A metal-organic framework with ultrahigh glass-forming ability

Ang Qiao; Thomas D. Bennett; Haizheng Tao; Andraẑ Krajnc; Gregor Mali; Cara M. Doherty; Aaron W. Thornton; John C. Mauro; G. Neville Greaves; Yuanzheng Yue

doi:10.1126/sciadv.aao6827

A metal-organic framework with ultrahigh glass-forming ability

Ang Qiao, Thomas D. Bennett, Haizheng Tao, Andraẑ Krajnc, Gregor Mali, Cara M. Doherty, Aaron W. Thornton, John C. Mauro, G. Neville Greaves, Yuanzheng Yue

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

214 Scopus citations

Abstract

Glass-forming ability (GFA) is the ability of a liquid to avoid crystallization during cooling. Metal-organic frameworks (MOFs) are a new class of glass formers (1-3), with hitherto unknown dynamic and thermodynamic properties. We report the discovery of a new series of tetrahedral glass systems, zeolitic imidazolate framework-62 (ZIF-62) [Zn(Im₂-xbIm_x)], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity h (10⁵ Pa·s) at the melting temperature T_m, a large crystal-glass network density deficit (δP/P_g)network, no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (v = 0.45), and the highest T_g/T_m ratio (0.84) ever reported. T_m and T_g both increase with benzimidazolate (bIm) content but retain the same ultrahigh T_g/T_m ratio, owing to high steric hindrance and frustrated network dynamics and also to the unusually low enthalpy and entropy typical of the soft and flexible nature of MOFs. On the basis of these versatile properties, we explain the exceptional GFA of the ZIF-62 system.

Original language	English (US)
Article number	eaao6827
Journal	Science Advances
Volume	4
Issue number	3
DOIs	https://doi.org/10.1126/sciadv.aao6827
State	Published - Mar 9 2018

All Science Journal Classification (ASJC) codes

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title = "A metal-organic framework with ultrahigh glass-forming ability",

abstract = "Glass-forming ability (GFA) is the ability of a liquid to avoid crystallization during cooling. Metal-organic frameworks (MOFs) are a new class of glass formers (1-3), with hitherto unknown dynamic and thermodynamic properties. We report the discovery of a new series of tetrahedral glass systems, zeolitic imidazolate framework-62 (ZIF-62) [Zn(Im2-xbImx)], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity h (105 Pa·s) at the melting temperature Tm, a large crystal-glass network density deficit (δP/Pg)network, no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (v = 0.45), and the highest Tg/Tm ratio (0.84) ever reported. Tm and Tg both increase with benzimidazolate (bIm) content but retain the same ultrahigh Tg/Tm ratio, owing to high steric hindrance and frustrated network dynamics and also to the unusually low enthalpy and entropy typical of the soft and flexible nature of MOFs. On the basis of these versatile properties, we explain the exceptional GFA of the ZIF-62 system.",

author = "Ang Qiao and Bennett, {Thomas D.} and Haizheng Tao and Andraẑ Krajnc and Gregor Mali and Doherty, {Cara M.} and Thornton, {Aaron W.} and Mauro, {John C.} and Greaves, {G. Neville} and Yuanzheng Yue",

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AU - Qiao, Ang

AU - Bennett, Thomas D.

AU - Tao, Haizheng

AU - Krajnc, Andraẑ

AU - Mali, Gregor

AU - Doherty, Cara M.

AU - Thornton, Aaron W.

AU - Mauro, John C.

AU - Greaves, G. Neville

AU - Yue, Yuanzheng

N1 - Publisher Copyright: © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

PY - 2018/3/9

Y1 - 2018/3/9

N2 - Glass-forming ability (GFA) is the ability of a liquid to avoid crystallization during cooling. Metal-organic frameworks (MOFs) are a new class of glass formers (1-3), with hitherto unknown dynamic and thermodynamic properties. We report the discovery of a new series of tetrahedral glass systems, zeolitic imidazolate framework-62 (ZIF-62) [Zn(Im2-xbImx)], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity h (105 Pa·s) at the melting temperature Tm, a large crystal-glass network density deficit (δP/Pg)network, no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (v = 0.45), and the highest Tg/Tm ratio (0.84) ever reported. Tm and Tg both increase with benzimidazolate (bIm) content but retain the same ultrahigh Tg/Tm ratio, owing to high steric hindrance and frustrated network dynamics and also to the unusually low enthalpy and entropy typical of the soft and flexible nature of MOFs. On the basis of these versatile properties, we explain the exceptional GFA of the ZIF-62 system.

AB - Glass-forming ability (GFA) is the ability of a liquid to avoid crystallization during cooling. Metal-organic frameworks (MOFs) are a new class of glass formers (1-3), with hitherto unknown dynamic and thermodynamic properties. We report the discovery of a new series of tetrahedral glass systems, zeolitic imidazolate framework-62 (ZIF-62) [Zn(Im2-xbImx)], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity h (105 Pa·s) at the melting temperature Tm, a large crystal-glass network density deficit (δP/Pg)network, no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (v = 0.45), and the highest Tg/Tm ratio (0.84) ever reported. Tm and Tg both increase with benzimidazolate (bIm) content but retain the same ultrahigh Tg/Tm ratio, owing to high steric hindrance and frustrated network dynamics and also to the unusually low enthalpy and entropy typical of the soft and flexible nature of MOFs. On the basis of these versatile properties, we explain the exceptional GFA of the ZIF-62 system.

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JO - Science Advances

JF - Science Advances

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A metal-organic framework with ultrahigh glass-forming ability

Abstract

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