CN110964210B - Porous organic material and preparation method and application thereof - Google Patents

Porous organic material and preparation method and application thereof Download PDF

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CN110964210B
CN110964210B CN201911367454.1A CN201911367454A CN110964210B CN 110964210 B CN110964210 B CN 110964210B CN 201911367454 A CN201911367454 A CN 201911367454A CN 110964210 B CN110964210 B CN 110964210B
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porous organic
organic material
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梁志强
刘雨川
宋晓伟
王顺
崔元正
孟宪宇
叶禹
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Jilin University
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Abstract

The invention belongs to the technical field of porous materials, and particularly relates to a porous organic material, and a preparation method and application thereof. The invention provides a preparation method of a porous organic material, which comprises the following steps: carrying out coupling polymerization reaction on an organic monomer to obtain a two-dimensional topological material; mixing the two-dimensional topological material, a catalyst, an external cross-linking agent and a solvent, and carrying out Friedel-crafts reaction to obtain a porous organic material; the organic monomer comprises one or more of aromatic halide, boric acid substituted aromatic compound, boric acid pinacol ester group substituted aromatic compound, alkynyl substituted aromatic compound and alkenyl substituted aromatic compound. The method comprises the steps of firstly preparing the two-dimensional topological material with the skeleton rigidity, and then inserting the substituent into the rigid organic network of the two-dimensional topological material and fixing the two-dimensional topological material through the covalent bond, so that the expansion of the porous skeleton in the original two-dimensional topological material is realized, and the specific surface area and the porosity of the two-dimensional topological material are obviously increased.

Description

Porous organic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a porous organic material, and a preparation method and application thereof.
Background
Porous organic materials are classified into hypercrosslinked polymers, self-contained microporous polymers, covalent organic framework materials, conjugated microporous polymers, covalent triazine framework materials and porous aromatic framework materials according to different types. The preparation cost of the hypercrosslinked polymer is low, but the monomer types are limited, and the preparation of the hypercrosslinked polymer with higher specific surface area is difficult to realize; the polymer with micropores has excellent solubility, and is beneficial to the field of membrane separationThe development of the method is still restricted by the small monomer types and the low specific surface area; the covalent organic framework material has an excellent long-range ordered structure, can realize effective regulation and control of pore size through structural design, and is difficult to realize commercial development at the present stage due to the relatively harsh preparation conditions and limited organic reaction types of the covalent organic framework material because the crystallinity of the covalent organic framework material usually shows higher specific surface area; the synthetic method of the conjugated microporous polymer has diversity, the raw materials are various, and the industrial production can be realized theoretically, but the specific surface area of most of the materials is lower; the covalent triazine framework material inherits partial advantages of a covalent organic framework material, but the traditional high-temperature ionic heat method usually causes structure carbonization to lose the self structural advantage, and is difficult to commercialize; the porous aromatic skeleton material is excellent in specific surface area, and the specific surface area of a plurality of cases exceeds 5000m2The porous aromatic skeleton material per gram has been successfully prepared and has good stability, but the preparation cost is too expensive and the monomer types are extremely limited, so that the commercialization is difficult at present.
The applicant has analyzed and summarized the BET specific surface areas of 1366 porous organic materials, and the results show that 21.1% of the porous organic materials have specific surface areas lower than 400m219.5 percent of porous organic material with specific surface area concentrated in 600-800 m2In g, high specific surface area (BET specific surface area)>1000m2The porous organic material per g) was only 29.1%. Therefore, the preparation of the porous organic material with higher specific surface area is still difficult to realize by technical means such as reaction condition optimization, more complex monomer design, new organic reaction type development and the like. In the face of the difficult problem of synthesizing the porous organic material with high specific surface area, a new synthesis method is explored to realize that the porous organic material with low preparation cost, simple preparation process, excellent pore structure, functionalized skeleton and high specific surface area has important industrial significance and economic value.
Disclosure of Invention
In view of the above, the present invention aims to provide a porous organic material and a preparation method thereof, and the porous organic material prepared by the preparation method provided by the present invention has characteristics of high specific surface area and excellent pore structure, and the preparation method has characteristics of low cost, simple process, and suitability for commercial production. The invention also provides application of the porous organic material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of a porous organic material, which comprises the following steps:
carrying out coupling polymerization reaction on an organic monomer to obtain a two-dimensional topological material;
mixing the two-dimensional topological material, a catalyst, an external cross-linking agent and a solvent, and carrying out Friedel-crafts reaction to obtain a porous organic material; the organic monomer comprises one or more of aromatic halide, boric acid substituted aromatic compound, boric acid pinacol ester group substituted aromatic compound, alkynyl substituted aromatic compound and alkenyl substituted aromatic compound.
Preferably, the organic monomer comprises one or more of 1,3, 5-tribromobenzene, 1, 4-dibromobenzene, 1,2,4, 5-tetrabromobenzene, 1, 4-diiodobenzene, 2,4, 6-tribromoaniline, 1, 4-phenylboronic acid, 4' -biphenyldiboronic acid dipentenol ester, 1, 4-benzenediboronic acid dipentenol ester, 1,3, 5-benzenetriborate ester, 1, 4-diethynylbenzene, 1,3, 5-triethynylbenzene and 1, 4-divinylbenzene.
