CN114433238B - 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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- 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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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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- C07C45/00—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
- C07C45/513—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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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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- 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
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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, which adopts the following technical scheme: placing MIL-101 (Cr), melamine and dimethyl sulfoxide into a polytetrafluoroethylene reaction kettle, performing ultrasonic treatment for 1h, adding paraformaldehyde and performing ultrasonic treatment for 30 minutes; heating the 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 vacuum heating to obtain MIL-101 (Cr) @ PMF core-shell material. The MIL-101 (Cr) @ PMF core-shell material has a simple preparation method and has ultrahigh catalytic capability in the dealumination-Knoevenagel series reaction.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method and application of a metal organic framework-based core-shell material MIL-101 (Cr) @ PMF, and specifically relates to a preparation method and application of a core-shell material for catalyzing a deacetylation-Knoevenagel series reaction.
Background
Metal Organic Frameworks (MOFs) are porous crystalline materials formed by coordination bonds between metal ions and organic ligands or clusters. Porous Organic Polymers (POPs) are a multifunctional material composed of atoms such as C, N, O, B. For catalytic application, the high crystallinity and molecular structure design of MOF are expected to improve catalytic efficiency, however, the research of MOFs@POP core-shell material in the catalytic field is rarely reported.
Tandem reactions refer to reactions in which the added reactants are continuously reacted in two or more steps in the same reaction environment without a new operation, the products of the previous reaction are usually reacted with the initial reactants or themselves in the next step, and the reaction conditions are similar. In the field of organic catalysis, tandem reactions have become a very potential reaction development.
Disclosure of Invention
The invention aims to construct a novel MIL-101 (Cr) @ PMF core-shell material by taking MIL-101 (Cr) as a core material and taking PMF generated by the reaction of melamine, paraformaldehyde and anhydrous dimethyl sulfoxide as a shell material through a dipping synthesis method, and research the novel MIL-101 (Cr) @ PMF core-shell material as a shell material with Lewis acid and Lewis acid at the same timeCatalytic performance of basic site bifunctional catalysts on Deacetification-Knoevenagel tandem reactions.
The technical scheme adopted by the invention is as follows: the preparation method of the core-shell material MIL-101 (Cr) @ PMF based on the metal-organic framework comprises the following steps:
1) Placing MIL-101 (Cr), melamine and dimethyl sulfoxide into a polytetrafluoroethylene reaction kettle, performing ultrasonic treatment for 1h, adding paraformaldehyde and performing ultrasonic treatment for 30 minutes;
2) Heating the 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 several times, and vacuum drying to obtain a target product;
in the core-shell material MIL-101 (Cr) @ PMF based on the metal organic framework, in the step 1), the molar ratio of MIL-101 (Cr) is MIL=1:4.2.
In the core-shell material MIL-101 (Cr) @ PMF based on the metal organic framework, in the step 1), melamine is prepared by the following weight ratio of paraformaldehyde=2.3:1.
In the above-mentioned core-shell material MIL-101 (Cr) @ PMF based on metal organic framework, in step 2), the heating reaction temperature is 393K, and the time is 1h.
In the above-mentioned core-shell material MIL-101 (Cr) @ PMF based on metal organic framework, in the step 2), the reaction was continued in an oven by placing at 443K for 72 hours.
In the above-mentioned core-shell material MIL-101 (Cr) @ PMF based on metal organic framework, in the step 3), the vacuum heating is performed for 24 hours under 353K.
The application of the core-shell material MIL-101 (Cr) @ PMF based on the metal-organic framework in catalyzing the dealumination-Knoevenagel tandem reaction.
The application method comprises the following steps: taking benzaldehyde dimethyl acetal, malononitrile, ethanol and a catalyst to react in a three-neck reaction vessel under the condition of 353K for 12 hours; the catalyst is the MIL-101 (Cr) @ PMF core-shell material.
In the MIL-101 (Cr) @ PMF core-shell material of the present invention, MIL-101 (Cr) provides rich Lewis acid sites (Cr clusters in MIL-101 (Cr)) to catalyze the first step of Deacetalization reaction, while PMF providesThe basic site (amino group in the PMF) catalyzes the second Knoevenagel condensation reaction, and the acidic site and the basic site synergistically catalyze the deacylation-Knoevenagel tandem reaction. The method comprises the following steps: taking malononitrile, benzaldehyde dimethyl acetal, ethanol and a catalyst to react in a three-neck reaction vessel under the condition of 353K for 12 hours; the catalyst is the core-shell material of MIL-101 (Cr) @ PMF. The reaction formula is as follows:
the beneficial effects of the invention are as follows: MIL-101 (Cr) @ PMF with MIL-101 (Cr) provides rich Lewis acid sites (Cr clusters in MIL-101 (Cr)) to catalyze the first step deacetalization reaction, whereas PMF providesThe basic site (amino group in the PMF) catalyzes the second Knoevenagel condensation reaction, which synergistically catalyzes the deacylation-Knoevenagel tandem reaction. In addition, all characterization methods demonstrate high physical and chemical stability. The MIL-101 (Cr) @ PMF core-shell material prepared by the method is simple in synthesis method and has a wide application prospect.
Drawings
FIG. 1 is a PXRD pattern for MIL-101 (Cr) @ PMF core-shell materials of the present invention.
