CN114433238A - Core-shell material MIL-101(Cr) @ PMF based on metal organic framework and preparation method and application thereof - Google Patents
Core-shell material MIL-101(Cr) @ PMF based on metal organic framework and preparation method and application thereof Download PDFInfo
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- CN114433238A CN114433238A CN202210181569.7A CN202210181569A CN114433238A CN 114433238 A CN114433238 A CN 114433238A CN 202210181569 A CN202210181569 A CN 202210181569A CN 114433238 A CN114433238 A CN 114433238A
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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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C45/513—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 etherified hydroxyl group
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Abstract
The invention relates to the technical field of catalysts, in particular to a preparation method and application of a core-shell material MIL-101(Cr) @ PMF based on a metal organic framework, and the technical scheme is as follows: putting MIL-101(Cr), melamine and dimethyl sulfoxide into a polytetrafluoroethylene reaction kettle, carrying out ultrasonic treatment for 1h, then adding paraformaldehyde, and carrying out ultrasonic treatment for 30 minutes; heating a polytetrafluoroethylene reaction kettle in an oven for reaction, stirring for half an hour to obtain a uniform solution, and continuing to react in the oven; slowly cooling to room temperature to obtain light green crystals, filtering and washing for several times, and heating in vacuum to obtain MIL-101(Cr) @ PMF core-shell material. The MIL-101(Cr) @ PMF core-shell material has a simple preparation method, and shows ultra-high catalytic capability in Deacetalization-Knoevenagel series reaction.
Description
Technical Field
The invention relates to the technical field of catalysts, relates to a preparation method and application of a core-shell material MIL-101(Cr) @ PMF based on a metal organic framework, and particularly relates to preparation and application of a core-shell material for catalyzing deacylation-Knoevenagel series reaction.
Background
Metal organic framework Materials (MOFs) are porous crystalline materials formed by coordination bonds of metal ions and organic ligands or clusters. A Porous Organic Polymer (POP) is a multifunctional material consisting of C, N, O, B etc atoms. For catalytic application, the high crystallinity and molecular structure design of MOF is expected to improve the catalytic efficiency, however, the research of MOFs @ POP core-shell materials in the field of catalysis is rarely reported.
The tandem reaction refers to that when new operation is not carried out in the same reaction environment, the added reactants are continuously subjected to two or more steps of reaction, the product of the former step of reaction is usually subjected to the next step of reaction with the initial reactants or the reactant, and the reaction conditions are similar. In the field of organic catalysis, the series reaction has become a potential reaction development direction.
Disclosure of Invention
The invention aims to construct a novel MIL-101(Cr) @ PMF core-shell material by using MIL-101(Cr) as a core material and PMF generated by the reaction of melamine, paraformaldehyde and anhydrous dimethyl sulfoxide as a shell material by using a dipping synthesis method, and researches the novel MIL-101(Cr) @ PMF core-shell material as a core material simultaneously containing Lewis acid and anhydrous dimethyl sulfoxide
The bifunctional catalyst of the basic site has the catalytic performance on Deacetalization-Knoevenagel tandem reaction.
The technical scheme adopted by the invention is as follows: a core-shell material MIL-101(Cr) @ PMF based on a metal organic framework is prepared by the following steps:
1) putting MIL-101(Cr), melamine and dimethyl sulfoxide into a polytetrafluoroethylene reaction kettle, carrying out ultrasonic treatment for 1h, then adding paraformaldehyde, and carrying out ultrasonic treatment for 30 minutes;
2) heating a polytetrafluoroethylene reaction kettle in an oven for reaction, stirring for half an hour to obtain a uniform solution, and continuing to react in the oven;
3) slowly cooling to room temperature to obtain light green crystals, filtering and washing for a plurality of times, and performing vacuum drying to obtain a target product;
in the core-shell material MIL-101(Cr) @ PMF based on a metal organic framework, step 1), MIL-101(Cr) and melamine are 1:4.2 in molar ratio.
In the above core-shell material MIL-101(Cr) @ PMF based on a metal organic framework, in step 1), the weight ratio of melamine to paraformaldehyde is 2.3: 1.