Preferably, the coupling polymerization reaction is suzuki-miyaura reaction, yamamoto coupling reaction, sonogashira coupling reaction, or oxidative coupling reaction.
Preferably, the catalyst is a lewis acid; the molar ratio of the two-dimensional topological material to the catalyst is 1: (0.1-10).
Preferably, the lewis acid comprises anhydrous AlCl3Anhydrous FeCl3Anhydrous SnCl4Or anhydrous ZrCl4。
Preferably, the external crosslinking agent comprises one or more of dimethoxymethane, dichloromethane, 1, 2-dichloroethane, octavinyl octasilsesquioxane, cyanuric chloride, p-dichlorobenzyl, o-dichlorobenzyl, m-dichlorobenzyl and biphenyl dichlorobenzyl; the mass ratio of the two-dimensional topological material to the external cross-linking agent is 1: (0.1 to 200).
Preferably, the solvent comprises dichloromethane, 1, 2-dichloroethane or nitrobenzene; the relative dosage ratio of the two-dimensional topological material to the solvent is 100 g: (1-50) L.
Preferably, the temperature of the Friedel-crafts reaction comprises a first-stage heat preservation, a second-stage heat preservation and a third-stage heat preservation which are sequentially carried out;
the temperature of the first stage heat preservation is 18-25 ℃, and the time is 0.5-12 h;
the temperature of the second stage heat preservation is 40-60 ℃, and the time is 0.5-24 h;
the temperature of the third stage heat preservation is 80-100 ℃, and the time is 10-72 hours.
The invention also provides the porous organic material prepared by the preparation method in the technical scheme.
The invention also provides application of the porous organic material in the technical scheme in the fields of catalyst carriers, guest molecule confinement materials, energy storage materials, gas storage materials, organic vapor capture materials and adsorption materials.
The invention provides a preparation method of a porous organic material, which comprises the following steps: carrying out coupling polymerization reaction on an organic monomer to obtain a two-dimensional topological material; mixing the two-dimensional topological material, a catalyst, an external cross-linking agent and a solvent, and carrying out Friedel-crafts reaction to obtain a porous organic material; the organic monomer comprises one or more of aromatic halide, boric acid substituted aromatic compound, boric acid pinacol ester group substituted aromatic compound, alkynyl substituted aromatic compound and alkenyl substituted aromatic compound. The invention creatively provides a preparation method of 'reassembling', firstly a porous organic network two-dimensional topological material with skeleton rigidity is prepared, then a substituent is inserted into the rigid organic network of the two-dimensional topological material and is fixed through a covalent bond, thereby realizing the expansion of a porous skeleton in the original two-dimensional topological material, obviously increasing the specific surface area and the porosity of the two-dimensional topological material, and leading the pore structure distribution of the obtained porous organic material to be more trend to a larger nano-aperture; in addition, the two-dimensional topological material in the preparation method provided by the invention has the advantages of abundant monomer types of synthetic raw materials, low cost, and capability of greatly reducing the synthetic difficulty and cost, thereby being beneficial to realizing commercialization.
The test results of the examples show that the porous organic material obtained by the preparation method provided by the invention has the highest BET specific surface area of 3083m2(ii)/g, exceeding the hypercrosslinked polymers and conjugated microporous polymers reported in the literature.
Drawings
FIG. 1 is a diagram showing a process for preparing a porous organic material in example 3 of the present invention;
FIG. 2 is a nitrogen adsorption isotherm graph of a two-dimensional topological material POF-Aa under a 77K condition in an embodiment of the invention;
FIG. 3 is a nitrogen adsorption isotherm graph of a two-dimensional topological material POF-Ab under 77K conditions in an embodiment of the invention;
FIG. 4 is a nitrogen adsorption isotherm graph of a two-dimensional topological material POF-Bb under a 77K condition in an embodiment of the present invention;
FIG. 5 is a nitrogen adsorption isotherm graph of a two-dimensional topological material POF-Ca under a 77K condition in an embodiment of the present invention;
FIG. 6 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 1 of the present invention;
FIG. 7 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 2 of the present invention;
FIG. 8 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 3 of the present invention;
FIG. 9 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 4 of the present invention;
FIG. 10 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 5 of the present invention;
FIG. 11 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 6 of the present invention;
FIG. 12 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 7 of the present invention;
FIG. 13 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 8 of the present invention;
FIG. 14 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 9 of the present invention;
FIG. 15 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 10 of the present invention;
FIG. 16 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 11 of the present invention;
FIG. 17 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 12 of the present invention;
FIG. 18 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 13 of the present invention;
FIG. 19 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 14 of the present invention;
FIG. 20 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 15 of the present invention;
FIG. 21 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 16 of the present invention;
FIG. 22 is a nitrogen adsorption isotherm plot under 77K conditions of the porous organic material obtained in example 17 of the present invention;
FIG. 23 is a pore size distribution curve (1-100 nm, obtained by calculation of a density functional theory DFT model) of a two-dimensional topological material POF-Aa in the embodiment of the invention;
FIG. 24 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of a two-dimensional topological material POF-Ab in the embodiment of the present invention;
FIG. 25 is a pore size distribution curve (1-100 nm, obtained by calculation of a density functional theory DFT model) of a two-dimensional topological material POF-Bb in the embodiment of the invention;
