CN115025762A - Metal organic framework aerogel and preparation method and application thereof - Google Patents
Metal organic framework aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal organic framework aerogel and a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a calcium carbonate suspension and a sodium alginate solution; mixing a metal organic framework, a calcium carbonate suspension and a sodium alginate solution, and freezing for pre-crosslinking; and (3) carrying out solvent exchange on the pre-crosslinked material by adopting an acetone acetate solution, washing by adopting an acetone solution, and drying to obtain the metal organic framework aerogel. The metal organic framework aerogel can be prepared by drying at normal temperature, and the preparation process is environment-friendly, low in energy consumption and simple and convenient to operate; the metal organic framework aerogel can be used for adsorbing and removing antibiotics in an environmental water body, has high removal efficiency and high adsorption rate, and has high practical application value and commercial prospect.
Description
Technical Field
The invention relates to the technical field of advanced environment-friendly materials, in particular to a metal organic framework aerogel and a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) are nanoporous materials constructed by metal and organic ligands through coordination bonds. As the MOFs have the advantages of various structural types, large specific surface area, adjustable pore size, convenience in post-modification and the like, the good adsorption property of the MOFs shows wide application prospect. The MOFs can be used as adsorbents for removing various environmental pollutants, and have become one of the research hotspots and fronts of advanced environment-friendly materials.
However, the pores of the MOFs are usually micropores, which results in poor surface affinity, reduces mass transfer efficiency between solid and liquid phases, and in addition, the powder-like texture of the MOFs causes difficult solid-liquid separation, and these problems limit the efficient application of the MOFs as an adsorbent in the field of environmental water pollution treatment. The MOFs is compounded with other functional materials, so that the defects of the MOFs can be overcome, and on the other hand, the MOFs composite material can provide more diversified active sites for the enrichment of pollutants due to different structural properties of organic pollutants in an environmental water body.
The aerogel is obtained by freeze-drying hydrogel, a hydrophilic polymer material having a three-dimensional cross-linked network structure. The aerogel material of the sponge body shows some unique structural characteristics, such as high porosity and large pore volume, ultra-low density, softness and easy cutting, however, the porous structure of the aerogel does not have good selective adsorption. The MOFs is combined with the aerogel material, so that the efficient selective adsorption characteristic of the MOFs is reserved, and the affinity and the mass transfer efficiency of the MOFs and target molecules are enhanced by the MOFs aerogel with the multi-level pore size. Furthermore, MOFs aerogels exhibit better mechanical strength compared to other aerogel materials.
Sodium alginate is a common renewable polymer material in nature, has the advantages of environmental friendliness, low cost, good hydrophilicity and the like, and the aerogel taking sodium alginate as the substrate is proved to be capable of efficiently adsorbing and removing pollutants in water.
Chinese patent application No. CN201911378601.5 discloses a method for preparing MOFs aerogel, which comprises preparing a porous solid containing a metal precursor, reacting the porous solid with a solvent containing an organic ligand to convert the metal precursor into a metal-organic framework material, and finally drying with supercritical fluid.
Chinese patent with application number CN202110439439.4 mixes, freezes and dries ZIF-L/gelatin aerogel obtained by mixing ZIF series metal organic framework material and gelatin, and then calcines the ZIF-L/gelatin aerogel composite material under the protection of nitrogen to obtain the three-dimensional metal organic framework/aerogel composite material.
The Chinese patent with application number of CN202110812440.7 prepares nano-cellulose/graphene oxide aerogel by a freeze-drying method, the nano-cellulose/graphene oxide aerogel is put into MOFs metal precursor solution, and the modified nano-cellulose/graphene oxide composite aerogel of UIO-66-COOH is prepared by a solvothermal in-situ synthesis method.
