| Summary: | A catalyst-free Schiff base reaction was applied to synthesize two imine-linked covalent organic frameworks (COFs). The condensation reaction of 1,3,5-tris-(4-aminophenyl)triazine (TAPT) with 4,4′-biphenyldicarboxaldehyde led to the structure of HHU-COF-1 (HHU = Heinrich-Heine University). The fluorinated analog HHU-COF-2 was obtained with 2,2′,3,3′,5,5′,6,6′-octafluoro-4,4′-biphenyldicarboxaldehyde. Solid-state NMR, infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis confirmed the successful formation of the two network structures. The crystalline materials are characterized by high Brunauer–Emmett–Teller surface areas of 2352 m<sup>2</sup>/g for HHU-COF-1 and 1356 m<sup>2</sup>/g for HHU-COF-2. The products of a larger-scale synthesis were applied to prepare mixed-matrix membranes (MMMs) with the polymer Matrimid. CO<sub>2</sub>/CH<sub>4</sub> permeation tests revealed a moderate increase in CO<sub>2</sub> permeability at constant selectivity for HHU-COF-1 as a dispersed phase, whereas application of the fluorinated COF led to a CO<sub>2</sub>/CH<sub>4</sub> selectivity increase from 42 for the pure Matrimid membrane to 51 for 8 wt% of HHU-COF-2 and a permeability increase from 6.8 to 13.0 Barrer for the 24 wt% MMM.
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