CN111001442A - Metal organic framework MIL-101(Cr) loaded chitosan material and preparation method and application thereof - Google Patents
Metal organic framework MIL-101(Cr) loaded chitosan material and preparation method and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 69
- 239000013178 MIL-101(Cr) Substances 0.000 title claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 4
- HEVMDQBCAHEHDY-UHFFFAOYSA-N (Dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=CC=C1 HEVMDQBCAHEHDY-UHFFFAOYSA-N 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
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- 238000006555 catalytic reaction Methods 0.000 description 8
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- 150000007517 lewis acids Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
The invention relates to the technical field of catalysts, and particularly relates to a metal organic framework MIL-101(Cr) loaded chitosan material, and a preparation method and application thereof. The metal organic framework MIL-101(Cr) loaded chitosan material is a core-shell structure formed by coating Chitosan (CS) on the outer surface of MIL-101 (Cr). The preparation method comprises the following steps: adding chitosan into acetic acid solution, stirring to dissolve, adding Cr (NO)3)3·9H2O, terephthalic acid (H)2BDC) is added into the acetic acid solution dissolved with the chitosan, and the mixture is stirred; mixing the aboveTransferring the obtained solution into a high-pressure kettle, sealing, putting into an oven, slowly heating to 463-483K, heating, and keeping for 7-9 h; slowly cooling to room temperature, washing, filtering and drying to obtain the target product. Shows good catalytic performance for deacetalization-Knoevenagel condensation reaction.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a metal organic framework MIL-101(Cr) loaded chitosan material, and a preparation method and application thereof.
Background
Metal organic framework Materials (MOFs) are two-dimensional and three-dimensional porous crystalline materials formed by combining metal nodes or metal clusters with organic ligands. MOFs have structural diversity, adjustable pore size and simple synthesis method, have wide application in the fields of catalysis, gas storage, sensing and the like, and are materials with high practicability. Because MOFs have large specific surface area, a large number of active sites and excellent stability, in recent years, MOFs have wide application in the field of catalysis and develop rapidly. The MOFs have unique three-dimensional ordered structures and can accommodate different active sites for concerted catalysis, so that the application of the MOFs in the field of catalytic tandem reaction is more possible.
The series reaction is a chemical reaction which is continuously carried out for two or more steps, can obtain a final reaction product in one pot, does not need to separate and purify an intermediate product, and has multiple advantages of environmental friendliness, economy, simple and convenient operation, time saving and the like. The tandem reaction is undoubtedly an effective solution for the preparation of complex industrial products, and is believed to become a new development trend in the field of catalysis in the future.
Disclosure of Invention
The invention aims to utilize an in-situ growth method to load chitosan on the outer surface of a metal organic framework MIL-101(Cr) to synthesize a composite material catalyst, and researches the composite material catalyst as a Lewis acid,
Acid and
alkali three-function catalyst, catalytic performance for deacetalization-Knoevenagel condensation reaction.
The technical scheme adopted by the invention is as follows: a metal organic framework MIL-101(Cr) loaded chitosan material is a core-shell structure formed by coating chitosan on the outer surface of MIL-101 (Cr).
The preparation method of the metal organic framework MIL-101(Cr) loaded chitosan material comprises the following steps:
(1) adding chitosan into the mixtureAdding into acetic acid solution, stirring at room temperature until chitosan is completely dissolved, and adding Cr (NO)3)3·9H2O，H2Adding BDC into the acetic acid solution dissolved with chitosan, and stirring at room temperature for 20-40 min;
(2) transferring the solution obtained in the step (1) to a high-pressure autoclave with a polytetrafluoroethylene lining, sealing, putting the autoclave into an oven, slowly heating to 463-483K, heating, and keeping for 7-9 h;
(3) slowly cooling to room temperature, washing with N, N-dimethylformamide and methanol in sequence, filtering and drying to obtain the target product.