The synthesis of the above synthesized MOFs aerogels often requires freeze drying or supercritical fluid drying, and these drying methods often require specialized equipment, are high in energy consumption and take a long time.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the metal organic framework aerogel and the preparation method thereof, the metal organic framework material is mixed in the sodium alginate gel, then the metal organic framework aerogel is prepared by a solvent exchange method, and the metal organic framework aerogel can be prepared by drying at normal temperature, so that the preparation process is environment-friendly, the energy consumption is lower, and the operation is simple and convenient; the metal organic framework aerogel disclosed by the invention can be used for adsorbing and removing antibiotics in an environmental water body, has high removal efficiency and high adsorption rate, and has high practical application value and commercial prospect.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of metal organic framework aerogel comprises the following steps:
preparing a calcium carbonate suspension and a sodium alginate solution;
mixing a metal organic framework, a calcium carbonate suspension and a sodium alginate solution, and freezing for pre-crosslinking;
and (3) carrying out solvent exchange on the pre-crosslinked material by adopting an acetone acetate solution, washing by adopting an acetone solution, and drying to obtain the metal organic framework aerogel, wherein the drying can be carried out at room temperature.
The preparation of the calcium carbonate suspension comprises the following steps:
dissolving sodium carbonate in water to prepare a sodium carbonate solution;
dissolving calcium chloride in water to prepare a calcium chloride solution;
adding a sodium carbonate solution into a calcium chloride solution, and stirring to obtain a calcium carbonate suspension;
the molar ratio of the sodium carbonate to the calcium chloride is 1: 1.1-1: 1.2.
the solvent in the sodium alginate solution is water, and the concentration of the sodium alginate solution is 9-11 g/L; preferably, the concentration of the sodium alginate solution is 10 g/L.
The volume ratio of the calcium carbonate suspension to the sodium alginate solution is about 3: 10.
the mass ratio of the metal organic framework to the calcium chloride to the sodium alginate is 0.2-1: 1.2-1.6: 1.
preferably, the mass ratio of the metal organic framework to the calcium chloride to the sodium alginate is 0.8: 1.4: 1.
the metal organic framework is one of HKUST-1, MIL-53(Al) and MIL-101 (Fe).
The freezing pre-crosslinking time is 40-60 hours, and the temperature is minus 15-minus 20 ℃.
The volume ratio of acetic acid to acetone in the acetone acetate solution is 3: 100.
the HKUST-1 can be an existing material, and can also be prepared by adopting the following method, wherein the preparation of the HKUST-1 comprises the following steps:
dissolving trimesic acid in a mixed solution of ethanol and N, N-dimethylformamide to obtain a mixed solution A, wherein the concentration of the trimesic acid in the mixed solution A is 8-12 g/L, and the volume ratio of the ethanol to the N, N-dimethylformamide is 1-2: 1; preferably, the concentration of the trimesic acid in the mixed solution a is 10 g/l, and the volume ratio of the ethanol to the N, N-dimethylformamide is 1.5: 1;
dissolving copper acetate in water to prepare a copper acetate solution with the concentration of 45-65 g/L, wherein the used water is preferably pure water or ultrapure water, and preferably, the concentration of the copper acetate solution is 55 g/L; adding a copper acetate solution into the mixed solution A, wherein the volume ratio of the copper acetate solution to the mixed solution A is (1-2): preferably, the volume ratio of the copper acetate solution to the mixed liquor A is 1.5: 5, stirring, heating and refluxing to obtain a reaction solution B;
and cooling the reaction solution B, centrifuging and collecting precipitate, washing and drying the precipitate to obtain HKUST-1 powder, preferably washing the precipitate by using ultrapure water and absolute ethyl alcohol for several times, preferably drying the precipitate in a vacuum drying box at the temperature of 50-80 ℃ for 10-15 hours, and preferably drying the precipitate in a vacuum drying box at the temperature of 60 ℃ for 12 hours.
The MIL-53(Al) can be an existing material, and can also be prepared by adopting the following method, wherein the preparation method of the MIL-53(Al) comprises the following steps:
dissolving aluminum nitrate nonahydrate in N, N-dimethylformamide to prepare an aluminum nitrate nonahydrate solution with the concentration of 70-80 g/L, preferably 75 g/L; dissolving terephthalic acid in ultrapure water, and preparing a terephthalic acid solution with the concentration of 55-70 g/L, preferably 65 g/L; mixing an aluminum nitrate nonahydrate solution and a terephthalic acid solution to obtain a mixed solution B, wherein the volume ratio of the aluminum nitrate nonahydrate solution to the terephthalic acid solution is (1.5-3): 1, preferably, the volume ratio of the aluminum nitrate nonahydrate solution to the terephthalic acid solution is 2.75: 1, stirring the mixed solution B for 1-3 hours at 35-45 ℃, preferably, mechanically stirring the mixed solution B for 2 hours under the condition of water bath at 40 ℃; reacting the stirred mixed solution B at 120-140 ℃ for 40-60 hours, preferably at 130 ℃ for 48 hours to obtain a reaction product; and (3) soaking the reaction product in N, N-dimethylformamide for 12-36 hours, and then drying at 140-160 ℃ for 10-15 hours, preferably, soaking the reaction product in N, N-dimethylformamide for 24 hours, and then drying at 150 ℃ for 12 hours to obtain white powder MIL-53 (Al).