FIG. 26 is a pore size distribution curve (1-100 nm, obtained by calculation of a density functional theory DFT model) of a two-dimensional topological material POF-Ca in the embodiment of the present invention;
FIG. 27 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 1 of the present invention;
FIG. 28 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 2 of the present invention;
FIG. 29 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 3 of the present invention;
FIG. 30 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 4 of the present invention;
FIG. 31 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 5 of the present invention;
FIG. 32 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 6 of the present invention;
FIG. 33 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 7 of the present invention;
FIG. 34 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 8 of the present invention;
FIG. 35 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 9 of the present invention;
FIG. 36 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 10 of the present invention;
FIG. 37 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 11 of the present invention;
FIG. 38 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 12 of the present invention;
FIG. 39 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 13 of the present invention;
FIG. 40 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 14 of the present invention;
FIG. 41 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 15 of the present invention;
FIG. 42 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 16 of the present invention;
FIG. 43 is a pore size distribution curve (1-100 nm, obtained by calculation using a density functional theory DFT model) of the porous organic material obtained in example 17 of the present invention;
FIG. 44 is an infrared spectrum of a two-dimensional topological material POF-Aa in an embodiment of the present invention;
FIG. 45 is an IR spectrum of a two-dimensional topology material POF-Ab in an embodiment of the present invention;
FIG. 46 is an IR spectrum of a two-dimensional topology material POF-Bb in an embodiment of the present invention;
FIG. 47 is an IR spectrum of POF-Ca, a two-dimensional topology material, according to an embodiment of the present invention;
FIG. 48 is an IR spectrum of a porous organic material obtained in example 1 of the present invention;
FIG. 49 is an IR spectrum of a porous organic material obtained in example 2 of the present invention;
FIG. 50 is an IR spectrum of a porous organic material obtained in example 3 of the present invention;
FIG. 51 is an IR spectrum of a porous organic material obtained in example 4 of the present invention;
FIG. 52 is an IR spectrum of a porous organic material obtained in example 5 of the present invention;
FIG. 53 is an IR spectrum of a porous organic material obtained in example 6 of the present invention;
FIG. 54 is an IR spectrum of a porous organic material obtained in example 7 of the present invention;
FIG. 55 is an IR spectrum of a porous organic material obtained in example 8 of the present invention;
FIG. 56 is an IR spectrum of a porous organic material obtained in example 9 of the present invention;
FIG. 57 is an IR spectrum of a porous organic material obtained in example 10 of the present invention;
FIG. 58 is an IR spectrum of a porous organic material obtained in example 11 of the present invention;
FIG. 59 is an IR spectrum of a porous organic material obtained in example 12 of the present invention;
FIG. 60 is an IR spectrum of a porous organic material obtained in example 13 of the present invention;
FIG. 61 is an IR spectrum of a porous organic material obtained in example 14 of the present invention;
FIG. 62 is an IR spectrum of a porous organic material obtained in example 15 of the present invention;
FIG. 63 is an IR spectrum of a porous organic material obtained in example 16 of the present invention;
FIG. 64 is an IR spectrum of a porous organic material obtained in example 17 of the present invention;
FIG. 65 is a hydrogen adsorption isotherm of the porous organic material obtained in example 10 of the present invention under 77K conditions.
FIG. 66 is a graph showing the adsorption isotherms of toluene and cyclohexane on a porous organic material obtained in example 10 of the present invention at room temperature.
FIG. 67 shows CO of two-dimensional topological material POF-Ab under 273K and 298K conditions in the present invention2Adsorption curve diagram;
FIG. 68 shows CO under 273K and 298K conditions of the porous organic material obtained in example 7 of the present invention2Adsorption curve diagram;
FIG. 69 shows CO of the porous organic material obtained in example 8 under 273K and 298K conditions2Adsorption curve diagram;
FIG. 70 shows CO under 273K and 298K conditions for the porous organic material obtained in example 17 of the present invention2Adsorption curve diagram;
fig. 71 is an adsorption isotherm diagram of the porous organic material obtained in example 13 of the present invention for the dyes congo red and rhodamine B in water at room temperature.
Detailed Description
The invention provides a preparation method of a porous organic material, which comprises the following steps:
carrying out coupling polymerization reaction on an organic monomer to obtain a two-dimensional topological material;
mixing the two-dimensional topological material, a catalyst, an external cross-linking agent and a solvent, and carrying out Friedel-crafts reaction to obtain a porous organic material;
the organic monomer preferably includes one or more of an aromatic halide, a boronic acid-substituted aromatic compound, a boronic acid pinacol ester group-substituted aromatic compound, an alkynyl-substituted aromatic compound, and an alkenyl-substituted aromatic compound.
In the present invention, the raw materials of the respective components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention carries out coupling polymerization reaction on organic monomers to obtain the two-dimensional topological material.
In the present invention, the organic monomer is preferably one or more of 1,3, 5-tribromobenzene, 1, 4-dibromobenzene, 1,2,4, 5-tetrabromobenzene, 1, 4-diiodobenzene, 2,4, 6-tribromoaniline, 1, 4-phenylboronic acid, 4' -biphenyldiboronic acid dipentenol ester, 1, 4-benzenediboronic acid dipentenol ester, 1,3, 5-benzenetriborate ester, 1, 4-diethynylbenzene, 1,3, 5-triethynylbenzene, and 1, 4-divinylbenzene.