Preferably, in the preparation method of the metal organic framework MIL-101(Cr) loaded chitosan material, in the step (1), Cr (NO) is used in a molar ratio3)3·9H2O：H2BDC：CS＝3-5:2-4:1。
More preferably, in the above method for preparing the metal organic framework MIL-101(Cr) -supported chitosan material, in the step (1), Cr (NO) is added according to a molar ratio3)3·9H2O：H2BDC：CS＝4.05:3.24:1。
Preferably, in the above preparation method of the metal-organic framework MIL-101(Cr) -supported chitosan material, in the step (1), the concentration of the acetic acid solution is, by mass, acetic acid: distilled water is 1: 100.
Preferably, in the above preparation method of the metal-organic framework MIL-101(Cr) -loaded chitosan material, in the step (2), the temperature rising rate of the slow temperature rising is 10 K.min-1。
Preferably, in the above preparation method of the metal organic framework MIL-101(Cr) -supported chitosan material, in the step (3), the temperature reduction rate of slowly cooling to room temperature is 10K · min-1。
The metal organic framework MIL-101(Cr) loaded chitosan material is applied to catalysis of deacetalization-Knoevenagel condensation reaction.
The application comprises the steps of putting benzaldehyde dimethyl acetal, malononitrile, acetonitrile, distilled water and a catalyst into a reaction tube, and introducing N under the stirring condition2Reacting for 12 hours at the temperature of 80 ℃; the above-mentionedThe catalyst of (a) is the metal organic framework MIL-101(Cr) supported chitosan material of claim 1.
The invention has the beneficial effects that: the metal organic framework MIL-101(Cr) has unsaturated metal sites, can be used as Lewis acid sites, has rich amino groups on chitosan, and can be used as Lewis acid sites
Basic site, hydroxy can be used as
An acidic site. Therefore, the composite material of the present invention can be used as a Lewis acid,
Acid and
the alkali three-functional catalyst shows good catalytic performance for deacetalization-Knoevenagel condensation reaction. The metal organic framework MIL-101(Cr) loaded chitosan composite material prepared by the invention has the advantages of simple synthesis method, cheap and easily obtained raw materials and application prospect.
Drawings
FIG. 1 is an XRD pattern of a metal organic framework MIL-101(Cr) supported chitosan material.
FIG. 2 is a thermogram of metal-organic framework MIL-101(Cr) supported chitosan material.
FIG. 3 is a scanning electron microscope image of a metal organic framework MIL-101(Cr) loaded chitosan material.
FIG. 4 is a gas phase adsorption graph of metal organic framework MIL-101(Cr) supported chitosan material.
FIG. 5 is a diagram of catalytic activity of metal organic framework MIL-101(Cr) supported chitosan material for five cycles of catalytic reaction.
FIG. 6 is an XRD pattern of a metal organic framework MIL-101(Cr) loaded chitosan material after five cycles of catalytic reactions.
FIG. 7 is a leaching experimental graph of a metal organic framework MIL-101(Cr) loaded chitosan material.
Detailed Description
Example 1 Metal organic framework MIL-101(Cr) loaded chitosan composite material
Adding chitosan (60mg, 0.37mmol) into 15mL of 1 wt% acetic acid solution, stirring at room temperature until chitosan is completely dissolved, and adding Cr (NO)3)3·9H2O(0.6g，1.50mmol)，H2Adding BDC (0.2g, 1.20mmol) into the acetic acid solution dissolved with chitosan, stirring at room temperature for 30min until the mixture is uniformly mixed, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the container, putting the container into an oven, and heating at a speed of 10 K.min-1Heating at 473K, and keeping for 8 h; slowly cooling to room temperature at a cooling rate of 10 K.min-1And washing with N, N-dimethylformamide and methanol, filtering and drying to obtain the metal organic framework MIL-101(Cr) loaded chitosan composite material.
