0000000000429684
AUTHOR
Joël Patarin
Improved hydrophobicity of inorganic–organic hybrid mesoporous silica with cage-like pores
International audience; Hydrophobic ordered mesoporous silica particles with cage-like pores (SBA-1 type) were prepared through co-condensation of phenyltriethoxysilane (PhTES) and tetraethylorthosilicate (TEOS) at different TEOS/PhTES molar ratios. It is shown that the hydrophobic character of the particles is enhanced by increasing the phenyl loading (decreasing the TEOS/PhTES molar ratio) and that it could be further enhanced by subsequent trimethylsilyl (TMS) grafting on remaining silanol groups (TMS-PhSBA-1 sample). This increase of hydrophobicity has been evidenced on the internal surface (mesoporosity) of the particles using water adsorption and, on the external surface of the partic…
Temperature-Induced Structural Transitions in the Gallium-Based MIL-53 Metal–Organic Framework
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 nonporo…
New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure.
International audience; The "water-silicalite-1" system is known to act as a molecular spring. The successive intrusion-extrusion cycles of liquid water in small crystallites (6 × 3 × 0.5 μm(3)) of hydrophobic silicalite-1 were studied by volumetric and calorimetric techniques. The experiments displayed a decrease of the intrusion pressure between the first intrusion-extrusion cycle and the consecutive ones, whereas the extrusion pressures remained unchanged. However, neither XRD studies nor SEM observations revealed any structural and morphological modifications of silicalite-1 at the long-range order. Such a shift in the value of the intrusion pressure after the first water intrusion-extr…
Mechanism of water adsorption in the large pore form of the gallium-based MIL-53 metal-organic framework
Abstract Water adsorption in the large pore ( lp_empty ) form of Ga-MIL-53 was studied by TGA, DSC and in situ XRD and FTIR at 298 K. The large pore form can be stabilized at room temperature after activation under vacuum at 553 K. The isotherm of water adsorption in this large pore form (pore dimensions: 1.67 × 1.33 nm) is very similar to that measured on the narrow pore ( np_empty ) form (pore dimensions: 1.97 × 0.76 nm). Such a similarity is rather unusual given that the pore sizes of these two phases are very different. In order to understand the origin of this effect in situ XRD and FTIR measurements were particularly helpful. It was found that the adsorption of even small amount of wa…
Water Adsorption in Flexible Gallium-Based MIL-53 Metal–Organic Framework
Understanding the adsorption of water in metal–organic frameworks (MOF), and particularly in soft porous crystals, is a crucial prerequisite before considering MOFs for industrial applications. We report here a joint experimental and theoretical study on the behavior of a gallium-based breathing MOF, Ga-MIL-53, upon water adsorption. By looking at the energetics and thermodynamics of Ga-MIL-53, we demonstrate why it behaves differently from its sibling Al-MIL-53, showing a different phase at room temperature (a nonporous phase) and the presence of a hydrated narrow-pore structure at gas saturation pressure. Moreover, we present a complete water vapor pressure vs temperature phase diagram of…