The MIL-101(Fe) can be an existing material, and can also be prepared by adopting the following method, wherein the preparation method of the MIL-101(Fe) comprises the following steps:
dissolving terephthalic acid and ferric chloride hexahydrate in N, N-dimethylformamide to prepare a mixed solution C, wherein the concentration of the terephthalic acid in the mixed solution C is 12-16 g/L, and the concentration of the ferric chloride hexahydrate in the mixed solution C is 25-30 g/L; preferably, the concentration of the terephthalic acid in the mixed solution C is 14 g/L, the concentration of the ferric chloride hexahydrate is 28 g/L, the mixed solution C is heated and reacted for 20-30 hours at 100-120 ℃, preferably, the mixed solution C is heated and reacted for 25 hours at 110 ℃, reaction products are sequentially washed by N, N-dimethylformamide and ethanol, and then dried for 10-15 hours at 80-120 ℃, preferably, dried for 12 hours at 100 ℃ to obtain brown MIL-101(Fe) powder.
A metal organic framework aerogel prepared by the method.
The application of the metal organic framework aerogel in adsorbing tetracycline antibiotics.
Compared with the prior art, the invention has the beneficial effects that:
1. the method adopts a normal-temperature drying method to prepare the metal organic framework aerogel, and has the advantages of environment-friendly preparation process, low energy consumption and simple and convenient operation.
2. When the metal organic framework aerogel is used for adsorbing and removing tetracycline antibiotics in an environmental water body, the metal organic framework aerogel has high removing efficiency and high adsorption rate, the blocky material is easy to separate solid and liquid, and the metal organic framework aerogel has good application prospect when being used as an adsorbent for antibiotic pollution in water, and the metal organic framework aerogel and the preparation method have high practical application value and commercial prospect.
Drawings
FIG. 1 is an SEM photograph of the HKUST-1 and HKUST-1 aerogels prepared in example 1 of the present invention.
FIG. 2 is an infrared spectrum.
FIG. 3 is an X-ray diffraction diagram.
FIG. 4 is a photograph of HKUST-1 aerogel.
Detailed Description
The present invention will be further described with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope defined in the present application.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers. In addition to the specific methods, devices, and materials used in the examples, the invention may be practiced using any method, device, and material that is similar or equivalent to the methods, devices, and materials described in examples herein, in addition to those described in prior art practice and the description herein.
Example 1
Example 1 an HKUST-1 metal organic framework aerogel was prepared by the following procedure:
s1, preparing a metal organic framework HKUST-1;
s11, dissolving 1 g of trimesic acid in a mixed solution of 60 ml of absolute ethyl alcohol and 40 ml of N, N-dimethylformamide to obtain a mixed solution A, stirring until the trimesic acid is completely dissolved, and transferring the mixed solution A to a round-bottom flask;
s12, dissolving 1.65 g of copper acetate in 30 ml of water to prepare a copper acetate solution, wherein the water is preferably pure water or ultrapure water, adding the copper acetate solution into the mixed solution A, stirring at the heating temperature of 70 ℃, and heating and refluxing for 7 hours to obtain a reaction solution B;
s13, cooling the reaction solution B to room temperature, centrifuging and collecting precipitate, washing the precipitate with 2 times of ultrapure water and 2 times of absolute ethyl alcohol in sequence, and drying the washed product in a vacuum drying oven at the drying temperature of 60 ℃ for 12 hours to obtain the HKUST-1 powder.