In the present invention, the coupling polymerization reaction is preferably a Suzuki cross-coupling reaction, a Yamamoto coupling reaction, a Sonogashira-Hagihara coupling reaction, or an Oxidative coupling (Oxidative coupling) reaction.
In the present invention, the solvent in the coupling polymerization reaction is preferably N, N-Dimethylformamide (DMF), dichloromethane or 1, 2-dichloroethane; the catalyst is preferably Pd (PhCN)2Cl2(ii) a The base is preferably potassium carbonate. In the present invention, the coupling polymerization reaction is preferably carried out under a protective gas condition; the shielding gas is preferably nitrogen.
The invention generates organic porous polymer with conjugated skeleton structure through coupling polymerization reaction, the building units are arranged in order in the topological structure in period, and pi conjugated effect is generated, namely the two-dimensional topological material obtained by the invention is the conjugated microporous polymer.
After the two-dimensional topological material is obtained, the two-dimensional topological material, the catalyst, the external cross-linking agent and the solvent are mixed to carry out Friedel-crafts reaction, and the porous organic material is obtained.
In the present invention, the catalyst is preferably a lewis acid; the Lewis acid is preferably anhydrous AlCl3Anhydrous FeCl3Anhydrous SnCl4Or anhydrous ZrCl4. In the present invention, the molar ratio of the two-dimensional topological material to the catalyst is preferably 1: (0.1 to 10), more preferably 1: (0.5 to 9.5), more preferably 1: (1-9), more preferably 1: (2.5-7.5).
In the present invention, the external crosslinking agent preferably includes one or more of dimethoxymethane, dichloromethane, 1, 2-dichloroethane, octavinyl octasilsesquioxane, cyanuric chloride, p-dichlorobenzyl, o-dichlorobenzyl, m-dichlorobenzyl and biphenyl dichlorobenzyl. In the present invention, the mass ratio of the two-dimensional topological material to the external cross-linking agent is preferably 1: (0.1 to 200), more preferably 1: (10-180), and more preferably 1: (50-120), more preferably 1: (80-110).
In the present invention, the solvent is preferably dichloromethane, 1, 2-dichloroethane or nitrobenzene. In the present invention, the relative dosage ratio of the two-dimensional topological material to the solvent is preferably 100 g: (1-50) L, more preferably 100 g: (10-40) L, more preferably 100 g: (15-35) L, more preferably 100 g: (20-30) L.
In the present invention, the temperature of the friedel-crafts reaction preferably includes a first-stage heat preservation, a second-stage heat preservation, and a third-stage heat preservation, which are performed in this order.
In the invention, the temperature of the first-stage heat preservation is preferably 18-25 ℃, and more preferably 19-24 ℃; the time is preferably 0.5 to 12 hours, more preferably 1 to 11 hours, and still more preferably 3 to 8 hours.
In the invention, the temperature of the second-stage heat preservation is preferably 40-60 ℃, more preferably 42-58 ℃, and further preferably 45-55 ℃; the time is preferably 0.5 to 24 hours, more preferably 1 to 22 hours, and still more preferably 5 to 17 hours. The temperature of the second stage heat preservation is preferably achieved by a heating mode, and the heating rate is preferably 1-5 ℃/min.
In the invention, the temperature of the third-stage heat preservation is preferably 80-100 ℃, more preferably 82-98 ℃, and further preferably 85-95 ℃; the time is preferably 10 to 72 hours, more preferably 15 to 68 hours, and still more preferably 20 to 60 hours. The temperature of the third stage heat preservation is preferably reached by a heating mode, and the heating rate is preferably 1-5 ℃/min.
Before performing the friedel-crafts reaction, the present invention preferably further comprises sequentially purifying and drying the two-dimensional topology material.
In the present invention, the purification is preferably a washing purification. In the present invention, the washing and purifying agent preferably includes water, methanol, tetrahydrofuran and dichloromethane. The washing and purifying process is not particularly limited in the invention, and a washing and purifying process well known to those skilled in the art can be adopted; according to the invention, the purity of the two-dimensional topological material is improved through washing and purification.
In the present invention, the drying temperature is preferably 100 ℃ and the drying time is preferably 10 hours. In the present invention, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is not limited in the present invention, and a vacuum degree known to those skilled in the art may be used.
After the Friedel-crafts reaction is finished, the invention preferably further comprises the steps of sequentially carrying out suction filtration, washing and drying on the obtained Friedel-crafts reaction product to obtain the porous organic material.
The suction filtration is not particularly limited in the present invention, and may be a suction filtration known to those skilled in the art. The invention removes the liquid material in the Friedel-crafts reaction product by suction filtration. The washing method is not particularly limited, and the washing method is well known to those skilled in the art, and specifically, the washing method comprises the steps of cleaning the surfaces and the channels of the friedel-crafts reaction product by using ethanol, water, tetrahydrofuran and methanol, removing the catalyst, the solvent and the external cross-linking agent in the surfaces and the channels of the friedel-crafts reaction product, and then extracting the surface and the channels of the friedel-crafts reaction product by using methanol or tetrahydrofuran to remove the trace catalyst in the channels of the friedel-crafts reaction product. The invention removes the catalyst and the by-product attached to the surface of the Friedel-crafts reaction product and in the pore channel by washing. In the present invention, the temperature and time for drying are not particularly limited, and the washing reagent may be removed. In the present invention, the drying is preferably drying under reduced pressure; in the present invention, the pressure for the reduced pressure drying is not particularly limited, and a pressure for reduced pressure drying known to those skilled in the art may be used.
