CN109575308B - Non-catalytic preparation method of two-dimensional fluorine-containing covalent organic framework compound - Google Patents
Non-catalytic preparation method of two-dimensional fluorine-containing covalent organic framework compound Download PDFInfo
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Abstract
The invention discloses a non-catalytic efficient preparation method of a two-dimensional fluorine-containing covalent organic framework compound. And filtering and washing the crude product, and drying to obtain the fluorine-containing covalent organic framework compound. According to the method, a catalyst is not needed, a product with good performance can be obtained after five minutes of reaction, the mesoporous structure has a high specific surface area and a regular and ordered mesoporous structure, contains a large amount of fluorine atoms, and has potential application prospects in the aspects of gas adsorption and storage, ion adsorption and the like.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a non-catalytic preparation method of a two-dimensional fluorine-containing Covalent Organic Frameworks (COFs).
Background
Covalent Organic Frameworks (COFs) are an emerging class of organic porous materials consisting of light atoms such as C, H, O, N, B, linked by covalent bonds, first reported in 2005 by the Omar. Yaghi group at Berkeley division, university of California (A.P.Cote, science.310(2005) 1166-1170.). The COFs have outstanding properties such as good material stability, low density, large specific surface area, rich pore channel structure and strong designability, and the constructed monomers are diverse and the like, so that the COFs have wide application in various aspects such as gas storage, adsorption, catalysis, photoelectricity, energy storage, biological drug loading and the like.
At present, the most commonly used method for preparing the covalent organic framework is a solvothermal method, acetic acid is used as a catalyst, and the reaction time is 3-10 days, wherein, the synthesis and performance research of the two-dimensional covalent organic framework structure of Beijing university (Chenlong. Beijing university of Physician technology, 2015.) and the synthesis of the fluorine-containing covalent organic framework containing the triazine ring of the university of China (D. -G.Wang, N.Li, Y.Hu, S.Wan, M. Song, G.Yu, Y.jin, W.Wei, K.Han, G. -C.Kuang, et al, ACS Applied Materials & Interfaces 2018, DOI 10.1021/acsami.8b14213) are researched, and the proposed synthesis methods all need to be catalyzed by acetic acid and react for three days. The existing method has long reaction time, needs a catalyst and is difficult to synthesize a product with good crystallinity.
Disclosure of Invention
The purpose of the invention is as follows: aiming at some defects in the existing research, the invention aims to provide a non-catalytic preparation method of a two-dimensional fluorine-containing covalent organic framework compound, which is used for preparing a covalent organic framework with good crystallinity, large specific surface area and high stability by a rapid catalyst-free method.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a two-dimensional fluorine-containing covalent organic framework compound is prepared by taking 2, 3, 5, 6-tetrafluoroterephthalaldehyde and a compound containing three 4-aminophenyl groups as construction units, and performing Schiff base amine aldehyde condensation reaction without catalysis to prepare a covalent organic framework compound; the reaction formula is as follows:
in the formula, R is nitrogen, phenyl or triazine ring.
The monomer structure of the compound containing three 4-aminophenyl groups is as follows:
the non-catalytic preparation method of the two-dimensional fluorine-containing covalent organic framework compound comprises the following steps:
1) adding 2, 3, 5, 6-tetrafluoroterephthalaldehyde, 2, 4, 6-tris (4-aminophenyl) -R and an organic solvent A in a molar ratio of 1: 0.1-3 into a heat-resistant reactor, freezing, vacuumizing, degassing, sealing, and performing ultrasonic dispersion to obtain a crude product;
2) filtering the crude product, washing with an organic solvent B, and refluxing in the solvent B for 1-24 h;
3) and drying the washed and refluxed product to obtain the two-dimensional fluorine-containing covalent organic framework compound.
The organic solvent A is one or a mixture of more of ethanol, DMF, dioxane, mesitylene, n-butanol, DMSO, m-cresol and o-dichlorobenzene.
The organic solvent B is one or a mixture of more of ethanol, DMF, dioxane, mesitylene, n-butanol, DMSO, m-cresol and o-dichlorobenzene.
In the step 1), the reaction temperature is 90-180 ℃, and the reaction time is 1 minute to 24 hours.
The drying method is any one of the following methods: putting the mixture into an oven, and drying the mixture for 0.1 to 24 hours at the temperature of between 60 and 200 ℃; or putting the mixture into a supercritical carbon dioxide separation kettle, introducing supercritical carbon dioxide, and washing and drying for 0.1-24 hours.