According to the synthesized metal organic framework MIL-101(Cr) loaded chitosan material, chitosan is loaded on the outer surface of MIL-101(Cr) to form a core-shell structure, XRD (X-ray diffraction) shows that the chitosan material loaded by the metal organic framework MIL-101(Cr) has characteristic peaks at positions of 5.25 degrees, 5.80 degrees, 8.55 degrees and 9.15 degrees, the peak position of the chitosan material is consistent with that of MIL-101(Cr), the chitosan material has characteristic peaks at about 20 degrees, due to the coating of the chitosan material, a bulge peak also appears at the position of MIL-101(Cr) @ CS, and XRD (X-ray diffraction) of the material is consistent with that of MIL-101(Cr) and the characteristic peaks of chitosan are shown in figure 1. As shown in the thermogravimetric analysis figure 2, the bearable temperature of the metal-organic framework MIL-101(Cr) loaded chitosan material can reach 470 ℃; the appearance of the metal organic framework MIL-101(Cr) -loaded chitosan material is shown in figure 3, the chitosan material is uniform in particle size, and the particle size is about 20 nm; the gas phase adsorption curve of the metal-organic framework MIL-101(Cr) loaded chitosan material is shown in FIG. 4, and when P/P0 is 1, the adsorption capacity of the material can reach 464.96cm3Per g, specific surface area of the material 1173.15m2/g。
Example 2 catalytic function of metal organic framework MIL-101(Cr) loaded chitosan composite material on deacetalization-Knoevenagel condensation reaction.
The method comprises the following steps: the deacylation-Knoevenagel condensation reaction was catalyzed by using the metal organic framework MIL-101(Cr) supported chitosan composite material prepared in example 1 as a catalyst.
1) Activating treatment of the catalyst: taking a certain amount of metal organic framework MIL-101(Cr) loaded chitosan composite material, and vacuumizing and drying for 12h under the heating condition of 393K.
The method comprises the following steps: taking 50mg of activated metal organic framework MIL-101(Cr) loaded chitosan composite material, 2.0mmol of benzaldehyde dimethyl acetal, 2.1mmol of malononitrile, 2mL of acetonitrile and 0.5mL of distilled water to a 10mL reaction tube, and introducing N under the stirring condition2The temperature is 80 ℃, and the reaction time is 12 h. The experimental results were checked by gas chromatography.
The deacylation-Knoevenagel condensation reaction is catalyzed by the metal organic framework MIL-101(Cr) loaded chitosan material, the yield of the reaction is gradually increased along with the reaction, and the conversion rate of the reaction reaches a maximum of 98.74 percent when the reaction is carried out for 12 hours.
2) Recyclability of the catalyst in deacylation-Knoevenagel condensation reactions.
And (3) recovering the catalyst: after the reaction is finished, filtering, separating the catalyst from the reaction mixture, washing with methanol, soaking in methanol for 4h, filtering and drying.
Specific operation of the cycling experiment: the recovered catalyst is used for catalyzing deacetalization-Knoevenagel condensation reaction for 12 hours at the temperature of 80 ℃.
As shown in fig. 5, when the circulation experiment is performed to the fifth round, the reactant conversion rate and the yield of the target product are still not significantly reduced, which indicates that the activity of the catalyst is kept good in the circulation experiment. As shown in fig. 6, the XRD pattern of the metal organic framework MIL-101(Cr) -supported chitosan material after five cycles of experiments is consistent with the main peak position of the XRD pattern of the catalytic material without cycles, characteristic peaks of MIL-101(Cr) appear at 5.25 °, 5.80 °, 8.55 ° and 9.15 °, and characteristic peaks belonging to chitosan appear at 20 °, indicating that the catalyst structure is intact and not damaged during the cyclic catalysis process. The result of a cyclic experiment shows that the metal organic framework MIL-101(Cr) loaded chitosan material can be recycled as a catalyst for catalyzing deacetalization-Knoevenagel condensation reaction.
