Insights into Solid-To-Solid Transformation of MOF Amorphous Phases.
Yuri A MezenovStephanie BruyereAndrei A KrasilinEkaterina KhrapovaSemyon V BachininPavel V AlekseevskiySergei ShipiloskikhPascal BouletSebastien HupontAlexandre NomineBrigitte VigoloKonstantin Yu ZhizhinThierry BelmonteValentin A MilichkoPublished in: Inorganic chemistry (2022)
Metal-organic frameworks (MOFs) have been recently explored as crystalline solids for conversion into amorphous phases demonstrating non-specific mechanical, catalytic, and optical properties. The real-time control of such structural transformations and their outcomes still remain a challenge. Here, we use in situ high-resolution transmission electron microscopy with 0.01 s time resolution to explore non-thermal (electron induced) amorphization of a MOF single crystal, followed by transformation into an amorphous nanomaterial. By comparing a series of M -BTC ( M : Fe 3+ , Co 3+ , Co 2+ , Ni 2+ , and Cu 2+ ; BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology of a metal cluster of the parent MOFs determines the rate of formation and the chemistry of the resulting phases containing an intact ligand and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence spectroscopies further confirm the integrity of the BTC ligand and coordination bond breaking, while high-resolution imaging with chemical and structural analysis over time allows for tracking the dynamics of solid-to-solid transformations. The revealed relationship between the initial and resulting structures and the stability of the obtained phase and its photoluminescence over time contribute to the design of new amorphous MOF-based optical nanomaterials.
Keyphrases
- metal organic framework
- high resolution
- room temperature
- electron microscopy
- solid state
- mass spectrometry
- quantum dots
- oxide nanoparticles
- high speed
- type diabetes
- tandem mass spectrometry
- optical coherence tomography
- adipose tissue
- high glucose
- photodynamic therapy
- raman spectroscopy
- energy transfer
- weight loss
- liquid chromatography
- drug discovery