The supercritical carbon dioxide treatment is carried out at the temperature of 30-80 ℃, the pressure of 6-50 MPa, the carbon dioxide flow of 0.1-100L/h and the pipe diameter of a reaction kettle of 1-10 cm.
This application adopts the monomer that contains a plurality of fluorine atoms, reduces aldehyde group electron cloud density through the great fluorine atom of electronegativity for aldehyde group's electrophilic reinforcing has greatly improved aldehyde group monomer's reactivity, and has strengthened the product crystallinity. The preparation method does not need to use a catalyst, not only simplifies the preparation process, provides possibility for industrial application of the covalent organic framework material, but also obviously accelerates the reaction rate. The introduction of fluorine element is also beneficial to further application, and fluorine-containing COFs have great application potential in batteries and the adsorption of water pollutants and gases, especially in the adsorption of fluorine-containing pollutants.
The method solves the difficulties that a catalyst is needed and the reaction time is long in the current research, the reaction process is simple, the reaction time is shortened from three days to five minutes, and the reaction speed is increased by eight hundred times. The method can provide reference for the synthesis of a new covalent organic framework structure, is beneficial to synthesizing various covalent organic framework structures containing fluorine atoms, and provides possibility for wide application of the covalent organic framework structures.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1) the monomers used in the method are 2, 3, 5, 6-tetrafluoroterephthalaldehyde and 2, 4, 6-tri (4-aminophenyl) -R, and the four fluorine atoms contained in the monomers can greatly enhance the reaction activity of aldehyde compounds, accelerate the reaction rate and improve the crystallization performance of reaction products.
2) The method adopts a catalyst-free method, simplifies the reaction steps and greatly accelerates the reaction speed.
3) The fluorine-containing covalent organic framework obtained by the method has high yield, excellent crystallinity and large specific surface area, rich pore channels and uniform pore diameter, contains a large amount of fluorine atoms and can be used as active sites, and is favorable for adsorbing various large-size dye pollutants and fluorine-containing organic pollutants.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a fluorine-containing covalent organic framework prepared;
FIG. 2 is a graph showing the isothermal nitrogen desorption curve and pore size distribution curve of the prepared fluorine-containing covalent organic framework at 77K;
FIG. 3 is a scanning electron micrograph of a fabricated fluorine-containing covalent organic framework;
FIG. 4 is a graph of the results of energy dispersive X-ray analysis of a fabricated fluorine-containing covalent organic framework;
FIG. 5 is a Fourier infrared spectrum of a fabricated fluorine-containing covalent organic framework;
FIG. 6 is a thermogravimetric analysis plot of a fluorine-containing covalent organic framework prepared.
Detailed Description
The present application will be described in detail with reference to examples.
Example 1
A non-catalytic preparation method of a two-dimensional fluorine-containing covalent organic framework compound comprises the following steps:
1) weighing 2, 3, 5, 6-tetrafluoroterephthalaldehyde (82.4mg) and 2, 4, 6-tris (4-aminophenyl) -1, 3, 5-triazine (94.4mg) in a molar ratio of 1: 1.5 into a 2mL heat-resistant glass tube, and adding 1mL dioxane/mesitylene (v/v ═ 1: 1) solvent;
2) freezing the glass tube with liquid nitrogen, vacuumizing to 0mbar for three minutes, degassing, repeating for three times, and sealing the vacuum glass tube; performing ultrasonic treatment on the glass tube for 20 minutes, and putting the glass tube into a 120 ℃ oven for reaction for 5 minutes to obtain a crude product;
3) taking out the crude product, filtering, washing with tetrahydrofuran solution, draining, wrapping with clean filter paper, putting into a Soxhlet extractor, and washing with tetrahydrofuran solution at 100 ℃ for 12 h;
4) and taking out the product after reflux washing, and putting the product into a separation kettle of a supercritical carbon dioxide extraction instrument in a wet state, wherein the pipe diameter is 10cm, the temperature is 35 ℃, the pressure is 10MPa, and the flow rate is about 20L/h. Carbon dioxide was refluxed for 2 h. This gave a powdery yellow solid with a mass of 62.89mg and a yield of 38.7%. An X-ray powder diffraction pattern is shown in figure 1A, a nitrogen isothermal adsorption and desorption curve under 77K is shown in figure 2A, and the specific surface area is 722m calculated according to the BET theory2The pore size distribution is shown in FIG. 2C.