S2, preparing a calcium carbonate suspension and a sodium alginate solution;
s21, preparing calcium carbonate suspension: 0.66 g of sodium carbonate (Na) 2 CO 3 ) Dissolving in 25 ml water to prepare sodium carbonate solution, adding 0.75 g calcium chloride (CaCl) 2 ) Dissolving the mixture in 25 ml of water to prepare a calcium chloride solution, dripping a sodium carbonate solution into the calcium chloride solution, and violently stirring for 30 minutes to obtain a calcium carbonate suspension; the water used for the sodium carbonate solution and the calcium chloride solution is preferably ultrapure water;
s22, preparing a sodium alginate solution: dispersing 0.5 g of sodium alginate in 50 ml of water, ultrasonically stirring for 1 hour, and standing for 20-60 minutes to obtain a uniform bubble-free sodium alginate solution.
S3, mixing the metal organic framework, the calcium carbonate suspension and the sodium alginate solution, and freezing for pre-crosslinking;
and (2) fully mixing 80 mg of metal organic framework powder and 3 ml of calcium carbonate suspension, adding the mixture into 10 ml of sodium alginate solution, fully and uniformly stirring to obtain mixed solution D, putting 2 ml of the mixed solution D into a 5 ml small beaker, and pre-crosslinking in a refrigerator freezing chamber for 48 hours.
S4, carrying out solvent exchange on the pre-crosslinked material by adopting a glacial acetic acid acetone solution, wherein the volume ratio of acetic acid to acetone in the acetic acid acetone solution is 3: and 100, washing with an acetone solution to remove acetic acid in the material, and drying the material in a fume hood to obtain the metal organic framework aerogel.
The metal-organic framework in this example is HKUST-1 prepared in step S1.
Example 2
This example prepares MIL-53(Al) metal organic framework aerogel by the following steps:
the difference from example 1 is that the metal-organic framework of the present example is MIL-53(Al), and the MIL-53(Al) is prepared by the following specific steps:
s11, dissolving 3.38 g of aluminum nitrate nonahydrate in 44 ml of N, N-dimethylformamide, dissolving 1.00 g of terephthalic acid in 16 ml of ultrapure water, uniformly mixing the two solutions to obtain a mixed solution B, and mechanically stirring the mixed solution B in a water bath at the temperature of 40 ℃ for 2 hours;
s12, transferring the mixed solution B into a reaction kettle, and reacting for 48 hours at the heating temperature of 130 ℃ to obtain a reaction product;
s13, naturally cooling the reaction kettle to room temperature, taking out a reaction product, soaking the reaction product in N, N-dimethylformamide for 24 hours, and then putting the reaction product into an oven at 150 ℃ for drying for 12 hours to obtain white powder MIL-53 (Al).
The rest corresponds to example 1.
Example 3
Example 1 MIL-101(Fe) metal organic framework aerogel was prepared by the following steps:
the difference from example 1 is that the metal organic framework of the present example is MIL-101(Fe), and the specific steps for preparing MIL-101(Fe) are as follows:
dissolving terephthalic acid and ferric chloride hexahydrate in N, N-dimethylformamide to prepare a mixed solution C, wherein the concentration of the terephthalic acid in the mixed solution C is 15 g/L, the concentration of the ferric chloride hexahydrate in the mixed solution C is 28 g/L, heating the mixed solution C at 110 ℃ for reaction for 25 hours, sequentially washing a reaction product by using the N, N-dimethylformamide and ethanol, and drying the product at 100 ℃ for 12 hours to obtain brown MIL-101(Fe) powder.
The rest corresponds to example 1.
Example 4
The application of the metal organic framework aerogel in adsorbing tetracycline antibiotics is characterized in that the HKUST-1 aerogel material obtained in the example 1 is used for static adsorption of the tetracycline antibiotics (aureomycin, doxycycline, oxytetracycline and tetracycline hydrochloride) in a water body. The standard powder of chlortetracycline, doxycycline, oxytetracycline, tetracycline hydrochloride was dissolved in 20 ml of ultrapure water and placed in a 250 ml Erlenmeyer flask. And (3) enabling the initial solubility of the four antibiotics to be 20mg/L, adding an HKUST-1 aerogel material, placing the conical flask in an oscillator for oscillation and adsorption for 40 minutes, measuring the absorbance of the adsorbed sample solution by an ultraviolet visible spectrophotometer after adsorption is finished, and determining the concentration of the adsorbed tetracycline hydrochloride. The concentrations of the four antibiotics after adsorption were 1.67mg/L, 2.10mg/L, 1.47mg/L, and 0.60mg/L, respectively. The removal rates of aureomycin, doxycycline, oxytetracycline, and tetracycline hydrochloride calculated by formula 1 respectively reach 91.63%, 89.51%, 92.67%, and 96.98%.