According to the invention, the pore size distribution and the specific surface area of the porous organic material can be regulated and controlled by changing the proportion and the type of the two-dimensional topological material and the external cross-linking agent, and the porous organic material with the same functional groups and high specific surface area can be obtained by using the two-dimensional topological material as an intermediate raw material; in the preparation method, one or more two-dimensional topological materials and an external cross-linking agent are used simultaneously, so that the pore structure and the specific surface area of the porous organic material can be adjusted.
The invention also provides the porous organic material prepared by the preparation method in the technical scheme.
The structure of the porous material is basically characterized by testing an infrared spectrogram, and the result shows that the prepared porous organic material is 2925cm in length due to the Friedel-crafts reaction of the cross-linking molecules and the two-dimensional topological material-1Nearby apparent-CH2Infrared peak of vibration, at 1500cm-1And 1600cm-1A strong benzene ring vibration peak is nearby; further, the specific surface area and the pore size distribution of the obtained porous organic material are characterized and analyzed through a nitrogen adsorption curve test, and the result shows that the BET specific surface area of the obtained porous organic material is 494-3083 m2The average pore size distribution of the obtained porous organic material is 2.6-8.6 nm.
The invention also provides application of the porous organic material in the technical scheme in the fields of catalyst carriers, guest molecule confinement materials, energy storage materials, gas storage materials, organic vapor capture materials and adsorption materials.
In the present invention, the storable gas of the gas storage material is preferably hydrogen, carbon dioxide or methane; the organic vapor that can be captured by the organic vapor capture material is preferably toluene vapor, cyclohexane vapor, or benzene vapor.
In order to further illustrate the present invention, the following examples are provided to describe in detail a porous organic material, a method for preparing the same, and applications thereof, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing a two-dimensional topological material: stirring 6mmol of 1,3, 5-tribromobenzene, 9mmol of p-phenylboronic acid and 300mL of DMF solvent at room temperature to fully dissolve raw materials of each component, and then adding 36mmol of K2CO3Adding into the mixed system, adding 0.3mmol of catalyst Pd (PhCN) under the protection of nitrogen2Cl2And (3) pumping and changing gas for 3 times, fully removing air in a reaction system, reacting at 80 ℃ for 12h, then heating to 120 ℃ for reacting for 48h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, fully stirring and cleaning a filter cake at 60 ℃ in tetrahydrofuran, methanol, water and dichloromethane in sequence, and drying at 120 ℃ in vacuum to obtain the two-dimensional topological material (marked as POF-Aa).
Preparing a porous organic material: with FeCl3Dispersing 1g of two-dimensional topological material POF-Aa into 200mL of 1, 2-dichloroethane solvent by using a Lewis acid catalyst and dimethoxymethane as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the two-dimensional topological material POF-Aa, then adding 12mmol of catalyst and 11mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 1h, then heating to 85 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water to quench, filtering, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HC-POF-Aa).
Example 2
The two-dimensional topological material POF-Aa was prepared according to the method in example 1.
Preparation of porousOrganic materials: with AlCl3Dispersing 1.87g of POF-Aa into 200mL of dichloromethane solvent as a Lewis acid catalyst and taking dichloromethane as an external cross-linking agent and a solvent, fully stirring under the protection of nitrogen to disperse the POF-Aa, then adding 7.5mmol of the catalyst into a reaction system, stirring for 0.25h at room temperature, then heating to 45 ℃ to react for 1h, then heating to 80 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding a hydrochloric acid aqueous solution to quench, carrying out suction filtration, washing with a large amount of ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, finally removing trace impurities by methanol extraction, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as SK-POF-Aa).
Example 3
The two-dimensional topological material POF-Aa was prepared according to the method in example 1.
Preparing a porous organic material: with FeCl3Dispersing 1.26g of POF-Aa in 300mL of 1, 2-dichloroethane solvent as a Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Aa, then adding 6mmol of catalyst and 5mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ for reaction for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HCCP-1).
The preparation process is shown in figure 1.
Example 4
The two-dimensional topological material POF-Aa was prepared according to the method in example 1.
Preparing a porous organic material: with FeCl3Dispersing 1.26g of POF-Aa in 300mL of 1, 2-dichloroethane solvent by using Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Aa, then adding 6mmol of catalyst and 7.5mmol of external crosslinking agent into the reaction system, and stirring at room temperatureAnd (3) 0.5h, heating to 45 ℃, stirring for 0.5h, heating to 85 ℃, reacting for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, performing suction filtration, washing with ethanol and water, fully stirring and cleaning a filter cake at 60 ℃ in tetrahydrofuran, methanol, water, dichloromethane and DMF in sequence, extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain the porous organic material (marked as HCCP-2).
Example 5
The two-dimensional topological material POF-Aa was prepared according to the method in example 1.
Preparing a porous organic material: with FeCl3Dispersing 1.26g of POF-Aa in 300mL of 1, 2-dichloroethane solvent as a Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Aa, then adding 8mmol of catalyst and 10mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ for reaction for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HCCP-3).
Example 6
The two-dimensional topological material POF-Aa was prepared according to the method in example 1.