In the step 2), the heating reaction temperature is 393K and the time is 1 h.
In the above core-shell material MIL-101(Cr) @ PMF based on metal organic framework, step 2), the reaction is continued in the oven for 72h under 443K.
In the step 3), the vacuum heating is performed for 24 hours at 353K.
The application of the core-shell material MIL-101(Cr) @ PMF based on the metal organic framework in catalyzing Deacetalization-Knoevenagel series reaction is provided.
The application and the method are as follows: benzaldehyde dimethyl acetal, malononitrile, ethanol and a catalyst are put into a three-neck reaction vessel and react for 12 hours under the condition of 353K; the catalyst is the MIL-101(Cr) @ PMF core-shell material.
In the MIL-101(Cr) @ PMF core-shell material, MIL-101(Cr) provides rich Lewis acid sites (Cr clusters in MIL-101 (Cr)) to catalyze the first step Deacetalization reaction, and PMF provides
Basic sites (amino groups in PMF) catalyze the second Knoevenagel condensation reaction, and acidic and basic sites synergistically catalyze Deacetalization-Knoevenagel tandem reaction. The method comprises the following steps: taking malononitrile, benzaldehyde dimethyl acetal, ethanol and a catalyst to react for 12 hours in a three-neck reaction vessel under the condition of 353K; the catalyst is the core-shell material of MIL-101(Cr) @ PMF. The reaction formula is as follows:
the invention has the beneficial effects that: MIL-101(Cr) @ PMF with MIL-101(Cr) provides rich Lewis acid sites (Cr clusters in MIL-101 (Cr)) to catalyze the first deacetalization reaction, while PMF provides
Basic sites (amino groups in PMF) catalyze the second Knoevenagel condensation reaction, which synergistically catalyzes Deacetalization-Knoevenagel tandem reactions. Furthermore, all characterization methods demonstrated high physical and chemical stability. The MIL-101(Cr) @ PMF core-shell material prepared by the invention has a simple synthesis method and a wide application prospect.
Drawings
FIG. 1 is a PXRD pattern of MIL-101(Cr) @ PMF core-shell material of the present invention.
FIG. 2 is FT-IR spectrum of MIL-101(Cr) @ PMF core-shell material of the present invention.
FIG. 3 is a TEM spectrum of MIL-101(Cr) @ PMF core-shell material of the present invention.
FIG. 4 shows catalytic activity of MIL-101(Cr) @ PMF core-shell material of the present invention for five catalytic cycles.
FIG. 5 is a PXRD diagram of MIL-101(Cr) @ PMF core-shell material of the present invention undergoing five times of catalytic reactions.
Detailed Description
Example 1 MIL-101(Cr) @ PMF core-shell material
MIL-101(Cr) (50mg), melamine (37.8mg) and dimethyl sulfoxide (16.8mL) were placed in a Teflon reactor, sonicated for 1h, then paraformaldehyde (16.2mg) was added and sonicated for 30 min. The teflon reaction kettle was heated in an oven at 393K for 1h and then stirred for half an hour to obtain a homogeneous solution, which was then placed in an oven at 443K for 72 h. And (3) washing the light green MIL-101(Cr) @ PMF crystals obtained by filtering with dimethyl sulfoxide, acetone, tetrahydrofuran and dichloromethane for 3 times respectively, and finally heating for 24 hours under 353K vacuum to obtain the target product, namely the core-shell material MIL-101(Cr) @ PMF.
FIG. 1 is powder X-ray diffraction (PXRD) of MIL-101(Cr) @ PMF core-shell material, which shows that the MIL-101(Cr) @ PMF core-shell material has the structure that is not destroyed and the structure is still intact during the preparation process. FIG. 2 is an infrared spectrum (FT-IR) of MIL-101(Cr) @ PMF core-shell material, the FT-IR spectrum of MIL-101(Cr) @ PMF matches well with the FT-IR spectrum of MIL-101(Cr) and PMF, further confirming the successful formation of MIL-101(Cr) @ PMF core-shell material. FIG. 3 is a Transmission Electron Microscope (TEM) of MIL-101(Cr) @ PMF core-shell material, and it can be seen that MIL-101(Cr) @ PMF has a significantly complete core-shell structure.
