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Pure Crystalline Covalent Organic Framework Aerogels
Dongyang Zhu ; Yifan Zhu ; Qianqian Yan , et al. Chem. Mater.,2021,33(11):4216-4224. DOI: 10.1021/acs.chemmater.1c01122
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Abstract: Covalent organic frameworks (COFs) are crystalline organic materials of interest for a wide range of applications due to their porosity, tunable architecture, and precise chemistry. However, COFs are typically produced in powder form and are difficult to process. Herein, we report a simple and versatile approach to fabricate macroscopic, crystalline COF gels and aerogels. Our method involves the use of dimethyl sulfoxide as a solvent and acetic acid as a catalyst to first produce a COF gel. The COF gel is then washed, dried, and reactivated to produce a pure macroscopic, crystalline, and porous COF aerogel that does not contain any binders or additives. We tested this approach for six different imine COFs and found that the crystallinities and porosities of the COF aerogels matched those of COF powders. Electron microscopy revealed a robust hierarchical pore structure, and we found that the COF aerogels could be used as absorbents in oil–water separations, for the removal of organic and inorganic micropollutants, and for the capture and retention of iodine. This study provides a versatile and simple approach for the fabrication of COF aerogels and will provide novel routes for incorporating COFs in applications that require macroscopic, porous materials.
Purchased from AmBeed: 623-27-8 ; 118727-34-7 ; 63525-48-4
CAS No. : | 63525-48-4 | MDL No. : | MFCD11521314 |
Formula : | C8H4Br2O2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | VSUKSWCSOBXUFG-UHFFFAOYSA-N |
M.W : | 291.92 | Pubchem ID : | 12353544 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
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10% | In a 100 ml flask, with a magnetic stirrer, thermometer and coolant, in an inert atmosphere, 2,5-dibromobenzene-1 ,4-dicarbaldehyde having formula (IV) obtained as described in Example 2 (0.292 g; 1.0 mmol) and potassium carbonate (K2CO3) (Aldrich) (0.691 g; 5.0 mmol) were added to a mixture of <strong>[6964-21-2]3-thiopheneacetic acid</strong> [heteroaryl compound having general formula (V) wherein Y = oxygen and Z = sulfur] (Aldrich) (0.312 g; 2.2 mmol), triphenylphosphine (Aldrich) (0.026 g; 0.1 mmol), palladium(ll)acetate (0233) [Pd(OAc)2] (0.112 g; 0.5 mmol) in L/,/V-dimethylformamide anhydrous (DMF) (Aldrich) (5 ml): the resulting reaction mixture was heated to 80C and maintained under stirring, at said temperature, for 24 hours. Subsequently, 1 -bromo-2-octyldodecane (Aldrich) [alkyl halide having general formula (VI) wherein R1 = 2-octyldodecyl and X - bromine] (0.672 g; 2.2 mmol) was added in a single portion: the reaction mixture obtained was left, under stirring, at 80C, for 24 hours. Subsequently, after cooling to room temperature (25C), the reaction mixture was placed in a 500 ml separator funnel: a solution of ammonium chloride (NH4CI) 0.1 M (Aldrich) (3 x 100 ml) was added to said reaction mixture and everything was extracted with ethyl acetate (Aldrich) (3 x 100 ml) obtaining an aqueous phase and an organic phase. The entire organic phase (obtained by joining the organic phases deriving from the three extractions) was separated and subsequently anhydrified on sodium sulfate (Aldrich) and evaporated. The residue obtained is purified through elution on a silica gel chromatography column [(eluent: n-heptane/ethylacetate 98/2) (Carlo Erba)], obtaining 0.083 g of bis(2-hexyldecyl)anthra[1 ,2-b:5,6-b’]dithiophene-4, 10- dicarboxylate having formula (la) as a white solid (yield 10%). |