Journal of physical chemistry. C, 2013-04, Vol.117 (16), p.8180-8188
2013
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Details
- Autor(en) / Beteiligte
- Titel
- Temperature-Induced Structural Transitions in the Gallium-Based MIL-53 Metal–Organic Framework
- Ist Teil von
- Journal of physical chemistry. C, 2013-04, Vol.117 (16), p.8180-8188
- Ort / Verlag
- Columbus, OH: American Chemical Society
- Erscheinungsjahr
- 2013
- Quelle
- Alma/SFX Local Collection
- Beschreibungen/Notizen
- We report a structural and thermodynamic investigation of the phase behavior of Ga(OH,F)-MIL-53, a gallium-based metal–organic framework (MOF) having the MIL-53 topology containing 0.7 wt % fluorine bonded to the metal. Despite some small structural differences, especially for the hydrated form, the overall physical chemistry behavior of Ga(OH,F)-MIL-53 is very similar to standard fluorine free Ga-MIL-53 material. A combination of in situ X-ray diffraction, in situ Fourier transform infrared spectroscopy, differential scanning calorimetry, and heat capacity measurements allowed us to establish that Ga(OH,F)-MIL-53 under vacuum (i.e., the empty material) exhibits two stable phases: a nonporous narrow-pore (np) phase favored at low temperature and a large-pore (lp) phase favored at high temperature, accompanied by a huge hysteresis effect. Structure determination of the hydrated material Ga(OH,F)-MIL-53_np_H2O obtained after synthesis, activation, and rehydration was also performed. Density functional theory calculations show that it is not a stable structure of Ga(OH,F)-MIL-53 in the absence of adsorbed water molecules. Instead, this hydrated structure is a swollen variant of the np phase, where the flexible framework has expanded to accommodate water molecules.
- Sprache
- Englisch
- Identifikatoren
- ISSN: 1932-7447eISSN: 1932-7455DOI: 10.1021/jp312179eTitel-ID: cdi_hal_primary_oai_HAL_hal_02113280v1
- Format
- –
- Schlagworte
- Chemical Sciences, Composition and phase identification, Condensed matter: electronic structure, electrical, magnetic, and optical properties, Condensed matter: structure, mechanical and thermal properties, Electron states, Equations of state, phase equilibria, and phase transitions, Exact sciences and technology, Material chemistry, Methods of electronic structure calculations, Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals, or physical chemistry, Physics, Specific phase transitions, Structural transitions in nanoscale materials, Structure of solids and liquids, crystallography, Surfaces and interfaces, thin films and whiskers (structure and nonelectronic properties), Theoretical and, Thin film structure and morphology