Preparing a porous organic material: with FeCl3Dispersing 1.26g of POF-Aa in 300mL of 1, 2-dichloroethane solvent for Lewis acid catalyst and p-dichlorobenzyl as an external cross-linking agent, fully stirring under the protection of nitrogen to disperse the POF-Aa, then adding 8mmol of catalyst and 12.5mmol of external cross-linking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ for reaction for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with a large amount of ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain the productTo porous organic materials (denoted as HCCP-4).
Example 7
Preparing a two-dimensional topological material: stirring 7mmol of 1,3, 5-tribromobenzene, 10.5mmol of 4, 4' -biphenyl diboronic acid and 200mL of DMF solvent at room temperature to fully dissolve the raw materials of each component, and then adding 42mmol of K2CO3Adding into the mixed system, adding 0.35mmol of catalyst Pd (PhCN) under the protection of nitrogen2Cl2And (3) pumping and changing gas for 3 times, fully removing oxygen in a reaction system, reacting at 80 ℃ for 12h, then heating to 120 ℃ for reacting for 48h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, and drying at 120 ℃ in vacuum to obtain the two-dimensional topological material (marked as POF-Ab).
Preparing a porous organic material: with FeCl3Dispersing 1g of POF-Ab into 200mL of 1, 2-dichloroethane solvent by using Lewis acid catalyst and dimethoxymethane as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Ab, then adding 8mmol of catalyst and 11mmol of external crosslinking agent into the reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 1h, then heating to 85 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water to quench, filtering, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, finally removing trace impurities by using methanol, and drying at 120 ℃ in vacuum to obtain a porous organic material (recorded as HC-POF-Ab).
Example 8
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with AlCl3Dispersing 3g of POF-Ab in 200mL of dichloromethane solvent by using dichloromethane as an external crosslinking agent and a solvent as a Lewis acid catalyst, fully stirring under the protection of nitrogen to disperse the POF-Ab, then adding 7.5mmol of the catalyst into a reaction system, stirring at room temperature for 15min, then heating to 45 ℃ for reaction for 1h, then heating to 80 ℃ for reaction for 16h, and after the reaction is finished,and cooling the reaction system to room temperature, adding hydrochloric acid aqueous solution for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning the filter cake in tetrahydrofuran, methanol, water and dichloromethane in sequence at 60 ℃, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain the porous organic material (marked as SK-POF-Ab).
Example 9
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with FeCl3Dispersing 1g of POF-Ab in 300mL of 1, 2-dichloroethane solvent by using Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Ab, then adding 8mmol of catalyst and 5mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water to quench, filtering, washing with ethanol and water, then fully stirring and cleaning a filter cake in organic solvents of tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally removing trace impurities by using methanol, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HCCP-5).
Example 10
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with FeCl3Dispersing 1g of POF-Ab in 300mL of 1, 2-dichloroethane solvent by using Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Ab, then adding 8mmol of catalyst and 6.7mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ for reaction for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HCCP-6).
Example 11
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with FeCl3Dispersing 1.26mg of POF-Ab into 300mL of 1, 2-dichloroethane solvent as a Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Ab, then adding 8mmol of catalyst and 8.3mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ for reaction for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HCCP-7).
Example 12
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with FeCl3Dispersing 1.26g of POF-Ab into 300mL of 1, 2-dichloroethane solvent as a Lewis acid catalyst and p-dichlorobenzyl as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Ab, then adding 8mmol of catalyst and 10mmol of external crosslinking agent into a reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 0.5h, then heating to 85 ℃ for reaction for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water, dichloromethane and DMF at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (marked as HCCP-8).
Example 13
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with AlCl31g of POF-Ab and 3.2mmol of a Lewis acid catalyst, 1, 2-dichloroethane as solvent and crosslinker, octavinyl octasilsesquioxane as additional external crosslinkerDispersing octavinyl octasilsesquioxane in 100mL of 1, 2-dichloroethane solvent, fully stirring under the protection of nitrogen to disperse the octavinyl octasilsesquioxane, then adding 7.5mmol of catalyst into a reaction system, heating to 85 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding hydrochloric acid aqueous solution to quench, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane in sequence at 60 ℃, finally removing trace impurities by methanol extraction, and drying at 120 ℃ in vacuum to obtain the porous organic material (marked as POF-OVS-19).
Example 14
Preparing a two-dimensional topological material: stirring 7mmol of amino-2, 4, 6-tribromobenzene, 10.5mmol of 4, 4' -biphenyl diboronic acid and 200mL of DMF solvent at room temperature to fully dissolve raw materials of each component, and then dissolving 42mmol of K2CO3Adding into the mixed system, adding 0.35mmol of catalyst Pd (PhCN) under the protection of nitrogen2Cl2And (3) pumping and changing gas for 3 times, fully removing oxygen in a reaction system, reacting at 80 ℃ for 12h, then heating to 120 ℃ for reacting for 48h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, and drying at 120 ℃ in vacuum to obtain the two-dimensional topological material (marked as POF-Bb).
