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Qiao, Ang
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Publications (4/4 displayed)
- 2022Mixed metal node effect in zeolitic imidazolate frameworkscitations
- 2020Fracture toughness of a metal–organic framework glasscitations
- 2018A metal-organic framework with ultrahigh glass-forming ability.
- 2017Mutual-stabilization in chemically bonded graphene oxide–TiO2 heterostructures synthesized by a sol–gel approachcitations
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article
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-x bIm x )], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity η (105 Pa·s) at the melting temperature Tm, a large crystal-glass network density deficit (Δρ/ρg)network, no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (ν = 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.