes of the EMT ice are blue-shifted due to their weaker hydrogen bonds.

Original languageEnglish (US)
Pages (from-to)12684-12691
Number of pages8
JournalProceedings of the National Academy of Sciences of the United States of America
Volume116
Issue number26
DOIs
StatePublished - Jan 1 2019

Fingerprint

Ice
Water
Zeolites
Hydrogen
Phonons
Pressure
Physics
Molecular Dynamics Simulation
Terminology
Hot Temperature

Keywords

  • EMT ice
  • Porous ice
  • Reconstructed temperature–pressure phase diagram
  • Record hydrogen storage capacity
  • Ultralow density

ASJC Scopus subject areas

  • General

Cite this

An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram. / Liu, Yuan; Huang, Yingying; Zhu, Chongqin; Li, Hui; Zhao, Jijun; Wang, Lu; Ojamäe, Lars; Francisco, Joseph S.; Zeng, Xiao Cheng.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 116, No. 26, 01.01.2019, p. 12684-12691.

Research output: Contribution to journalArticle

Liu, Yuan ; Huang, Yingying ; Zhu, Chongqin ; Li, Hui ; Zhao, Jijun ; Wang, Lu ; Ojamäe, Lars ; Francisco, Joseph S. ; Zeng, Xiao Cheng. / An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram. In: Proceedings of the National Academy of Sciences of the United States of America. 2019 ; Vol. 116, No. 26. pp. 12684-12691.
@article{93513dc7a9584f548fa5fa738f38809a,
title = "An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram",
abstract = "The recent back-to-back findings of low-density porous ice XVI and XVII have rekindled the century-old field of the solid-state physics and chemistry of water. Experimentally, both ice XVI and XVII crystals can be produced by extracting guest atoms or molecules enclosed in the cavities of preformed ice clathrate hydrates. Herein, we examine more than 200 hypothetical low-density porous ices whose structures were generated according to a database of zeolite structures. Hitherto unreported porous EMT ice, named according to zeolite nomenclature, is identified to have an extremely low density of 0.5 g/cm3 and the largest internal cavity (7.88 {\AA} in average radius). The EMT ice can be viewed as dumbbell-shaped motifs in a hexagonal close-packed structure. Our first-principles computations and molecular dynamics simulations confirm that the EMT ice is stable under negative pressures and exhibits higher thermal stability than other ultralow-density ices. If all cavities are fully occupied by hydrogen molecules, the EMT ice hydrate can easily outperform the record hydrogen storage capacity of 5.3 wt {\%} achieved with sII hydrogen hydrate. Most importantly, in the reconstructed temperature–pressure (T-P) phase diagram of water, the EMT ice is located at deeply negative pressure regions below ice XVI and at higher temperature regions next to FAU. Last, the phonon spectra of empty-sII, FAU, EMT, and other zeolite-like ice structures are computed by using the dispersion corrected vdW-DF2 functional. Compared with those of ice XI (0.93 g/cm3), both the bending and stretching vibrational modes of the EMT ice are blue-shifted due to their weaker hydrogen bonds.",
keywords = "EMT ice, Porous ice, Reconstructed temperature–pressure phase diagram, Record hydrogen storage capacity, Ultralow density",
author = "Yuan Liu and Yingying Huang and Chongqin Zhu and Hui Li and Jijun Zhao and Lu Wang and Lars Ojam{\"a}e and Francisco, {Joseph S.} and Zeng, {Xiao Cheng}",
year = "2019",
month = "1",
day = "1",
doi = "10.1073/pnas.1900739116",
language = "English (US)",
volume = "116",
pages = "12684--12691",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
number = "26",

}

TY - JOUR

T1 - An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram

AU - Liu, Yuan

AU - Huang, Yingying

AU - Zhu, Chongqin

AU - Li, Hui

AU - Zhao, Jijun

AU - Wang, Lu

AU - Ojamäe, Lars

AU - Francisco, Joseph S.

AU - Zeng, Xiao Cheng

PY - 2019/1/1

Y1 - 2019/1/1

N2 - The recent back-to-back findings of low-density porous ice XVI and XVII have rekindled the century-old field of the solid-state physics and chemistry of water. Experimentally, both ice XVI and XVII crystals can be produced by extracting guest atoms or molecules enclosed in the cavities of preformed ice clathrate hydrates. Herein, we examine more than 200 hypothetical low-density porous ices whose structures were generated according to a database of zeolite structures. Hitherto unreported porous EMT ice, named according to zeolite nomenclature, is identified to have an extremely low density of 0.5 g/cm3 and the largest internal cavity (7.88 Å in average radius). The EMT ice can be viewed as dumbbell-shaped motifs in a hexagonal close-packed structure. Our first-principles computations and molecular dynamics simulations confirm that the EMT ice is stable under negative pressures and exhibits higher thermal stability than other ultralow-density ices. If all cavities are fully occupied by hydrogen molecules, the EMT ice hydrate can easily outperform the record hydrogen storage capacity of 5.3 wt % achieved with sII hydrogen hydrate. Most importantly, in the reconstructed temperature–pressure (T-P) phase diagram of water, the EMT ice is located at deeply negative pressure regions below ice XVI and at higher temperature regions next to FAU. Last, the phonon spectra of empty-sII, FAU, EMT, and other zeolite-like ice structures are computed by using the dispersion corrected vdW-DF2 functional. Compared with those of ice XI (0.93 g/cm3), both the bending and stretching vibrational modes of the EMT ice are blue-shifted due to their weaker hydrogen bonds.

AB - The recent back-to-back findings of low-density porous ice XVI and XVII have rekindled the century-old field of the solid-state physics and chemistry of water. Experimentally, both ice XVI and XVII crystals can be produced by extracting guest atoms or molecules enclosed in the cavities of preformed ice clathrate hydrates. Herein, we examine more than 200 hypothetical low-density porous ices whose structures were generated according to a database of zeolite structures. Hitherto unreported porous EMT ice, named according to zeolite nomenclature, is identified to have an extremely low density of 0.5 g/cm3 and the largest internal cavity (7.88 Å in average radius). The EMT ice can be viewed as dumbbell-shaped motifs in a hexagonal close-packed structure. Our first-principles computations and molecular dynamics simulations confirm that the EMT ice is stable under negative pressures and exhibits higher thermal stability than other ultralow-density ices. If all cavities are fully occupied by hydrogen molecules, the EMT ice hydrate can easily outperform the record hydrogen storage capacity of 5.3 wt % achieved with sII hydrogen hydrate. Most importantly, in the reconstructed temperature–pressure (T-P) phase diagram of water, the EMT ice is located at deeply negative pressure regions below ice XVI and at higher temperature regions next to FAU. Last, the phonon spectra of empty-sII, FAU, EMT, and other zeolite-like ice structures are computed by using the dispersion corrected vdW-DF2 functional. Compared with those of ice XI (0.93 g/cm3), both the bending and stretching vibrational modes of the EMT ice are blue-shifted due to their weaker hydrogen bonds.

KW - EMT ice

KW - Porous ice

KW - Reconstructed temperature–pressure phase diagram

KW - Record hydrogen storage capacity

KW - Ultralow density

UR - http://www.scopus.com/inward/record.url?scp=85068166026&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85068166026&partnerID=8YFLogxK

U2 - 10.1073/pnas.1900739116

DO - 10.1073/pnas.1900739116

M3 - Article

C2 - 31182582

AN - SCOPUS:85068166026

VL - 116

SP - 12684

EP - 12691

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

SN - 0027-8424

IS - 26

ER -