Preparing a porous organic material: with AlCl3Dispersing 3g of POF-Bb in 200mL of dichloromethane solvent by using dichloromethane as an external cross-linking agent and a solvent as a Lewis acid catalyst, fully stirring under the protection of nitrogen to disperse the POF-Bb, adding 22.5mmol of the catalyst into a reaction system, stirring at room temperature for 15min, heating to 45 ℃ to react for 1h, heating to 80 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding a hydrochloric acid aqueous solution to quench, performing suction filtration, washing with ethanol and water, fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane in sequence at 60 ℃, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain the porous organic material (marked as SK-POF-Bb).
Example 15
Preparing a two-dimensional topological material: stirring 5mmol of 3,4', 5-tribromo-1, 1' -biphenyl, 7.5mmol of p-phenylboronic acid and 200mL of DMF (dimethyl formamide) solvent at room temperature to fully dissolve raw materials of each component, and then adding 4.1g of K2CO3Adding into the mixed system, adding 0.35mmol of catalyst Pd (PhCN) under the protection of nitrogen2Cl2And (3) pumping and changing gas for 3 times, fully removing oxygen in a reaction system, reacting at 80 ℃ for 12h, then heating to 120 ℃ for reacting for 48h, cooling the reaction system to room temperature after the reaction is finished, adding water for quenching, carrying out suction filtration, washing with ethanol and water, fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, and drying at 120 ℃ in vacuum to obtain the two-dimensional topological material (marked as POF-Ca).
Preparing a porous organic material: with FeCl3Dispersing 1g of POF-Ca into 200mL of 1, 2-dichloroethane solvent by using a Lewis acid catalyst and dimethoxymethane as an external crosslinking agent, fully stirring under the protection of nitrogen to disperse the POF-Ca, then adding 8mmol of catalyst and 11mmol of external crosslinking agent into the reaction system, stirring at room temperature for 0.5h, then heating to 45 ℃ and stirring for 1h, then heating to 85 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding water to quench, filtering, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃ in sequence, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain a porous organic material (recorded as HC-POF-Ca).
Example 16
The two-dimensional topology material POF-Ca was prepared according to the method in example 15.
Preparing a porous organic material: with AlCl3Dispersing 2.5g of POF-Ca in 200mL of dichloromethane solvent, fully stirring under the protection of nitrogen to disperse the POF-Ca, adding 22.5mmol of catalyst into a reaction system, stirring at room temperature for 15min, heating to 45 ℃ to react for 1h, heating to 80 ℃ to react for 16h, cooling the reaction system to room temperature after the reaction is finished, adding hydrochloric acid aqueous solution to quench, carrying out suction filtration, washing with ethanol and water, and washing with waterAnd (3) fully stirring and cleaning the filter cake in tetrahydrofuran, methanol, water and dichloromethane at 60 ℃, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain the porous organic material (marked as SK-POF-Ca).
Example 17
The two-dimensional topology material POF-Ab was prepared according to the method in example 7.
Preparing a porous organic material: with AlCl3In the presence of Lewis acid catalyst, 1, 2-dichloroethane as solvent and crosslinking agent, cyanuric chloride as another external crosslinking agent, 303mg of POF-Ab and 1mmol of cyanuric chloride are dispersed in 20mL of 1, 2-dichloroethane methane solvent, fully stirring under the protection of nitrogen to disperse the catalyst, then adding 3mmol of catalyst into a reaction system, stirring at room temperature for 15min, then heating to 45 ℃ for reaction for 1h, then heating to 85 ℃ for reaction for 16h, after the reaction is finished, cooling the reaction system to room temperature, adding a hydrochloric acid aqueous solution for quenching, carrying out suction filtration, washing with ethanol and water, then fully stirring and cleaning a filter cake in tetrahydrofuran, methanol, water and dichloromethane in sequence at 60 ℃, finally extracting with methanol to remove trace impurities, and drying at 120 ℃ in vacuum to obtain the porous organic material (marked as CT-POF-Ab).
The two-dimensional topology materials prepared in examples 1, 7, 14 and 15 and the porous organic materials obtained in examples 1 to 17 were subjected to N under 77K temperature condition using ASAP2020 gas adsorption apparatus of Michkok, USA2Isothermal adsorption test, resulting in N2The results of the data analysis of the isothermal adsorption curves are shown in Table 1.
TABLE 1 two-dimensional topology materials and N of porous organic materials2Data sheet of isothermal adsorption curve
Figure BDA0002338805980000181
Figure BDA0002338805980000191
In the embodiment of the invention, a nitrogen adsorption isotherm curve chart of two-dimensional topological materials POF-Aa, POF-Ab, POF-Bb and POF-Ca under the condition of 77K is shown in figures 2-5. The nitrogen adsorption isotherm curves of the porous organic materials obtained in examples 1 to 17 of the present invention under the 77K condition are shown in FIGS. 6 to 22. As can be seen from Table 1 in combination with FIGS. 2 to 22, the specific surface area and the average pore diameter of the porous organic material obtained after the Friedel-crafts reaction of the two-dimensional topological material prepared by the invention are greatly changed compared with the original two-dimensional topological material.
The pore size distribution curve graph of the two-dimensional topological materials POF-Aa, POF-Ab, POF-Bb and POF-Ca in the embodiment of the invention is shown in figures 23-26; the pore size distribution curves of the porous organic materials obtained in examples 1 to 17 of the present invention are shown in FIGS. 27 to 43. As can be seen from FIGS. 23 to 43, the porous organic material provided by the present invention has a wide pore size distribution range, and a large number of micropores and mesopores coexist.