3) Heterogeneity of the catalyst in deacetalization-Knoevenagel condensation reactions.
The leaching experiment comprises the following specific operations: when the reaction proceeded for 6h, the catalyst was removed by centrifugation and the reaction was allowed to continue for 12 h.
The leaching experiment result is shown in fig. 7, the catalyst is taken out when the experiment is carried out for 6 hours, the reaction is continued, and the yield of the target product is hardly improved when the reaction reaches 12 hours, which indicates that the catalyst does not leach out active components, and proves the heterogeneity of the catalyst.
Claims (9)
1. A metal organic framework MIL-101(Cr) loaded chitosan material is characterized in that chitosan is coated on the outer surface of MIL-101(Cr) to form a core-shell structure.
2. The preparation method of the metal-organic framework MIL-101(Cr) supported chitosan material as claimed in claim 1, which is characterized by comprising the following steps:
(1) adding chitosan into acetic acid solution, stirring at room temperature until chitosan is completely dissolved, adding Cr (NO)3)3·9H2O，H2Adding BDC into the acetic acid solution dissolved with chitosan, and stirring at room temperature for 20-40 min;
(2) transferring the solution obtained in the step (1) to a high-pressure autoclave with a polytetrafluoroethylene lining, sealing, putting the autoclave into an oven, slowly heating to 463-483K, heating, and keeping for 7-9 h;
(3) slowly cooling to room temperature, washing with N, N-dimethylformamide and methanol in sequence, filtering and drying to obtain the target product.
3. The method for preparing the metal-organic framework MIL-101(Cr) -supported chitosan material as claimed in claim 2, wherein in the step (1), Cr (NO) is added according to molar ratio3)3·9H2O：H2BDC：CS＝3-5:2-4:1。
4. The method for preparing the metal-organic framework MIL-101(Cr) -supported chitosan material as claimed in claim 3, wherein in the step (1), Cr (NO) is added according to molar ratio3)3·9H2O：H2BDC：CS＝4.05:3.24:1。
5. The preparation method of the metal-organic framework MIL-101(Cr) supported chitosan material as claimed in claim 2, wherein in the step (1), the concentration of the acetic acid solution is as follows, by mass ratio, acetic acid: distilled water is 1: 100.
6. The method for preparing the metal-organic framework MIL-101(Cr) -supported chitosan material as claimed in claim 2, wherein in the step (2), the temperature rising rate of the slow temperature rising is 10K-min-1。
7. The method for preparing the metal-organic framework MIL-101(Cr) -supported chitosan material as claimed in claim 2, wherein in the step (3), the slow cooling rate to room temperature is 10K-min-1。
8. The use of the metal-organic framework MIL-101(Cr) supported chitosan material of claim 1 in catalyzing deacetalization-Knoevenagel condensation reactions.
9. The method of claim 8, wherein benzaldehyde dimethyl acetal, malononitrile, acetonitrile, distilled water and catalyst are put into a reaction tube, and N is introduced into the reaction tube under stirring2Reacting for 12 hours at the temperature of 80 ℃; the catalyst is the metal organic framework MIL-101(Cr) supported chitosan material of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433238A (en) * | 2022-02-25 | 2022-05-06 | 辽宁大学 | Core-shell material MIL-101(Cr) @ PMF based on metal organic framework and preparation method and application thereof |
| CN114433238B (en) * | 2022-02-25 | 2023-09-15 | 辽宁大学 | Core-shell material MIL-101 (Cr) @ PMF based on metal-organic framework and preparation method and application thereof |
| CN115041234A (en) * | 2022-06-20 | 2022-09-13 | 辽宁大学 | MIL-101(Cr) @ MOF-867 core-shell material and preparation method and application thereof |
| CN115041234B (en) * | 2022-06-20 | 2023-04-07 | 辽宁大学 | MIL-101 (Cr) @ MOF-867 core-shell material and preparation method and application thereof |
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