In the formula c 0 Represents the initial concentration of the antibiotic, c e Represents the concentration of antibiotic at equilibrium of adsorption after 40 minutes of adsorption.
Example 5
0.03 g of the HKUST-1 aerogel material obtained in example 1 was packed in a glass column having an inner diameter of 1 cm for dynamic adsorption of oxytetracycline in water. Dissolving the standard terramycin powder in ultrapure water to prepare a 100 microgram/liter terramycin polluted water sample. Pouring the oxytetracycline contaminated water sample into a glass column filled with the HKUST-1 aerogel material, so that the HKUST-1 aerogel dynamically adsorbs the oxytetracycline in the water in real time. And (3) determining the oxytetracycline concentration before and after dynamic adsorption by adopting a liquid chromatograph tandem mass spectrum, and determining the concentration of the water sample after adsorption after every 0.5L of oxytetracycline polluted water sample is adsorbed. The adsorption column prepared by the HKUST-1 aerogel can continuously treat an oxytetracycline polluted water sample under the driving of gravity, the water inlet flow rate can reach 12 ml/min, and after 10 liters of oxytetracycline polluted water sample with the initial concentration of 100 micrograms/liter is adsorbed by the HKUST-1 aerogel, the concentration of the oxytetracycline in the outlet water approaches 100 micrograms/liter and gradually reaches saturation.
From the above, the invention adopts the normal temperature drying method to prepare the metal organic framework aerogel material,
the HKUST-1 aerogel prepared by the method of the present invention was characterized as represented by example 1, and the characterization results of the HKUST-1 aerogel prepared by the other examples were substantially similar to those of example 1 and were not provided.
(I) morphology characterization
The surface morphology of the HKUST-1 powder and the HKUST-1 aerogel was characterized by using a ZEISSSigma model 300 scanning electron microscope manufactured by Zeiss, and the results are shown in FIG. 1, wherein A, B is an SEM image of the HKUST-1 powder, and C, D is an SEM image of the HKUST-1 aerogel.
The A, B graph of the attached figure 1 shows that the HKUST-1 powder is of a cubic structure of 10-20 micrometers, the C, D graph of the attached figure 1 shows that the HKUST-1 aerogel has a macroporous layered structure, the surface of the HKUST-1 aerogel has a plurality of folds, and HKUST-1 crystals are uniformly embedded in an aerogel lamellar structure.
(II) infrared spectroscopic analysis
The samples of example 1 of the present invention were tested using a PerkinElmer frontier model infrared spectrometer manufactured by PerkinElmer corporation. Analysis FIG. 2 is an infrared spectrum of a test sample, wherein a is an infrared spectrum of HKUST-1 powder, b is an infrared spectrum of sodium alginate gel, and c is an infrared spectrum of HKUST-1 aerogel. a median wave number of 1444cm -1 And 1650cm -1 The absorption peak at (b) is related to the-O-C-O-group, and the wave number is 1383cm -1 And 1590cm -1 The absorption peak comes from C ═ C stretching vibration, and the wave number is 730cm -1 And 760cm -1 The absorption peaks at (A) are derived from the Cu-O bond, which demonstrates the successful synthesis of HKUST-1. 2930cm in b -1 And 1025cm -1 Cycloalkyl C-H stretching vibration and C-O stretching vibration from sodium alginate. c contains characteristic peaks of HKUST-1 and sodium alginate, and the successful synthesis of the HKUST-1 sodium alginate aerogel is proved.
