Rapid Room‐Temperature Synthesis of Metal–Organic Framework HKUST‐1 Crystals in Bulk and as Oriented and Patterned Thin Films

Abstract

Whereas the preparation of defined metal–organic framework (MOF) materials via hydrothermal or diffusion methods typically requires hours to days, our simple precipitation route opens the access to the well‐known HKUST‐1 frameworks within minutes. Crucial for the formation of a well‐defined, crystalline material is the choice of suitable precipitating solvents, with methanol and ethanol being the most favorable ones. This approach could be extended to the formation of dense, surface‐mounted MOF films (so‐called SURMOFs), in particular if the surfaces are decorated with suitable binding groups by formation of self‐assembled monolayers (SAMs). By combination with micro‐contact printing (μCP), patterned SURMOFs became accessible, in which the precipitating solvent is decisive on the formation of either spatially restricted films or single particles.

Pervaporation and membrane reactor performance of polyimide based mixed matrix membranes containing MOF HKUST-1

“…The absence of bands at 1730-1690 cm À 1 related to the stretching vibration of the C ¼O and C-OH groups of the free BTC indicates that protonated free ligands did not remain in the sample. However, a band between 1500 and 1600 cm À 1 can be observed; this relates to carboxylate groups acting as bidentate intercluster bridges (Zhuang et al, 2011) which may lead to some MOF particle aggregation. The absorbances of the 20 and 20 wt% Cu 3 (BTC) 2 MMMs after the esterification reaction are similar to that of the bare PI membrane, where the peaks at 1720 cm À 1 relate to the symmetric and asymmetric stretching of the C ¼O groups in the imide and those at 1510 and 1485 cm À 1 relate to aromatic stretching of the paradisubstituted phenyl groups.…”

“…1b), from 9.0 72.0 mm to 0.60 70.15 mm. The small particle size was caused by the combination of low temperature and ethanol as precipitating solvent, a condition in which the nucleation occurs so fast that it suppresses the formation of larger crystals (Wee et al, 2012;Zhuang et al, 2011).…”

Multi-scale crystal engineering of metal organic frameworks

“…Octahedral HKUST-1 crystals with an uniform size of about 2 µm have been synthesized by Zhuan et al [205] using methanol or ethanol as an initiation solvent, while ill-defined, nano-crystalline aggregates resulted when acetone or acetonitrile were used as initiation solvents.…”

The surface barrier phenomenon at the loading of metal-organic frameworks

“…Powder HKUST-1 was solvothermally synthesized by mixing 0.30 g (1.5 mmol) copper(II) acetate and 0.21 g (1 mmol) BTC in 12 ml pure ethanol in a sealed glass bottle 37 . The reagents were mixed and dissolved in ultrasonic bath for 30 min, followed by heating at 65°C for 2 days and cooling down to room temperature.…”