CN115041234B - MIL-101 (Cr) @ MOF-867 core-shell material and preparation method and application thereof - Google Patents
MIL-101 (Cr) @ MOF-867 core-shell material and preparation method and application thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000008358 core component Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010523 cascade reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000306 component Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000011257 shell material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 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
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000000527 sonication Methods 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000013177 MIL-101 Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WAVNYPVYNSIHNC-UHFFFAOYSA-N 2-benzylidenepropanedinitrile Chemical class N#CC(C#N)=CC1=CC=CC=C1 WAVNYPVYNSIHNC-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- B01J35/50—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to an MIL-101 (Cr) @ MOF-867 core-shell material and a preparation method and application thereof. The technical scheme is as follows: MIL-101 (Cr) powder as a core component is added to DMF, zrCl 4 2,2 '-bipyridine-5, 5' -dicarboxylic acid and glacial acetic acid. And the suspension was transferred to a 40mL reactor and after 40 minutes of sonication it was placed in an oven at 393K and heated for 24h. Cooling to room temperature, centrifuging, washing, and vacuum drying to obtain core-shell structure crystal MIL-101 (Cr) @ MOF-867. The MIL-101 (Cr) @ MOF-867 core-shell material provided by the invention is simple in preparation method, and shows higher stability and catalytic performance in Deacetalization-Knoevenagel series reaction.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a core-shell material MIL-101 (Cr) @ MOF-867 and a preparation method and application thereof.
Background
Metal organic framework Materials (MOFs) are porous crystalline materials formed by coordination bonds of metal ions and organic ligands or clusters. For catalytic application, the high crystallinity and molecular structure design of the MOFs is expected to improve the catalytic efficiency, but the MOFs has the defects of poor chemical stability and the like, so that the application prospect is limited. In order to meet the practical application of MOFs, it is necessary to further enhance the performance thereof and introduce new functional materials. Fortunately, in recent years, researchers have suggested combining MOFs with other MOFs to combine the advantages of both.
Benzylidene Malononitrile Derivatives (BMDs) have unique chemical and biological activities and are main intermediates for the synthesis of pesticides, medicines, dyes and the like. Over the past decade, scientists have been working on a comprehensive strategy to prepare BMDs. Despite some advances in this regard, improvements are still needed. Therefore, it is a great challenge to find a green and energy-saving method for synthesizing BMDs.
In recent years, the tandem reaction has received increasing attention due to its simple operation process, no need to purify intermediate products, obvious economic effects and environmental friendliness. deacetization-Knoevenagel tandem reactions require catalysts with both acidic and basic active sites to catalyze. Therefore, there is a need to develop bifunctional catalysts with both acid-base catalytic centers to catalyze such reactions.
Disclosure of Invention
The invention aims to provide a bifunctional catalyst core-shell material MIL-101 (Cr) @ MOF-867 which can efficiently catalyze deacetylation-Knoevenagel tandem reaction and has an acid-base catalysis center.
In order to achieve the purpose, the invention adopts the technical scheme that: a MIL-101 (Cr) @ MOF-867 core-shell material is prepared from a core component MIL-101 (Cr) and a shell component MOF-867.
The preparation method of the MIL-101 (Cr) @ MOF-867 core-shell material comprises the following steps:
1) Adding MIL-101 (Cr) powder into DMF and ZrCl 4 2,2 '-bipyridine-5, 5' -dicarboxylic acid and glacial acetic acid, and uniformly stirring to obtain a suspension;
2) Transferring the suspension into a reaction kettle, carrying out ultrasonic treatment for 40 minutes, and then putting the suspension into an oven for hydrothermal reaction;
3) Cooling to room temperature, collecting the product by centrifugation, washing with a solvent, and drying in vacuum to obtain the product.
Further, in the above-mentioned production method, step 1), MIL-101 (Cr): zrCl is added in a molar ratio 4 2,2' -bipyridine-5,5' -dicarboxylic acid = 1.
Further, in the preparation method, step 1), glacial acetic acid is added to adjust the reaction system to be acidic.
Further, in the preparation method, in the step 2), the hydrothermal reaction is carried out at 393K for 24h.
Further, in the above preparation method, step 3), the solvent is DMF and methanol.
The invention provides an application of an MIL-101 (Cr) @ MOF-867 core-shell material in catalysis of Deacetalization-Knoevenagel series reaction.
Further, the method comprises the following steps: taking benzaldehyde dimethyl acetal, malononitrile, DMSO and a catalyst to react in a three-neck reaction vessel for 12 hours under the condition of 353K; the catalyst is MIL-101 (Cr) @ MOF-867 core-shell material.