Example 2
A non-catalytic preparation method of a two-dimensional fluorine-containing covalent organic framework compound comprises the following steps:
1) weighing 2, 3, 5, 6-tetrafluoroterephthalaldehyde (82.4mg) and 2, 4, 6-tris (4-aminophenyl) -1, 3, 5-triazine (94.4mg) in a molar ratio of 1: 1.5 into a 2mL heat-resistant glass tube, and adding 1mL dioxane/mesitylene (v/v ═ 1: 1) solvent;
2) the glass tube was frozen with liquid nitrogen, evacuated to 0mbar for three minutes, degassed, repeated three times and sealed. Performing ultrasonic treatment on the glass tube for 20 minutes, and putting the glass tube into an oven at the temperature of 120 ℃ for reaction for 24 hours to obtain a crude product;
3) taking out the crude product, filtering, washing with tetrahydrofuran solution, draining, wrapping with clean filter paper, putting into a Soxhlet extractor, and washing with tetrahydrofuran solution at 100 ℃ for 12 h;
4) and taking out the product after reflux washing, and putting the product into a separation kettle of a supercritical carbon dioxide extraction instrument in a wet state, wherein the pipe diameter is 10cm, the temperature is 35 ℃, the pressure is 10MPa, and the flow rate is about 20L/h. Carbon dioxide was refluxed for 2 h. This gave a powdery orange-red solid with a mass of 153.0mg and a yield of 94.2%.
The X-ray diffraction pattern of the fluorine-containing covalent organic framework prepared in this example is shown in fig. 1B, which shows a strong X-ray diffraction peak at 2.85 ° and weaker crystalline peaks at 4.92 °, 5.73 °, 7.60 ° and 25.90 °. The test result is completely consistent with the simulation calculation result.
The nitrogen adsorption and desorption curve at 77K is shown in FIG. 2C, and a higher specific surface area is obtained according to the test data and the BET theory, and is 1927m2/g。
The pore size distribution is shown in figure 2D, and the pore size is 2-3 nm.
The SEM image is shown in FIG. 3, which is a sphere with irregular surface, and the size is about 300-400 nm.
Energy dispersive X-ray analysis (EDX) of FCOFs is shown in fig. 4, which has a fluorine content of 15% close to the actual value of 18.72%.
The infrared spectrum is shown in figure 5, and a clear-C-N characteristic peak appears.
The thermogravimetric analysis shows that the decomposition temperature reaches 481.2 ℃ as shown in figure 6, and the good stability is proved.
Example 3
A non-catalytic preparation method of a two-dimensional fluorine-containing covalent organic framework compound comprises the following steps:
1) weighing 2, 3, 5, 6-tetrafluoroterephthalaldehyde (82.4mg) and 2, 4, 6-tris (4-aminophenyl) -benzene (93.6mg) in a molar ratio of 1: 1.5 into a 2mL heat-resistant glass tube, and adding 1mL dioxane/mesitylene (v/v ═ 1: 1) solvent;
2) the glass tube was frozen with liquid nitrogen, evacuated to 0mbar for three minutes, degassed, repeated three times and sealed. And (3) performing ultrasonic treatment on the glass tube for 20 minutes, and putting the glass tube into an oven at 180 ℃ for reaction for 1 minute to obtain a crude product.
3) Taking out the crude product, filtering, washing with tetrahydrofuran solution, draining, wrapping with clean filter paper, putting into a Soxhlet extractor, and washing with tetrahydrofuran solution at 100 ℃ for 12 h;
4) and taking out the product after the reflux washing, and drying (putting the product into an oven, and drying for 0.1-24 hours at the temperature of 60-200 ℃) to obtain 90.0mg of orange red powdery solid. The yield was 55.4%.
Example 4
A non-catalytic preparation method of a two-dimensional fluorine-containing covalent organic framework compound comprises the following steps:
1) weighing 2, 3, 5, 6-tetrafluoroterephthalaldehyde (82.4mg) and 2, 4, 6-tris (4-aminophenyl) -benzene (93.6mg) in a molar ratio of 1: 1.5 into a 2mL heat-resistant glass tube, and adding 1mL dioxane/mesitylene (v/v ═ 1: 1) solvent;
2) the glass tube was frozen with liquid nitrogen, evacuated to 0mbar for three minutes, degassed, repeated three times and sealed. Performing ultrasonic treatment on the glass tube for 20 minutes, and putting the glass tube into an oven at the temperature of 120 ℃ for reaction for 24 hours to obtain a crude product;
3) taking out the crude product, filtering, washing with tetrahydrofuran solution, draining, wrapping with clean filter paper, putting into a Soxhlet extractor, and washing with tetrahydrofuran solution at 100 ℃ for 12 h;
4) and taking out the product after reflux washing, and putting the product into a separation kettle of a supercritical carbon dioxide extraction instrument in a wet state, wherein the pipe diameter is 10cm, the temperature is 35 ℃, the pressure is 10MPa, and the flow rate is about 20L/h. Carbon dioxide was refluxed for 2 h. This gave a powdery brown solid with a mass of 99.3mg and a yield of 61.0%.