(III) XRD analysis
The crystal structure of example 1 of the present invention was characterized using a bruker d8Advance model X-ray diffractometer, manufactured by bruker instruments. The results are shown in FIG. 3, where a is the XRD profile of HKUST-1 powder and b is the XRD profile of HKUST-1 aerogel, and a shows distinct characteristic peaks at 9.6 ° (220), 11.5 ° (222), 13.2 ° (440), 16.3 ° (422), 17.3 ° (511), 20.0 ° (660), 29.3 ° (751), 35.0 ° (773) and 46.8 ° (751) at 2 θ, demonstrating the successful synthesis of HKUST-1, and these characteristic peaks in b remain, indicating that the step of synthesizing aerogel does not affect the crystal structure of HKUST-1.
As described above, HKUST-1 aerogel materials have been successfully prepared.
Claims (10)
1. The preparation method of the metal organic framework aerogel is characterized by comprising the following steps:
preparing a calcium carbonate suspension and a sodium alginate solution;
mixing a metal organic framework, a calcium carbonate suspension and a sodium alginate solution, and freezing for pre-crosslinking;
and (3) carrying out solvent exchange on the pre-crosslinked material by adopting an acetone acetate solution, washing by adopting an acetone solution, and drying to obtain the metal organic framework aerogel.
2. The method for preparing the metal-organic framework aerogel according to claim 1, wherein the preparing the calcium carbonate suspension comprises:
dissolving sodium carbonate in water to prepare a sodium carbonate solution;
dissolving calcium chloride in water to prepare a calcium chloride solution;
adding a sodium carbonate solution into a calcium chloride solution, and stirring to obtain a calcium carbonate suspension;
the molar ratio of the sodium carbonate to the calcium chloride is 1: 1.1-1: 1.2.
3. the preparation method of the metal organic framework aerogel according to claim 1, wherein a solvent in the sodium alginate solution is water, and the concentration of the sodium alginate solution is 9-11 g/L;
the mass ratio of the metal organic framework to the calcium chloride to the sodium alginate is (0.2-1): 1.2-1.6: 1.
4. the preparation method of the metal organic framework aerogel according to claim 1, wherein the freezing pre-crosslinking time is 40-60 hours, and the temperature is-15 to-20 ℃; the volume ratio of acetic acid to acetone in the acetone acetate solution is 3: 100.
5. the method for preparing aerogel containing metal organic framework as claimed in claim 1, wherein the metal organic framework is one of HKUST-1, MIL-53(Al) and MIL-101 (Fe).
6. The method for preparing metal organic framework aerogel according to claim 5, wherein the preparation of HKUST-1 comprises the following steps:
dissolving trimesic acid in a mixed solution of ethanol and N, N-dimethylformamide to obtain a mixed solution A, wherein the concentration of the trimesic acid in the mixed solution A is 8-12 g/L, and the volume ratio of the ethanol to the N, N-dimethylformamide is (1-2): 1;
dissolving copper acetate in water to prepare a copper acetate solution with the concentration of 45-65 g/L, adding the copper acetate solution into the mixed solution A, stirring, heating and refluxing to obtain a reaction solution B, wherein the volume ratio of the copper acetate solution to the mixed solution A is (1-2): 5;
and cooling the reaction solution B, centrifuging and collecting a precipitate, and washing and drying the precipitate to obtain the HKUST-1.
7. The method for preparing metal organic framework aerogel according to claim 5, wherein the MIL-53(Al) is prepared by the following steps:
dissolving aluminum nitrate nonahydrate in N, N-dimethylformamide, preparing an aluminum nitrate nonahydrate solution with the concentration of 70-80 g/L, dissolving terephthalic acid in ultrapure water, preparing a terephthalic acid solution with the concentration of 55-70 g/L, and mixing the aluminum nitrate nonahydrate solution and the terephthalic acid solution to obtain a mixed solution B, wherein the volume ratio of the aluminum nitrate nonahydrate solution to the terephthalic acid solution is (1.5-3): stirring the mixed solution B at 35-45 ℃ for 1-3 hours, then reacting at 120-140 ℃ for 40-60 hours, soaking the reaction product in N, N-dimethylformamide for 12-36 hours, and drying at 140-160 ℃ for 10-15 hours to obtain white powder MIL-53 (Al).