In the MIL-101 (Cr) @ MOF-867 core-shell material, MIL-101 (Cr) and MOF-867 provide rich Lewis acid sites (Cr clusters in MIL-101 (Cr) and Zr clusters in MOF-867) for catalyzing the first-step reaction, and MOF-867 provides rich Lewis acid sites for catalyzing the first-step reaction
The base site (C = N group in bipyridine) catalyzes the second Knoevenagel condensation reaction. Thereby synergistically catalyzing the series reaction. The reaction formula is as follows:
the invention has the beneficial effects that: the invention takes MIL-101 (Cr) with good stability and porous structure as a core component, and grows the shell component MOF-867 by a post-impregnation synthesis method to form the material MIL-101 (Cr) @ MOF-867 with the core-shell structure. In the present invention, cr clusters in the core component MIL-101 (Cr) and Zr clusters in the shell component MOF-867 provide acidic sites, and bipyridine in the shell component MOF-867 provides basic sites. The core-shell material MIL-101 (Cr) @ MOF-867 has larger specific surface area, higher chemical stability and thermal stability. In addition, MIL-101 (Cr) @ MOF-867 after 5 cycles of tests still keeps higher catalytic activity, and has higher stability and recoverability. The MIL-101 (Cr) @ MOF-867 has excellent catalytic performance in deacetylization-Knoevenagel tandem reaction preparation of BMDs.
Drawings
FIG. 1 is a PXRD pattern of MIL-101 (Cr) @ MOF-867 core-shell material of the present invention.
FIG. 2 is FT-IR spectrum of MIL-101 (Cr) @ MOF-867 core-shell material of the present invention.
FIG. 3 is a TEM spectrum of MIL-101 (Cr) @ MOF-867 core-shell material of the present invention;
wherein, a is a TEM image of MIL-101; a TEM image of MOF-867; MIL-101 (Cr) @ MOF-867.
FIG. 4 shows the catalytic activity of MIL-101 (Cr) @ MOF-867 core-shell material of the present invention in five catalytic cycles.
FIG. 5 is a PXRD comparison graph before and after five times of catalytic reactions of MIL-101 (Cr) @ MOF-867 core-shell materials of the invention.
Detailed Description
Example 1 MIL-101 (Cr) @ MOF-867 core-shell material
The preparation method comprises the following steps:
1. synthesis of MIL-101 (Cr) powder
Mixing Cr (NO) 3 ) 3 ·9H 2 O(3.20g,8.00mmol)、H 2 BDC (1.31g, 7.88mmol) and acetic acid (2.17mL, 0.038mmol) were added to 40mL of ultra-pure water. The mixture was sonicated at room temperature, placed in an 80mL teflon reactor, the reactor sealed, placed in an oven and stored at 473K for 8 hours. The good green suspension was collected, washed three times with DMF and ethanol, respectively, centrifuged (10000rpm, 15 min) and sonicated. Finally, the MIL-101 pellets were evacuated in a 423K vacuum oven for 12 hours to obtain a dehydrated product for use.
2. Synthesis of MIL-101 (Cr) @ MOF-867 core-shell material
MIL-101 (Cr) (50mg, 0.07mmol) powder was added to 25mL DMF, zrCl 4 (46.6mg, 0.2mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (48.8mg, 0.2mmol) and glacial acetic acid (0.4 mL) in a mixed solution, and stirring to obtain a suspension. Will hangThe suspension was transferred to a 40mL reaction kettle and after sonication for 40 minutes, it was placed in an oven at 393K and heated for 24h. After cooling to room temperature, the product was collected by centrifugation, washed three times with DMF and methanol respectively, and dried in a 353K vacuum oven for 12h to obtain light green core-shell structure crystal MIL-101 (Cr) @ MOF-867.
(II) detection
FIG. 1 is powder X-ray diffraction (PXRD) of MIL-101 (Cr) @ MOF-867 core-shell material, which shows that the structures of MIL-101 (Cr) @ MOF-867 crystals are not destroyed and the structures are still intact in the preparation process of the MIL-101 (Cr) @ MOF-867 core-shell material.
FIG. 2 is an infrared spectrum (FT-IR) of MIL-101 (Cr) @ MOF-867 core-shell material, the FT-IR spectrum of MIL-101 (Cr) @ MOF-867 is well matched with the FT-IR spectrum of MIL-101 (Cr) and MOF-867, further confirming the successful formation of MIL-101 (Cr) @ MOF-867 core-shell material.
FIG. 3 is a Transmission Electron Microscope (TEM) of MIL-101 (Cr) @ MOF-867 core-shell material, which shows that MIL-101 (Cr) @ MOF-867 has a significantly complete core-shell structure.
Example 2
Catalysis function of MIL-101 (Cr) @ MOF-867 core-shell material for Deacetalization-Knoevenagel tandem reaction
(I) catalyzing Deacetalization-Knoevenagel tandem reaction by using MIL-101 (Cr) @ MOF-867 core-shell material prepared in example 1 as a catalyst.
The method comprises the following steps:
activating treatment of the catalyst: taking a certain amount of MIL-101 (Cr) @ MOF-867 core-shell material, and vacuumizing and drying for 24 hours under the heating condition of 353K.
