CN107177038B - Moisture-resistant MOF-5-like compound, preparation method and application - Google Patents

Moisture-resistant MOF-5-like compound, preparation method and application Download PDF

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CN107177038B
CN107177038B CN201710266335.1A CN201710266335A CN107177038B CN 107177038 B CN107177038 B CN 107177038B CN 201710266335 A CN201710266335 A CN 201710266335A CN 107177038 B CN107177038 B CN 107177038B
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naphthyl
mof
methylthiophene
dicarboxylic acid
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CN107177038A (en
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姜春杰
杨广生
刘雪婷
程聪
闫俐宏
王晓慧
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Liaoning Normal University
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Abstract

The invention discloses a moisture-resistant MOF-5-like compound, which is characterized in that: the MOF-5-like compound is 3- (2-naphthyl) -4-methylthiophene [2,3-b]And thiophene-2,5-dicarboxylic acid with Zn2+The preparation method is simple and the cost is low. Due to hydrophobic aryl groups in Zn4A hydrophobic environment is formed around the O structural unit, so that the MOF-5 compound has obvious moisture resistance and high practical application value on the premise of high specific surface area and porosity. Meanwhile, the MOF-5-like compound has the performance of adsorbing iodine molecules, can be recycled, and can be applied to treatment of iodine-polluted environments.