8. The method for preparing metal organic framework aerogel according to claim 5, wherein the MIL-101(Fe) is prepared by the following steps:
dissolving terephthalic acid and ferric chloride hexahydrate in N, N-dimethylformamide to prepare a mixed solution C, wherein the concentration of the terephthalic acid in the mixed solution C is 12-16 g/L, and the concentration of the ferric chloride hexahydrate is 25-30 g/L; and heating the mixed solution C at 100-120 ℃ for reaction for 20-30 hours, washing the reaction product by using N, N-dimethylformamide and ethanol in sequence, and drying at 80-120 ℃ for 10-15 hours to obtain brown MIL-101(Fe) powder.
9. A metal organic framework aerogel prepared according to the method of any one of claims 1 to 8.
10. Use of the metal organic framework aerogel according to claim 9 for adsorbing tetracycline antibiotics.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115501862A (en) * | 2022-09-20 | 2022-12-23 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
| CN115739046A (en) * | 2022-11-15 | 2023-03-07 | 武汉大学 | HKUST-1/alginate gel particle composite material, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498695A (en) * | 2015-12-02 | 2016-04-20 | 南京师范大学 | Sodium alginate-MOF (metal organic framework) composite spherule as well as preparation method and application thereof |
| CN107899559A (en) * | 2017-11-29 | 2018-04-13 | 中南大学 | A kind of defect MIL 53 (Al) metal organic framework and its preparation method and application |
| CN110102267A (en) * | 2019-05-27 | 2019-08-09 | 华南理工大学 | A kind of aluminium base MOFs/ chitosan compound microsphere and its preparation method and application |
| US20190367395A1 (en) * | 2018-05-31 | 2019-12-05 | Soochow University | Graphene aerogel metallic organic frame composite material loaded with microorganism as well as preparation method and application thereof in the treatment of azo dye |
| CN112619616A (en) * | 2020-12-31 | 2021-04-09 | 陕西科技大学 | High-load SA/GO/ZIFs composite adsorbent and preparation method and application thereof |
| CN114100582A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Hydrogel type composite material, preparation method thereof, method for removing benzene series by using hydrogel type composite material and application of hydrogel type composite material |
-
2022
- 2022-06-02 CN CN202210623390.2A patent/CN115025762A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498695A (en) * | 2015-12-02 | 2016-04-20 | 南京师范大学 | Sodium alginate-MOF (metal organic framework) composite spherule as well as preparation method and application thereof |
| CN107899559A (en) * | 2017-11-29 | 2018-04-13 | 中南大学 | A kind of defect MIL 53 (Al) metal organic framework and its preparation method and application |
| US20190367395A1 (en) * | 2018-05-31 | 2019-12-05 | Soochow University | Graphene aerogel metallic organic frame composite material loaded with microorganism as well as preparation method and application thereof in the treatment of azo dye |
| CN110102267A (en) * | 2019-05-27 | 2019-08-09 | 华南理工大学 | A kind of aluminium base MOFs/ chitosan compound microsphere and its preparation method and application |
| CN114100582A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Hydrogel type composite material, preparation method thereof, method for removing benzene series by using hydrogel type composite material and application of hydrogel type composite material |
| CN112619616A (en) * | 2020-12-31 | 2021-04-09 | 陕西科技大学 | High-load SA/GO/ZIFs composite adsorbent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JOWAN ROSTAMI ET AL.: ""Hierarchical build-up of bio-based nanofibrous materials with tunable metal-organic framework biofunctionality"", 《MATERIALS TODAY》, vol. 48, pages 47 - 58, XP086835820, DOI: 10.1016/j.mattod.2021.04.013 * |
| XUEQI CHEN ET AL.: ""One-step fabrication of novel MIL-53(Fe, Al) for synergistic adsorption-photocatalytic degradation of tetracycline"", 《CHEMOSPHERE》, vol. 291, pages 133032 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115501862A (en) * | 2022-09-20 | 2022-12-23 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
| CN115501862B (en) * | 2022-09-20 | 2023-11-21 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
| CN115739046A (en) * | 2022-11-15 | 2023-03-07 | 武汉大学 | HKUST-1/alginate gel particle composite material, and preparation method and application thereof |
| CN115739046B (en) * | 2022-11-15 | 2024-01-16 | 武汉大学 | HKUST-1/alginate gel particle composite material, and preparation method and application thereof |
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