Example 2 catalysis of MIL-101(Cr) @ PMF core-shell materials for Deacetalization-Knoevenagel tandem reactions
The method comprises the following steps: the Deacetalization-Knoevenagel tandem reaction was catalyzed with MIL-101(Cr) @ PMF core-shell material prepared in example 1 as a catalyst.
1) Activating treatment of the catalyst: taking a certain amount of MIL-101(Cr) @ PMF core-shell material, and vacuumizing and drying for 24 hours under the heating condition of 353K.
The method comprises the following steps: 50mg of activated MIL-101(Cr) @ PMF core-shell material is added into a 10mL three-neck reaction vessel, and then 1.0mmol of malononitrile, 1.0mmol of benzaldehyde dimethyl acetal and 4.0mL of ethanol are sequentially added for reaction at the temperature of 353K. The yield of product was monitored by Gas Chromatography (GC).
During the reaction, the experimental results of the core-shell material MIL-101(Cr) @ PMF on the catalytic performance of the tandem reaction were checked by GC, and the yield of the reaction gradually increased as the reaction proceeded, and reached 99.9% by 12 h.
2) Recyclability of the catalyst in deacylation-Knoevenagel tandem reactions.
And (3) recovering the catalyst: after the reaction is finished, centrifugal filtration is carried out, the reaction mixture is separated from the catalyst, and the catalyst is washed by methanol, filtered and dried.
Specific operation of the cycling experiment: the recovered catalyst is used for catalyzing Deacetalization-Knoevenagel tandem reaction for 12 hours at 353K.
The results of the experiment are shown in fig. 4 and 5, and the activity of the catalyst is still not reduced after 5 times of the cycle experiment. The MIL-101(Cr) @ PMF core-shell material can be recycled as a Deacetalization-Knoevenagelmkjn series reaction catalyst.
Claims (8)
1. A core-shell material MIL-101(Cr) @ PMF based on a metal organic framework is characterized in that the preparation method comprises the following steps:
1) putting MIL-101(Cr), melamine and dimethyl sulfoxide into a polytetrafluoroethylene reaction kettle, carrying out ultrasonic treatment for 1h, then adding paraformaldehyde, and carrying out ultrasonic treatment for 30 minutes;
2) heating a polytetrafluoroethylene reaction kettle in an oven for reaction, stirring for half an hour to obtain a uniform solution, and continuing to react in the oven;
3) slowly cooling to room temperature to obtain light green crystals, filtering and washing for a plurality of times, and heating in vacuum to obtain the target product.
2. The metal-organic framework-based core-shell material MIL-101(Cr) @ PMF according to claim 1, wherein: in step 1), MIL-101(Cr) and melamine were 1:4.2 in mole ratio.
3. The metal-organic framework-based core-shell material MIL-101(Cr) @ PMF according to claim 1, wherein: in the step 1), the weight ratio of melamine to paraformaldehyde is 2.3: 1.
4. The metal-organic framework-based core-shell material MIL-101(Cr) @ PMF according to claim 1, wherein: in the step 2), the heating reaction temperature is 393K, and the time is 1 h.
5. The metal-organic framework-based core-shell material MIL-101(Cr) @ PMF according to claim 1, wherein: in step 2), the reaction is continued in the oven for 72h at 443K.
6. The metal-organic framework-based core-shell material MIL-101(Cr) @ PMF according to claim 1, wherein: in the step 3), the vacuum heating is performed for 24 hours at 353K.
7. The use of the metal organic framework based core-shell material MIL-101(Cr) @ PMF of claim 1 for catalyzing Deacetalization-Knoevenagel tandem reaction.
8. Use according to claim 7, characterized in that the method is as follows: benzaldehyde dimethyl acetal, malononitrile, ethanol 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) @ PMF core-shell material of claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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