Example 5
A non-catalytic preparation method of a two-dimensional fluorine-containing covalent organic framework compound comprises the following steps:
1) weighing 2, 3, 5, 6-tetrafluoroterephthalaldehyde (82.4mg) and 2, 4, 6-tris (4-aminophenyl) -benzene (93.6mg) in a molar ratio of 1: 1.5 into a 2mL heat-resistant glass tube, and adding 1mL dioxane/mesitylene (v/v ═ 1: 1) solvent;
2) the glass tube was frozen with liquid nitrogen, evacuated to 0mbar for three minutes, degassed, repeated three times and sealed. Performing ultrasonic treatment on the glass tube for 20 minutes, and putting the glass tube into a 90 ℃ oven for reaction for 3 days to obtain a crude product;
3) taking out the crude product, filtering, washing with tetrahydrofuran solution, draining, wrapping with clean filter paper, putting into a Soxhlet extractor, and washing with tetrahydrofuran solution at 100 ℃ for 12 h;
4) and taking out the product after reflux washing, and drying (putting the product into an oven, and drying for 0.1-24 hours at the temperature of 60-200 ℃) to obtain powdery brown solid with the mass of 94.4mg and the yield of 58.0%.
Claims (5)
1. A two-dimensional fluorine-containing covalent organic framework compound non-catalytic preparation method is characterized in that 2, 3, 5, 6-tetrafluoroterephthalaldehyde and a compound containing three 4-aminophenyl groups are used as construction units, and Schiff base amine-aldehyde condensation reaction is carried out without catalysis to prepare the covalent organic framework compound; the reaction formula is as follows:
in the formula, R is nitrogen, phenyl or triazine ring;
the method specifically comprises the following steps:
1) adding 2, 3, 5, 6-tetrafluoroterephthalaldehyde, 2, 4, 6-tris (4-aminophenyl) -R and an organic solvent A in a molar ratio of 1: 0.1-3 into a heat-resistant reactor, freezing, vacuumizing, degassing, sealing, and performing ultrasonic dispersion to obtain a crude product; the reaction temperature is 90-180 ℃, and the reaction time is 1 minute to 24 hours;
2) filtering the crude product, washing with an organic solvent B, and refluxing in the organic solvent B for 1-24 h;
3) and drying the washed and refluxed product to obtain the two-dimensional fluorine-containing covalent organic framework compound.
2. The non-catalytic preparation method of two-dimensional fluorine-containing covalent organic framework compound according to claim 1, wherein the organic solvent A is one or a mixture of ethanol, DMF, dioxane, mesitylene, n-butanol, DMSO, m-cresol, o-dichlorobenzene.
3. The non-catalytic preparation method of two-dimensional fluorine-containing covalent organic framework compound according to claim 1, wherein the organic solvent B is one or more of ethanol, DMF, dioxane, mesitylene, n-butanol, DMSO, m-cresol, and o-dichlorobenzene.
4. The non-catalytic preparation method of two-dimensional fluorine-containing covalent organic framework compound according to claim 1, wherein in step 3), the drying method is any one of the following methods: putting the mixture into an oven, and drying the mixture for 0.1 to 24 hours at the temperature of between 60 and 200 ℃; or putting the mixture into a supercritical carbon dioxide separation kettle, introducing supercritical carbon dioxide, and washing and drying for 0.1-24 hours.
5. The non-catalytic preparation method of the two-dimensional fluorine-containing covalent organic framework compound according to claim 4, wherein the supercritical carbon dioxide treatment is carried out at a temperature of 30-80 ℃, a pressure of 6-50 MPa, a carbon dioxide flow rate of 0.1-100L/h, and a reaction vessel diameter of 1-10 cm.
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| GB201913355D0 (en) * | 2019-09-16 | 2019-10-30 | Cambridge Entpr Ltd | Covalent-organic framework materials and methods of making thereof |
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| CN110922605B (en) * | 2019-12-09 | 2022-03-08 | 海南大学 | Method for preparing covalent organic framework material by using supercritical carbon dioxide |
| CN111777730B (en) * | 2020-07-13 | 2021-05-07 | 齐鲁工业大学 | Reticular covalent organic framework material and preparation method and application thereof |
| CN112316929A (en) * | 2020-08-28 | 2021-02-05 | 广东省测试分析研究所（中国广州分析测试中心） | Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof |
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