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  • Title: Three-step nucleation of metal-organic framework nanocrystals.
    Author: Liu X, Chee SW, Raj S, Sawczyk M, Král P, Mirsaidov U.
    Journal: Proc Natl Acad Sci U S A; 2021 Mar 09; 118(10):. PubMed ID: 33649204.
    Abstract:
    Metal-organic frameworks (MOFs) are crystalline nanoporous materials with great potential for a wide range of industrial applications. Understanding the nucleation and early growth stages of these materials from a solution is critical for their design and synthesis. Despite their importance, the pathways through which MOFs nucleate are largely unknown. Using a combination of in situ liquid-phase and cryogenic transmission electron microscopy, we show that zeolitic imidazolate framework-8 MOF nanocrystals nucleate from precursor solution via three distinct steps: 1) liquid-liquid phase separation into solute-rich and solute-poor regions, followed by 2) direct condensation of the solute-rich region into an amorphous aggregate and 3) crystallization of the aggregate into a MOF. The three-step pathway for MOF nucleation shown here cannot be accounted for by conventional nucleation models and provides direct evidence for the nonclassical nucleation pathways in open-framework materials, suggesting that a solute-rich phase is a common precursor for crystallization from a solution.
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