Description

Moisture-resistant MOF-5-like compound, preparation method and application
Technical Field
The invention relates to an MOFs compound, in particular to an anti-humidity MOF-5 compound, a preparation method and application thereof.
Background
MOFSThe compound is a metal-organic framework material constructed by organic ligands and inorganic metal unitsThe composite material has the advantages of large specific surface area, large pores, various structural compositions, good thermal stability and the like. The MOF-5 compound is prepared from terephthalic acid (H)2BDC) and Zn2+The metal-organic framework compound is constructed, has the characteristics of high specific surface area and high porosity as a classical metal-organic framework compound, and has wide application prospects in the fields of energy storage, molecular selective absorption and separation, catalyst loading, drug transmission and the like. However, the structural framework of MOF-5 is very sensitive to water molecules, so that the MOF-5 is very easy to absorb moisture and decompose in air, and the practical application of the MOF-5 is severely limited. In addition, no report on the function of adsorbing iodine molecules of MOF-5 compounds has been provided so far.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides an anti-moisture MOF-5-like compound, a preparation method and application thereof.
The technical solution of the invention is as follows: a MOF-5-like compound that is resistant to moisture, characterized by: the MOF-5-like compound is 3- (2-naphthyl) -4-methylthiophene [2,3-b]And thiophene-2,5-dicarboxylic acid with Zn2+And constructing the product.
A process for the preparation of a MOF-5-like compound resistant to moisture as described above, characterised in that it is carried out in sequence according to the following steps:
a. placing 1- (2-naphthyl) -1, 3-butanedione, carbon disulfide, anhydrous potassium carbonate and N, N-dimethylformamide into a three-neck flask, stirring for 30min at room temperature, adding ethyl bromoacetate in an ice bath, and reacting for 4-10 h under the condition of a water bath at 30 ℃, wherein the dosage ratio of the 1- (2-naphthyl) -1, 3-butanedione, the carbon disulfide, the anhydrous potassium carbonate, the N, N-dimethylformamide to the ethyl bromoacetate is 10 mmol: 10 mmol: 60 mmol: 10mL of: 20mmol of the active carbon;
b. pouring the reaction solution into ice water, separating to obtain a solid, and recrystallizing with ethyl acetate or ethanol to obtain a recrystallized solid;
c. hydrolyzing the obtained recrystallized solid in ethanol or water solution dissolved with KOH, adjusting pH value to 2, filtering and drying to obtain 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid;
d. dissolving 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid and zinc nitrate in N, N-dimethylformamide, and reacting at 85-100 ℃ for 24-72 h to obtain a transparent cubic crystal, wherein the dosage ratio of the 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid, the zinc nitrate and the N, N-dimethylformamide is 0.1 mmol: 0.4-0.6 mmol: 10 mL.
Use of a MOF-5-like compound as described above which is resistant to moisture in the absorption of iodine molecules.
The invention uses 3- (2-naphthyl) -4-methylthiophene [2,3-b ] containing hydrophobic aryl groups]And thiophene-2,5-dicarboxylic acid with Zn2+Successfully constructs the MOF-5-like compound, and has simple preparation method and low cost. Due to hydrophobic aryl groups in Zn4A hydrophobic environment is formed around the O structural unit, so that the MOF-5 compound has obvious moisture resistance and high practical application value on the premise of high specific surface area and porosity. Meanwhile, the MOF-5-like compound has the performance of adsorbing iodine molecules, can be recycled, and can be applied to treatment of iodine-polluted environments.
Drawings
FIG. 1 is a graph showing the adsorption curve of iodine molecules of the compound of example 1 of the present invention.
FIG. 2 is N of a compound of example 1 of the present invention2Adsorption heat profile.
FIG. 3 is a PXRD spectrum of the compound of example 1 of the present invention exposed to air for various periods of time.
Detailed Description
Example 1:
a. placing 10mmol of 1- (2-naphthyl) -1, 3-butanedione (1- (naphthalene-2-yl) butane-1, 3-dione), 10mmol of carbon disulfide, 60mmol of anhydrous potassium carbonate and 10mL of N, N-Dimethylformamide (DMF) in a three-neck flask, stirring at room temperature for 30min, adding 20mmol of ethyl bromoacetate in an ice bath, and reacting at 30 ℃ for 6h in a water bath;
b. pouring the reaction liquid into ice water, separating to obtain a solid, and recrystallizing with ethyl acetate to obtain a recrystallized solid;
c. hydrolyzing the obtained recrystallized solid in a solution of ethanol dissolved with KOH, adjusting the pH value to 2, performing suction filtration and drying to obtain 3- (2-naphthyl) -4-methylthiophene [2,3-b ] benzothiophene-2, 5-dicarboxylic acid (3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid);
d. 0.1mmol of 3- (2-naphthyl) -4-methylthiophene [2,3-b ]]Bithiophene-2, 5-dicarboxylic acid with 0.6mmol of zinc nitrate (Zn (NO)3)2·6H2O) is dissolved in 10mL of N, N-dimethylformamide and reacts for 24h in a polytetrafluoroethylene reaction kettle at the temperature of 100 ℃ to obtain transparent cubic crystals.
Example 2:
a. placing 10mmol of 1- (2-naphthyl) -1, 3-butanedione (1- (naphthalene-2-yl) butane-1, 3-dione), 10mmol of carbon disulfide, 60mmol of anhydrous potassium carbonate and 10mL of N, N-Dimethylformamide (DMF) in a three-neck flask, stirring at room temperature for 30min, adding 20mmol of ethyl bromoacetate in an ice bath, and reacting at 30 ℃ for 4h in a water bath;
b. pouring the reaction liquid into ice water, separating to obtain a solid, and recrystallizing with ethanol to obtain a recrystallized solid;
c. hydrolyzing the obtained recrystallized solid in a solution of ethanol dissolved with KOH, adjusting the pH value to 2, performing suction filtration and drying to obtain 3- (2-naphthyl) -4-methylthiophene [2,3-b ] benzothiophene-2, 5-dicarboxylic acid (3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid);
d. 0.1mmol of 3- (2-naphthyl) -4-methylthiophene [2,3-b ]]Bithiophene-2, 5-dicarboxylic acid with 0.6mmol of zinc nitrate (Zn (NO)3)2·6H2O) is dissolved in 10mL of N, N-dimethylformamide and reacts for 72h at 85 ℃ in a polytetrafluoroethylene reaction kettle to obtain transparent cubic crystals.
Example 3:
a. placing 10mmol of 1- (2-naphthyl) -1, 3-butanedione (1- (naphthalene-2-yl) butane-1, 3-dione), 10mmol of carbon disulfide, 60mmol of anhydrous potassium carbonate and 10mL of N, N-Dimethylformamide (DMF) in a three-neck flask, stirring at room temperature for 30min, adding 20mmol of ethyl bromoacetate in an ice bath, and reacting at 30 ℃ for 10h in a water bath;
b. pouring the reaction liquid into ice water, separating to obtain a solid, and recrystallizing with ethyl acetate to obtain a recrystallized solid;
c. hydrolyzing the obtained recrystallized solid in an aqueous solution dissolved with KOH, adjusting the pH value to 2, filtering and drying to obtain 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid (3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid);
d. 0.1mmol of 3- (2-naphthyl) -4-methylthiophene [2,3-b ]]Bithiophene-2, 5-dicarboxylic acid with 0.6mmol of zinc nitrate (Zn (NO)3)2·6H2O) is dissolved in 10mL of N, N-dimethylformamide and reacts for 48 hours at 90 ℃ in a polytetrafluoroethylene reaction kettle to obtain transparent cubic crystals.
Example 4:
the transparent cubic crystal (compound) obtained in example 1 was refluxed in methylene chloride for 3 hours, and then the crystal was separated and placed in a vacuum oven, and kept at 80 ℃ for 1 hour to remove solvent molecules in the porous structure. 0.5g of the compound from which the solvent was removed was put in iodine vapor at 80 ℃ and the iodine absorbability of the compound was measured by a gravimetric method. The iodine molecule adsorption curve is shown in figure 1, the compound after removing the solvent can absorb iodine molecules, and the absorption amount can reach 33.9 within 10hwPercent, the maximum can reach 36.0w% of the total weight of the composition. Meanwhile, the compound can remove absorbed iodine molecules in a heating or organic solvent extraction mode, so that the compound can be recycled, can be used for iodine molecule absorption, and is applied to treatment of iodine pollution in the environment.
Experimental example 1:
the crystals of transparent cubes obtained in examples 1, 2 and 3 were subjected to single crystal diffraction data measurement on a Bruker Apex CCD single crystal diffractometer and analyzed and refined using the SHELXS-97 program. The results show that the compound crystallized in the Cubic crystal system, Fm-3m space group. In the structural unit, four zinc metal ions are tetrahedrally connected with a central oxygen atom to form Zn4O cluster structural units, each Zn4The O cluster connects six carboxylic acid ligands in orthogonal directions through a linear dicarboxylic acid, forming a classical MOF-5-like structure. The reasonable bond length and angle prove the single crystal dataAnd (6) reliability. The powder X-ray diffraction experiment is carried out on a Bruker D8 ADVANCE X-ray polycrystal diffractometer, the diffraction pattern is consistent with single crystal simulation data, and the compound is proved to have good purity.
Experimental example 2:
the crystals of the transparent cube obtained in example 1 were characterized for the porosity of the compound by an AUTOSORB-1MP full-automatic specific surface area and micropore analyzer, Quantachrome, usa. N is a radical of2The adsorption heat profile is shown in FIG. 2, N2The isothermal adsorption curve shows a type I reversible adsorption of a typical microporous material with a Brunauer-Emmett-Teller (BET) surface area of 1102.5 m2g-1Pore volume of 0.52 cm3g-1The average pore diameter was 1.8 nm. The results show that the compound structure has higher specific surface area and remarkable porous characteristic.
Experimental example 3:
the stability of the structure in air was examined by a powder diffraction experiment using the transparent cubic crystal obtained in example 1. Crystals of this compound were exposed to air and the powder diffraction patterns were collected on day 1, day 3 and day seven, respectively. The PXRD pattern is shown in figure 3: compared with the freshly synthesized crystal diffraction pattern, the main diffraction characteristic peaks are well matched, which indicates that the framework structure still keeps stable, and the reduction of the strength of the characteristic peaks and the increase of the half-peak width value are attributed to the reduction of the crystallinity of the crystals. Clearly, this compound exhibited significant moisture resistance compared to MOF-5.