FIG. 2 is a FT-IR spectrum of MIL-101 (Cr) @ PMF core-shell material according to the invention.
FIG. 3 is a TEM spectrum of MIL-101 (Cr) @ PMF core-shell material of the present invention.
FIG. 4 shows the catalytic activity of the MIL-101 (Cr) @ PMF core-shell material of the present invention for five cycles of catalytic reactions.
FIG. 5 is a PXRD diagram of a five-cycle catalytic reaction of MIL-101 (Cr) @ PMF core-shell material of the present invention.
Detailed Description
Example 1 MIL-101 (Cr) @ PMF core-shell Material
MIL-101 (Cr) (50 mg), melamine (37.8 mg) and dimethyl sulfoxide (16.8 mL) were placed in a polytetrafluoroethylene reaction vessel, sonicated for 1h, then paraformaldehyde (16.2 mg) was added and sonicated for 30 min. The polytetrafluoroethylene autoclave was heated in a 393K oven for 1 hour and then stirred for half an hour to obtain a uniform solution, which was then placed in a 443K oven for 72 hours. And washing the light green MIL-101 (Cr) @ PMF crystal obtained by filtering with dimethyl sulfoxide, acetone, tetrahydrofuran and dichloromethane respectively for 3 times, and finally heating under 353K vacuum for 24 hours to obtain a target product, namely a core-shell material MIL-101 (Cr) @ PMF.
FIG. 1 is powder X-ray diffraction (PXRD) of MIL-101 (Cr) @ PMF core-shell material, showing that the MIL-101 (Cr) @ PMF core-shell material has no damaged structure of MIL-101 (Cr) crystal and the structure is still complete in the preparation process. FIG. 2 is an infrared spectrum (FT-IR) of MIL-101 (Cr) @ PMF core-shell material, with the FT-IR spectrum of MIL-101 (Cr) @ PMF matching well with the FT-IR spectra of MIL-101 (Cr) and PMF, further confirming 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 catalytic function of MIL-101 (Cr) @ PMF core-shell Material on Deacentation-Knoevenagel series reactions
The method comprises the following steps: the deacetylation-Knoevenagel tandem reaction was catalyzed with MIL-101 (Cr) @ PMF core-shell material prepared in example 1 as a catalyst.
1) And (3) activating the catalyst: taking a certain amount of MIL-101 (Cr) @ PMF core-shell material, and vacuumizing and drying for 24 hours under 353K heating condition.
The method comprises the following steps: 50mg of the activated MIL-101 (Cr) @ PMF core-shell material was added to a 10mL three-necked reaction vessel, followed by 1.0mmol malononitrile, 1.0mmol benzaldehyde dimethyl acetal and 4.0mL ethanol in sequence, and reacted at 353K. The yield of the product was monitored by Gas Chromatography (GC).
During the reaction, the experimental result of the catalytic performance of the core-shell material of MILs-101 (Cr) @ PMF on the tandem reaction was detected by GC, and as the reaction proceeded, the yield of the reaction gradually increased, and by the time the reaction proceeded for 12 hours, the yield of the reaction had reached 99.9%.
2) Catalyst recyclability in the Deacetification-Knoevenagel series reaction.
And (3) catalyst recovery: after the reaction, the reaction mixture was separated from the catalyst by centrifugal filtration, washed with methanol, filtered and dried.
Specific operation of the cycling experiment: deacetenation-Knoevenagel tandem reaction was catalyzed with the recovered catalyst and reacted at 353K for 12h.
The results of the experiment are shown in fig. 4 and 5, and the activity of the catalyst is not reduced after the cyclic experiment is carried out for 5 times. The MIL-101 (Cr) @ PMF core-shell material can be used as a catalyst for the deacetylation-Knoevenagelmkjn series reaction for recycling.
Claims (1)
1. The application of a metal organic framework-based core-shell material MIL-101 (Cr) @ PMF in catalyzing a deacetylation-Knoevenagel tandem reaction is characterized by comprising the following steps of: taking benzaldehyde dimethyl acetal, malononitrile, ethanol and a catalyst to react in a three-neck reaction vessel under the condition of 353 and K to obtain a mixture of 12 and h; the catalyst is MIL-101 (Cr) @ PMF core-shell material,
the preparation method of the core-shell material MIL-101 (Cr) @ PMF based on the metal organic framework comprises the following steps:
1) Placing MIL-101 (Cr), melamine and dimethyl sulfoxide into a polytetrafluoroethylene reaction kettle, performing ultrasonic treatment on the mixture for 1h, adding paraformaldehyde and performing ultrasonic treatment on the mixture for 30 minutes;
2) Heating the 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 several times, and vacuum heating to obtain a target product;
in step 1), MIL-101 (Cr) is melamine=1:4.2 according to the mole ratio;
in the step 1), melamine is paraformaldehyde=2.3:1 according to the weight ratio;
in step 2), the temperature of the heating reaction is 393 a K and the time is 1 h;
in step 2), the reaction is continued in an oven by placing 72h under 443K;
in step 3), the vacuum heating is performed under 353K, and the vacuum heating is performed under 24h.
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| 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 |
| CN116651509A (en) * | 2023-05-30 | 2023-08-29 | 辽宁大学 | Method for catalyzing Suzuki reaction based on MOF Pi Keling emulsion of metal organic framework |
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