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

Research output: Contribution to journalArticle

30 Citations (Scopus)

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.

Original languageEnglish (US)
Article numbereaao6827
JournalScience Advances
Volume4
Issue number3
DOIs
StatePublished - Mar 9 2018

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Glass
Metals
Crystallization
Entropy
Thermodynamics
Viscosity
Freezing
Temperature

All Science Journal Classification (ASJC) codes

  • General

Cite this

Qiao, A., Bennett, T. D., Tao, H., Krajnc, A., Mali, G., Doherty, C. M., ... Yue, Y. (2018). A metal-organic framework with ultrahigh glass-forming ability. Science Advances, 4(3), [eaao6827]. https://doi.org/10.1126/sciadv.aao6827
Qiao, Ang ; Bennett, Thomas D. ; Tao, Haizheng ; Krajnc, Andraẑ ; Mali, Gregor ; Doherty, Cara M. ; Thornton, Aaron W. ; Mauro, John C. ; Greaves, G. Neville ; Yue, Yuanzheng. / A metal-organic framework with ultrahigh glass-forming ability. In: Science Advances. 2018 ; Vol. 4, No. 3.
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Qiao, A, Bennett, TD, Tao, H, Krajnc, A, Mali, G, Doherty, CM, Thornton, AW, Mauro, JC, Greaves, GN & Yue, Y 2018, 'A metal-organic framework with ultrahigh glass-forming ability', Science Advances, vol. 4, no. 3, eaao6827. https://doi.org/10.1126/sciadv.aao6827

A metal-organic framework with ultrahigh glass-forming ability. / Qiao, Ang; Bennett, Thomas D.; Tao, Haizheng; Krajnc, Andraẑ; Mali, Gregor; Doherty, Cara M.; Thornton, Aaron W.; Mauro, John C.; Greaves, G. Neville; Yue, Yuanzheng.

In: Science Advances, Vol. 4, No. 3, eaao6827, 09.03.2018.

Research output: Contribution to journalArticle

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AU - Greaves, G. Neville

AU - Yue, Yuanzheng

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Qiao A, Bennett TD, Tao H, Krajnc A, Mali G, Doherty CM et al. A metal-organic framework with ultrahigh glass-forming ability. Science Advances. 2018 Mar 9;4(3). eaao6827. https://doi.org/10.1126/sciadv.aao6827