Claims (1)

1. A method for preparing a MOF-5-like compound resistant to moisture, said MOF-5-like compound being prepared from 3- (2-naphthyl) -4-methylthiophene [2,3-b ]]And thiophene-2,5-dicarboxylic acid with Zn2+The construction method is characterized by comprising the following steps in sequence:
a. placing 1- (2-naphthyl) -1, 3-butanedione, carbon disulfide, anhydrous potassium carbonate and N, N-dimethylformamide into a three-neck flask, stirring for 30min at room temperature, adding ethyl bromoacetate in an ice bath, and reacting for 4-10 h under the condition of a water bath at 30 ℃, wherein the dosage ratio of the 1- (2-naphthyl) -1, 3-butanedione, the carbon disulfide, the anhydrous potassium carbonate, the N, N-dimethylformamide to the ethyl bromoacetate is 10 mmol: 10 mmol: 60 mmol: 10mL of: 20mmol of the active carbon;
b. pouring the reaction solution into ice water, separating to obtain a solid, and recrystallizing with ethyl acetate or ethanol to obtain a recrystallized solid;
c. hydrolyzing the obtained recrystallized solid in ethanol or water solution dissolved with KOH, adjusting pH value to 2, filtering and drying to obtain 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid;
d. dissolving 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid and zinc nitrate in N, N-dimethylformamide, and reacting at 85-100 ℃ for 24-72 h to obtain a transparent cubic crystal, wherein the dosage ratio of the 3- (2-naphthyl) -4-methylthiophene [2,3-b ] thiophene-2,5-dicarboxylic acid, the zinc nitrate and the N, N-dimethylformamide is 0.1 mmol: 0.4-0.6 mmol: 10 mL.
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