The two-dimensional topological materials POF-Aa, POF-Ab, POF-Bb and POF-Ca in the embodiment of the invention and the porous organic materials obtained in the embodiments 1-17 are subjected to infrared tests, and the obtained infrared spectrogram is shown in figures 44-64. As can be seen from FIGS. 44 to 64, the porous organic material provided by the invention is 2920cm in comparison with a two-dimensional topological material-1The preparation method has the advantages that a strong absorption peak is nearby, the absorption peak belongs to an infrared vibration peak of methylene, an effective Friedel-crafts reaction is performed on the cross-linking agent and the two-dimensional topological material, and the preparation method is further verified to be realized through generation of a new covalent bond.
The porous organic material obtained in example 10 was subjected to a hydrogen adsorption test, and the resulting hydrogen adsorption isotherm under 77K conditions is shown in fig. 65. As can be seen from fig. 65, the porous organic material provided by the present invention has good hydrogen storage capacity.
The porous organic material obtained in example 10 was subjected to a toluene/cyclohexane adsorption test, and the resulting adsorption isotherm of toluene and cyclohexane at room temperature is shown in FIG. 66. As can be seen from fig. 66, the porous organic material provided by the present invention has good organic vapor trapping ability.
CO treatment under 273K and 298K conditions on a two-dimensional topological material POF-Ab and the porous organic materials obtained in examples 7, 8 and 172Adsorption test, two-dimensional topology Material POF-Ab obtained, examples 7, 8 and 17Obtaining CO of the porous organic material under the conditions of 273K and 298K2The adsorption curves are shown in FIGS. 67-70. As can be seen from FIGS. 67 to 70, the porous organic material provided by the present invention has a good carbon dioxide storage capacity.
The adsorption test of the dye congo red and rhodamine B in water was performed on the porous organic material obtained in example 13 at room temperature, and the adsorption isotherm diagram of the porous organic material for the dye congo red and rhodamine B in water at room temperature is shown in fig. 71. As can be seen from fig. 71, the porous organic material provided by the present invention has good dye adsorption capacity in water.
The porous organic material prepared by the preparation method provided by the invention has the characteristics of high specific surface area and excellent pore structure, and the preparation method has low cost and simple process, provides a new way for preparing the porous organic material with high specific surface area, is suitable for commercial production, and has good industrial application value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A preparation method of a porous organic material is characterized by comprising the following steps:
carrying out coupling polymerization reaction on an organic monomer to obtain a two-dimensional topological material;
mixing the two-dimensional topological material, a catalyst, an external cross-linking agent and a solvent, and carrying out Friedel-crafts reaction to obtain a porous organic material;
the organic monomer comprises one or more of aromatic halide, boric acid substituted aromatic compound, boric acid pinacol ester group substituted aromatic compound, alkynyl substituted aromatic compound and alkenyl substituted aromatic compound;
the coupling polymerization reaction is Suzuki-Gomphu reaction, Shanben coupling reaction, sonogashira coupling reaction or oxidation coupling reaction;
the temperature of the Friedel-crafts reaction comprises a first-stage heat preservation, a second-stage heat preservation and a third-stage heat preservation which are sequentially carried out;
the temperature of the first stage heat preservation is 18-25 ℃, and the time is 0.5-12 h;
the temperature of the second stage heat preservation is 40-60 ℃, and the time is 0.5-24 h;
the temperature of the third stage heat preservation is 80-100 ℃, and the time is 10-72 hours.
2. The method of claim 1, wherein the organic monomer comprises one or more of 1,3, 5-tribromobenzene, 1, 4-dibromobenzene, 1,2,4, 5-tetrabromobenzene, 1, 4-diiodobenzene, 2,4, 6-tribromoaniline, 1, 4-phenylboronic acid, 4' -biphenyldiboronic acid dipicolinate, 1, 4-benzenediboronic acid dipicolinate, 1,3, 5-benzenetriborate, 1, 4-diethynylbenzene, 1,3, 5-triethynylbenzene, and 1, 4-divinylbenzene.
3. The production method according to claim 1, characterized in that the catalyst is a lewis acid; the molar ratio of the two-dimensional topological material to the catalyst is 1: (0.1-10).
4. The method of claim 3, wherein the Lewis acid comprises anhydrous AlCl3Anhydrous FeCl3Anhydrous SnCl4Or anhydrous ZrCl4。
5. The method of claim 1, wherein the external crosslinker comprises one or more of dimethoxymethane, dichloromethane, 1, 2-dichloroethane, octavinyl octasilsesquioxane, cyanuric chloride, p-dichlorobenzyl, o-dichlorobenzyl, m-dichlorobenzyl, and biphenyl dichlorobenzyl; the mass ratio of the two-dimensional topological material to the external cross-linking agent is 1: (0.1 to 200).
6. The method of claim 1, wherein the solvent comprises dichloromethane, 1, 2-dichloroethane, or nitrobenzene; the relative dosage ratio of the two-dimensional topological material to the solvent is 100 g: (1-50) L.
7. A porous organic material prepared by the preparation method of any one of claims 1 to 6.
8. The porous organic material of claim 7, wherein the porous organic material is used in the fields of catalyst supports, guest molecule confinement materials, energy storage materials, gas storage materials, organic vapor capture materials and adsorption materials.
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