Adding 20mg of activated MIL-101 (Cr) @ MOF-867 core-shell material into a 10mL three-neck reaction vessel, sequentially adding 1.0mmol of malononitrile, 1.0mmol of benzaldehyde dimethyl acetal and 4.0mL of DMSO, and reacting at 353K to generate Benzylidene Malononitrile Derivatives (BMDs). The yield of the product was monitored by Gas Chromatography (GC).
During the reaction, the experimental result of the MIL-101 (Cr) @ MOF-867 core-shell material on the catalytic performance of the tandem reaction is detected by GC, the yield of the reaction gradually increases along with the reaction, and the yield of the reaction reaches 99.9% already when the reaction is carried out for 12 hours.
And (II) recovering the catalyst.
After the reaction was completed, the catalyst was filtered and separated, washed thoroughly with methanol, and evacuated to be reused in the next cycle of the reaction.
Specific operation of the cycling experiment: the recovered catalyst is used for catalyzing Deacetalization-Knoevenagel tandem reaction, the reaction is carried out for 12 hours at 353K, and the cycle experiment is carried out for 5 times.
The results of the experiment are shown in FIG. 4, and the activity of the catalyst still did not decrease after 5 times of the cycle experiment. The MIL-101 (Cr) @ MOF-867 core-shell material can be recycled as a Deacetalization-Knoevenagelmkjn series reaction catalyst.
FIG. 5 is a PXRD comparison graph of MIL-101 (Cr) @ MOF-867 core-shell materials before and after five cycles of reaction. The crystal structure of the material is not changed after five cycles of catalytic reaction and remains intact.
Claims (7)
1. An MIL-101 (Cr) @ MOF-867 core-shell material is characterized in that: the MIL-101 (Cr) @ MOF-867 core-shell material is prepared from a core component MIL-101 (Cr) and a shell component MOF-867; the preparation method of the MIL-101 (Cr) @ MOF-867 core-shell material comprises the following steps:
1) Adding MIL-101 (Cr) powder into DMF and ZrCl 4 2,2 '-bipyridine-5, 5' -dicarboxylic acid and glacial acetic acid, and uniformly stirring to obtain a suspension; MIL-101 (Cr): zrCl in molar ratio 4 2,2 '-bipyridine-5, 5' -dicarboxylic acid =1: 2.5-3.0;
2) Transferring the suspension into a reaction kettle, carrying out ultrasonic treatment for 40 minutes, and then putting the suspension into an oven for hydrothermal reaction;
3) Cooling to room temperature, collecting the product by centrifugation, washing with a solvent, and drying in vacuum to obtain the product.
2. The method for preparing MIL-101 (Cr) @ MOF-867 core-shell material of claim 1, wherein: the preparation method comprises the following steps:
1) Adding MIL-101 (Cr) powder into DMF and ZrCl 4 2,2 '-bipyridine-5, 5' -dicarboxylic acid and glacial acetic acid, and uniformly stirring to obtain a suspension;
2) Transferring the suspension into a reaction kettle, carrying out ultrasonic treatment for 40 minutes, and then putting the suspension into an oven for hydrothermal reaction;
3) Cooling to room temperature, collecting the product by centrifugation, washing with a solvent, and drying in vacuum to obtain the product.
3. The method of claim 2, wherein: in the step 1), glacial acetic acid is added to adjust the reaction system to be acidic.
4. The production method according to claim 2, characterized in that: in the step 2), the hydrothermal reaction is carried out at 393K for 24h.
5. The method of claim 2, wherein: in the step 3), the solvent is DMF and methanol.
6. The use of MIL-101 (Cr) @ MOF-867 core-shell material of claim 1 to catalyze Deacetalization-Knoevenagel tandem reactions.
7. Use according to claim 6, characterized in that: the method comprises the following steps: benzaldehyde dimethyl acetal, malononitrile, DMSO and a catalyst are put into a three-neck reaction vessel and react for 12 hours under the condition of 353K; the catalyst is MIL-101 (Cr) @ MOF-867 core-shell material of claim 1.
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| CN108273555A (en) * | 2018-01-12 | 2018-07-13 | 辽宁大学 | A kind of porous crystalline nucleocapsid hybrid material and its preparation method and application based on UiO-66@SNW-1 |
| CN111001442A (en) * | 2019-12-19 | 2020-04-14 | 辽宁大学 | Metal organic framework MIL-101(Cr) loaded chitosan material and preparation method and application thereof |
| 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 |
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| CN108273555A (en) * | 2018-01-12 | 2018-07-13 | 辽宁大学 | A kind of porous crystalline nucleocapsid hybrid material and its preparation method and application based on UiO-66@SNW-1 |
| CN111001442A (en) * | 2019-12-19 | 2020-04-14 | 辽宁大学 | Metal organic framework MIL-101(Cr) loaded chitosan material and preparation method and application thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Manman Mu et al.."Post-modified acid-base bifunctionalMIL-101(Cr) for one-pot deacetalization-Knoevenagel reaction".《J Nanopart Res》.2017,第第19卷卷(第第19卷期),第1-13页. * |
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