Assessing Chemical Heterogeneity at the Nanoscale in Mixed-Ligand Metal–Organic Frameworks with the PTIR Technique

Authors

  • Dr. Aaron M. Katzenmeyer,

    1. Center for Nanoscale Science and Technology, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899 (USA)
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  • Dr. Jerome Canivet,

    1. Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON), Université Lyon 1, CNRS, 2, Avenue Albert Einstein, 69626 Villeurbanne (France)
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  • Glenn Holland,

    1. Center for Nanoscale Science and Technology, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899 (USA)
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  • Dr. David Farrusseng,

    1. Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON), Université Lyon 1, CNRS, 2, Avenue Albert Einstein, 69626 Villeurbanne (France)
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  • Dr. Andrea Centrone

    Corresponding author
    1. Center for Nanoscale Science and Technology, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899 (USA)
    • Center for Nanoscale Science and Technology, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899 (USA)

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  • PTIR=photothermal induced resonance.

Abstract

Recently, the use of mixtures of organic-building-block linkers has given chemists an additional degree of freedom for engineering metal–organic frameworks (MOFs) with specific properties; however, the poor characterization of the chemical complexity of such MixMOF structures by conventional techniques hinders the verification of rational design. Herein, we describe the application of a technique known as photothermal induced resonance to individual MixMOF microcrystals to elucidate their chemical composition with nanoscale resolution. Results show that MixMOFs isoreticular to In-MIL-68, obtained either directly from solution or by postsynthetic linker exchange, are homogeneous down to approximately 100 nm. Additionally, we report a novel in situ process that enables the engineering of anisotropic domains in MOF crystals with submicron linker-concentration gradients.

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