Premium
Solvent Impact on the Properties of Benchmark Metal–Organic Frameworks: Acetonitrile‐Based Synthesis of CAU‐10, Ce‐UiO‐66, and Al‐MIL‐53
Author(s) -
Leubner Sebastian,
Stäglich Robert,
Franke Julia,
Jacobsen Jannick,
Gosch Jonas,
Siegel Renée,
Reinsch Helge,
Maurin Guillaume,
Senker Jürgen,
Yot Pascal G.,
Stock Norbert
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905376
Subject(s) - metal organic framework , acetonitrile , adsorption , materials science , solvent , molecule , porosimetry , chemical engineering , chemistry , organic chemistry , composite material , porosity , porous medium , engineering
Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal–organic frameworks (MOFs) CAU‐10, Ce‐UiO‐66, and Al‐MIL‐53 of idealized composition [Al(OH)(ISO)], [Ce 6 O 4 (OH) 4 (BDC) 6 ], and [Al(OH)(BDC)], respectively (ISO 2− : isophthalate, BDC 2− : terephthalate). Its use allowed the synthesis of Ce‐UiO‐66 on a gram scale. While CAU‐10 and Ce‐UiO‐66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al‐MIL‐53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large‐pore form over a broad temperature range (130–450 K). The stabilization of the large‐pore form of Al‐MIL‐53 was attributed to a high percentage of noncoordinating −COOH groups as determined by solid‐state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g −1 within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa).