Conjugated microporous polymer based on dicarbazole structure as well as preparation method and application of conjugated microporous polymer

Abstract

The invention relates to a conjugated microporous polymer based on a dicarbazole structure and a preparation method and application thereof, the conjugated microporous polymer has a dicarbazole structure unit and a nitrogen-containing aromatic structure unit, the dicarbazole monomer structure is represented by the formula (I): # imgabs0 #, in the structure represented by the formula (I): R = H, R1 = C = H or R1 = H, R = C = H; the structure of the nitrogen-containing aromatic monomer is shown as a formula (II): # imgabs 1 #, wherein the aromatic structure in the structure shown as the formula (II) is any one of benzene, pyridine, pyrimidine, pyrazine and pyridazine. A plurality of conjugated microporous polymers with excellent photocatalytic performance are obtained by changing aromatic monomers with different nitrogen contents, and the conjugated microporous polymers can be applied to high-efficiency production of hydrogen peroxide under photocatalytic conditions.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic materials, and in particular relates to a conjugated microporous polymer based on a dicarbazole structure and a preparation method and application thereof. Background Art

[0002] With the increasing concern about environmental pollution, renewable energy has become the mainstay of sustainable development. As one of the most commonly used chemicals in the world, hydrogen peroxide (H2O2) has been widely used as an efficient green oxidant in chemical synthesis, wastewater treatment, paper bleaching and disinfection. In addition, since hydrogen peroxide has a calorific value comparable to that of hydrogen, it is regarded as one of the important energy sources. To date, the industrial production of H2O2 is mainly through the anthraquinone (AQ) oxidation process, which is energy-intensive and produces a large amount of hazardous waste. Therefore, it is imperative to develop an efficient, economical, green and environmentally friendly process for hydrogen peroxide production.

[0003] Photocatalytic production of hydrogen peroxide is an ideal method for artificial photosynthesis of hydrogen peroxide. It can directly use the abundant water and air on the earth as raw materials, thereby making full use of the water oxidation and oxygen reduction half reactions to produce hydrogen peroxide. It is considered to be the most promising alternative. In recent years, various non-metallic photocatalysts, such as graphitic carbon nitride (g-C3N4) and covalent triazine framework (CTF), have been widely studied to enhance artificial photosynthesis of hydrogen peroxide. However, the development of this field is still limited by the low generation efficiency. In the absence of sacrificial agents, it is difficult to exceed 1 mol g -1 h -1 , which is far from the actual application needs. Therefore, it is urgent to develop a conjugated microporous polymer as an efficient photocatalyst. Summary of the invention

[0004] In order to solve at least one of the above problems, the present invention provides a conjugated microporous polymer based on a biscarbazole structure and a preparation method and application thereof.

[0005] The first aspect of the present invention provides a conjugated microporous polymer based on a biscarbazole structure, wherein the conjugated microporous polymer has a biscarbazole structural unit and a nitrogen-containing aromatic structural unit, wherein the biscarbazole monomer structure is formula (I): Wherein, in the structure shown in formula (I), R=H, R1=C≡H or R1=H, R=C≡H;

[0006] The nitrogen-containing aromatic monomer has a structure of formula (II): Wherein, the aromatic structure in the structure shown in formula (II) is any one of benzene, pyridine, pyrimidine, pyrazine and pyridazine.

[0007] A conjugated microporous polymer with a D-π-A structure was designed and synthesized, in which biscarbazole was used as an electron donor and aromatic units with different nitrogen contents were used as electron acceptors, which were connected through acetylenic bonds.

[0008] The second aspect of the present invention provides a method for preparing a conjugated microporous polymer based on a biscarbazole structure. The conjugated microporous polymer is synthesized in one step by a Sonogashira coupling reaction of a biscarbazole derivative and aromatic monomers with different nitrogen contents.

[0009] Further: The specific steps are

[0010] (1) adding a biscarbazole monomer and a nitrogen-containing aromatic monomer into an organic solvent and stirring to dissolve them to obtain a reaction solution 1;

[0011] (2) adding a catalyst to the reaction solution, heating the reaction solution under a protective gas atmosphere, and obtaining a reaction solution 2;

[0012] (3) After the reaction is completed, the reaction solution 2 is filtered to obtain a solid, and the obtained solid is washed with solvents in sequence to obtain a solid powder;

[0013] (4) The obtained solid powder is eluted in a Soxhlet extractor and vacuum dried to obtain a conjugated microporous polymer based on a biscarbazole structure.

[0014] Furthermore, in the step (1), the organic solvent is one or a combination of chloroform, N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, triethylamine, N,N-diisopropylethylamine, 1,4-dioxane and acetonitrile.

[0015] Furthermore, in step (2), the catalyst is one or a combination of cuprous iodide, tetrakis(triphenylphosphine)palladium, 1,1-(bis(diphenylphosphine)) and ferrocenepalladium dichloride.

[0016] Furthermore: in the step (2), the protective gas is argon or nitrogen.

[0017] Furthermore: in the step (2), the reaction conditions are a temperature of 100 to 130° C. and a reaction time of 24 to 96 hours.

[0018] Furthermore, in step (3), the solvent for washing the filter cake is one or a combination of dichloromethane, methanol, tetrahydrofuran, water, dilute hydrochloric acid, acetone, ether, and N,N-dimethylformamide.

[0019] Furthermore, in step (4), the elution solvent is one or a combination of dichloromethane, methanol, tetrahydrofuran, acetone, and ether; the elution time is 12 to 48 hours; and the vacuum drying temperature is 60 to 80°C.

[0020] The third aspect of the present invention provides an application of the above-mentioned conjugated microporous polymer based on a biscarbazole structure, specifically for photocatalytic production of hydrogen peroxide. The conjugated microporous polymer based on a biscarbazole structure has excellent hydrogen peroxide production performance under photocatalytic conditions, and does not require the addition of a sacrificial agent or the introduction of additional oxygen.

[0021] The beneficial effects of the present invention over the prior art are as follows: the present invention provides a conjugated microporous polymer based on a biscarbazole structure, wherein a conjugated microporous polymer having a D-π-A structure is synthesized in one step by a Sonogashira coupling reaction of a biscarbazole derivative monomer and aromatic monomers with different nitrogen contents, and multiple conjugated microporous polymers with excellent photocatalytic performance are obtained by changing aromatic monomers with different nitrogen contents. The polymers can be used to efficiently produce hydrogen peroxide under photocatalytic conditions, have good application prospects and application value in the field of organic photocatalysis, and provide new ideas and methods for the design and synthesis of organic photocatalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The carbon element spectrum of the X-ray photoelectron spectrum of the conjugated microporous polymer 36cz12 based on the biscarbazole structure prepared in Example 3;

[0023] Figure 2 The nitrogen element spectrum of the X-ray photoelectron spectrum of the conjugated microporous polymer 36cz12 based on the biscarbazole structure prepared in Example 3;

[0024] Figure 3 This is the Fourier transform infrared spectrum of the conjugated microporous polymer 36cz12 based on the biscarbazole structure prepared in Example 3;

[0025] Figure 4 The water contact angle of the conjugated microporous polymer 36cz12 based on the dicarbazole structure prepared in Example 3;

[0026] Figure 5 The solid ultraviolet of the conjugated microporous polymer 36cz12 based on the dicarbazole structure prepared in Example 3;

[0027] Figure 6 The photocurrent of the conjugated microporous polymer 36cz12 based on the biscarbazole structure prepared in Example 3;

[0028] Figure 7 Performance diagram of photocatalytic production of hydrogen peroxide by conjugated microporous polymers based on biscarbazole structure prepared in Example 1, Example 2, Example 3, Example 4, and Example 5; DETAILED DESCRIPTION

[0029] The technical scheme of the present invention will be described clearly and completely below in conjunction with the examples. If no specific conditions are specified in the examples, the conditions are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not used to limit the present invention. The term "and" or "and" used herein includes any and all combinations of one or more related listed items.

[0031] On the one hand, a conjugated microporous polymer based on a biscarbazole structure is provided, wherein the conjugated microporous polymer has a biscarbazole structural unit and a nitrogen-containing aromatic structural unit, wherein the biscarbazole monomer structure is of formula (I): Wherein, in the structure shown in formula (I), R=H, R1=C≡H or R1=H, R=C≡H;

[0032] The nitrogen-containing aromatic monomer has a structure of formula (II): Wherein, the aromatic structure in the structure shown in formula (II) is any one of benzene, pyridine, pyrimidine, pyrazine and pyridazine.

[0033] The present invention provides a method for preparing the conjugated microporous polymer based on the biscarbazole structure, and the specific preparation route is:

[0034]

[0035] The specific steps are: (1) adding a biscarbazole monomer and a nitrogen-containing aromatic monomer into an organic solvent, stirring to dissolve

[0036] Solve to obtain reaction solution 1;

[0037] (2) adding a catalyst to the reaction solution, heating the reaction solution under a protective gas atmosphere, and obtaining a reaction solution 2;

[0038] (4) After the reaction is completed, the reaction solution 2 is filtered to obtain a solid, and the obtained solid is washed with solvents in sequence to obtain a solid powder;

[0039] (4) The obtained solid powder is eluted in a Soxhlet extractor and vacuum dried to obtain a conjugated microporous polymer based on a biscarbazole structure.

[0040] Example 1

[0041] According to the following synthetic route:

[0042]

[0043] (1) Add [9,9'-bicarbazole]-3,3',6,6'-tetraethynyl (85.6 mg, 0.2 mmol), 1,4-dibromobenzene (94 mg, 0.4 mmol), 15 mL of N,N-dimethylformamide and 7.5 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod and stir for 15-30 minutes under a nitrogen atmosphere;

[0044] (2) After the solid in step (1) is completely dissolved, cuprous iodide (9.2 mg, 0.048 mmol), tetrakis(triphenylphosphine)palladium (27.7 mg, 0.024 mmol), and triphenylphosphine (10.5 mg, 0.04 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0045] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0046] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 36czb based on a dicarbazole structure with a yield of 85%.

[0047] Example 2

[0048] According to the following synthetic route:

[0049]

[0050] (1) Add [9,9'-bicarbazole]-3,3',6,6'-tetraethynyl (85.6 mg, 0.2 mmol), 2,5-dibromopyrimidine (94.4 mg, 0.4 mmol), 15 mL of N,N-dimethylformamide and 7.5 mL of diisopropylamine into a Shrek bottle equipped with a magnetic particle and stir for 15-30 minutes under a nitrogen atmosphere;

[0051] (2) After the solid in step (1) is completely dissolved, cuprous iodide (9.2 mg, 0.048 mmol), tetrakis(triphenylphosphine)palladium (27.7 mg, 0.024 mmol), and triphenylphosphine (10.5 mg, 0.04 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0052] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0053] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 36czp based on a dicarbazole structure with a yield of 89%.

[0054] Example 3

[0055] According to the following synthetic route:

[0056]

[0057] (1) Add [9,9'-bicarbazole]-3,3',6,6'-tetraethynyl (600 mg, 1.4 mmol), 3,6-dibromopyridazine (666 mg, 2.8 mmol), 70 mL of N,N-dimethylformamide and 35 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar and stir under a nitrogen atmosphere for 15-30 minutes;

[0058] (2) After the solid in step (1) is completely dissolved, cuprous iodide (63.9 mg, 0.336 mmol), tetrakis(triphenylphosphine)palladium (194 mg, 0.168 mmol), and triphenylphosphine (73 mg, 0.28 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0059] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0060] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 36cz12 based on a dicarbazole structure with a yield of 86%.

[0061] The X-ray photoelectron spectrum of the conjugated microporous polymer 36cz12 prepared in Example 3 of the present invention is shown in Figure 1 From the C1s spectrum, we can see that there are three peaks at 283.3eV, 284.8eV, and 287.3eV, corresponding to CC=C, C≡C, and C=N bonds respectively; the X-ray diffraction pattern of 36cz12 is shown in Figure 2 According to its 20° peak, it can be inferred that it is an amorphous polymer; the Fourier transform infrared spectrum of 36cz12 is shown in Figure 3 , a characteristic peak of C≡C can be observed near 2240cm-1. The above structural characterization can confirm the successful synthesis of conjugated microporous polymer 36cz12. In addition, the water contact angle of 36cz12 is shown in Figure 4 , the angle is less than 90°, indicating that it has good hydrophilicity; the UV absorption of 36cz12 is shown in Figure 4 , mainly concentrated in 200-800nm, indicating its wide-spectrum absorption characteristics; the photocurrent of 36cz12 is shown in Figure 6 , indicating that it has good photoelectric response characteristics.

[0062] Example 4

[0063] According to the following synthetic route:

[0064]

[0065] (1) Add [9,9'-bicarbazole]-3,3',6,6'-tetraethynyl (600 mg, 1.4 mmol), 2,5-dibromopyrimidine (666 mg, 2.8 mmol), 70 mL of N,N-dimethylformamide and 35 mL of diisopropylamine into a Shrek bottle equipped with a magnetic particle and stir for 15-30 minutes under a nitrogen atmosphere;

[0066] (2) After the solid in step (1) is completely dissolved, cuprous iodide (63.9 mg, 0.336 mmol), tetrakis(triphenylphosphine)palladium (194 mg, 0.168 mmol), and triphenylphosphine (73 mg, 0.28 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0067] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0068] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60°C for 24 hours to obtain a conjugated microporous polymer 36cz13 based on a dicarbazole structure with a yield of 84%.

[0069] Example 5

[0070] According to the following synthetic route:

[0071]

[0072] (1) Add [9,9'-bicarbazole]-3,3',6,6'-tetraethynyl (600 mg, 1.4 mmol), 2,5-dibromopyrazine (666 mg, 2.8 mmol), 70 mL of N,N-dimethylformamide and 35 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar and stir for 15-30 minutes under a nitrogen atmosphere;

[0073] (2) After the solid in step (1) is completely dissolved, cuprous iodide (63.9 mg, 0.336 mmol), tetrakis(triphenylphosphine)palladium (194 mg, 0.168 mmol), and triphenylphosphine (73 mg, 0.28 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0074] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0075] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 36cz14 based on a dicarbazole structure with a yield of 87%.

[0076] Example 6

[0077] According to the following synthetic route:

[0078]

[0079] (1) Add [9,9'-bicarbazole]-2,2',7,7'-tetraethynyl (85.6 mg, 0.2 mmol), 1,4-dibromobenzene (94 mg, 0.4 mmol), 15 mL of N,N-dimethylformamide and 7.5 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod and stir for 15-30 minutes under a nitrogen atmosphere;

[0080] (2) After the solid in step (1) is completely dissolved, cuprous iodide (9.2 mg, 0.048 mmol), tetrakis(triphenylphosphine)palladium (27.7 mg, 0.024 mmol), and triphenylphosphine (10.5 mg, 0.04 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0081] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0082] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 27czb based on a dicarbazole structure with a yield of 90%.

[0083] Example 7

[0084] According to the following synthetic route:

[0085]

[0086] (1) Add [9,9'-bicarbazole]-2,2',7,7'-tetraethynyl (85.6 mg, 0.2 mmol), 2,5-dibromopyrimidine (94.4 mg, 0.4 mmol), 15 mL of N,N-dimethylformamide and 7.5 mL of diisopropylamine into a Shrek bottle equipped with a magnetic particle and stir for 15-30 minutes under a nitrogen atmosphere;

[0087] (2) After the solid in step (1) is completely dissolved, cuprous iodide (9.2 mg, 0.048 mmol), tetrakis(triphenylphosphine)palladium (27.7 mg, 0.024 mmol), and triphenylphosphine (10.5 mg, 0.04 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0088] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0089] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 27czp based on a dicarbazole structure with a yield of 87%.

[0090] Example 8

[0091] According to the following synthetic route:

[0092]

[0093] (1) Add [9,9'-bicarbazole]-2,2',7,7'-tetraethynyl (600 mg, 1.4 mmol), 3,6-dibromopyridazine (666 mg, 2.8 mmol), 70 mL of N,N-dimethylformamide and 35 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar and stir for 15-30 minutes under a nitrogen atmosphere;

[0094] (2) After the solid in step (1) is completely dissolved, cuprous iodide (63.9 mg, 0.336 mmol), tetrakis(triphenylphosphine)palladium (194 mg, 0.168 mmol), and triphenylphosphine (73 mg, 0.28 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0095] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0096] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 27cz12 based on a dicarbazole structure with a yield of 89%.

[0097] Example 9

[0098] According to the following synthetic route:

[0099]

[0100] (1) Add [9,9'-bicarbazole]-2,2',7,7'-tetraethynyl (600 mg, 1.4 mmol), 2,5-dibromopyrimidine (666 mg, 2.8 mmol), 70 mL of N,N-dimethylformamide and 35 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar and stir for 15-30 minutes under a nitrogen atmosphere;

[0101] (2) After the solid in step (1) is completely dissolved, cuprous iodide (63.9 mg, 0.336 mmol), tetrakis(triphenylphosphine)palladium (194 mg, 0.168 mmol), and triphenylphosphine (73 mg, 0.28 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0102] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0103] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60°C for 24 hours to obtain a conjugated microporous polymer 27cz13 based on a dicarbazole structure with a yield of 85%.

[0104] Example 10

[0105] According to the following synthetic route:

[0106]

[0107] (1) Add [9,9'-bicarbazole]-2,2',7,7'-tetraethynyl (600 mg, 1.4 mmol), 2,5-dibromopyrazine (666 mg, 2.8 mmol), 70 mL of N,N-dimethylformamide and 35 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar and stir under a nitrogen atmosphere for 15-30 minutes;

[0108] (2) After the solid in step (1) is completely dissolved, cuprous iodide (63.9 mg, 0.336 mmol), tetrakis(triphenylphosphine)palladium (194 mg, 0.168 mmol), and triphenylphosphine (73 mg, 0.28 mmol) are added to the above solution in sequence, dispersed under a nitrogen atmosphere, and the reaction system is heated to 110° C. and refluxed for 72 hours;

[0109] (3) After the reaction is completed, the reaction system is cooled to room temperature, an appropriate amount of potassium iodide is added, and ultrasonication is performed for 1 hour. The reaction solution is filtered to obtain a filter cake, which is then washed with potassium iodide solution, methanol, and dichloromethane in sequence;

[0110] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 60° C. for 24 hours to obtain a conjugated microporous polymer 27cz14 based on a dicarbazole structure with a yield of 87%.

[0111] The results of the above embodiments are summarized as shown in Table 1:

[0112] Table 1

[0113]

[0114]

[0115] Application Example 1

[0116] Study on photocatalytic production of hydrogen peroxide by different conjugated microporous polymers:

[0117] The conjugated microporous polymers based on the biscarbazole structure obtained in Examples 1, 2, 3, 4 and 5 were used to study the photocatalytic production of hydrogen peroxide;

[0118] Test samples: conjugated microporous polymers based on biscarbazole structure obtained in Example 1, Example 2, Example 3, Example 4, and Example 5;

[0119] Test method: Weigh 5 mg of the conjugated microporous polymer based on the dicarbazole structure prepared in Examples 1 to 5 above into a centrifuge tube, add 20 mL of pure water and disperse it completely by ultrasonication, then transfer it to a reactor, circulate water to keep it at 25°C, and use a 300-watt xenon lamp to continuously illuminate the reactor. Stop irradiation after 60 minutes, take 2 mL of the reaction solution and filter it through a 0.22 μm filter, take 1.5 mL of the filtrate into a centrifuge tube, and add 1 mL of 1 mol L -1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, and then the absorbance was measured by a UV-visible spectrophotometer. The concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 2.

[0120] Table 2

[0121]

[0122]

[0123] Application Example 2

[0124] Study on photocatalytic production of hydrogen peroxide under different catalyst concentrations:

[0125] The conjugated microporous polymer based on the biscarbazole structure obtained in Example 3 was used to study the photocatalytic production of hydrogen peroxide at different catalyst concentrations.

[0126] Experimental sample: the conjugated microporous polymer based on the biscarbazole structure obtained in Example 3;

[0127] Test method: Weigh 2.5 mg, 5 mg, and 10 mg of the conjugated microporous polymer with a biscarbazole structure prepared in Example 3 above and place them in a centrifuge tube. Add 20 mL of pure water and disperse them completely by ultrasonication. Then transfer them to a reactor, circulate water to keep it at 25°C, and use a 300-watt xenon lamp to continuously illuminate the reactor. Stop irradiation after 60 minutes, take 2 mL of the reaction solution and filter it through a 0.22 μm filter. After taking 1.5 mL of the filtrate in a centrifuge tube, add 1 mL of 1 mol L-1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, and then the absorbance was measured by a UV-visible spectrophotometer. The concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 3.

[0128] Table 3

[0129]

[0130] Application Example 3

[0131] Study on photocatalytic production of hydrogen peroxide under different atmospheres:

[0132] The conjugated microporous polymer based on the biscarbazole structure obtained in Example 3 was used to study the photocatalytic production of hydrogen peroxide under different atmospheres.

[0133] Experimental sample: the conjugated microporous polymer based on the dicarbazole structure obtained in Example 3; Experimental method: 5 mg of the conjugated microporous polymer based on the dicarbazole structure prepared in Example 3 was taken into a centrifuge tube, 20 mL of pure water was added for complete ultrasonic dispersion, and then the mixture was transferred to a reactor, stirred for 30 minutes under nitrogen and oxygen atmospheres, and circulating water was passed to keep the mixture at 25°C. A 300-watt xenon lamp was used to continuously illuminate the reactor. After 60 minutes, the illumination was stopped, 2 mL of the reaction solution was taken and filtered through a 0.22 μm filter, 1.5 mL of the obtained filtrate was taken into a centrifuge tube, and 1 mL of 1 mol L -1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, and then the absorbance was measured by a UV-visible spectrophotometer. The concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 4.

[0134] Table 4

[0135]

Claims

1. A conjugated microporous polymer based on a biscarbazole structure, characterized in that: The conjugated microporous polymer has a biscarbazole structural unit and a nitrogen-containing aromatic structural unit, wherein the monomer structure of the biscarbazole is formula (I): Wherein, in the structure shown in formula (I), R=H, R1=C≡H or R1=H, R=C≡H; The structure of the nitrogen-containing aromatic monomer is formula (II): Wherein, the aromatic structure in the structure shown in formula (II) is any one of benzene, pyridine, pyrimidine, pyrazine and pyridazine.

2. A method for preparing a conjugated microporous polymer based on a biscarbazole structure as claimed in claim 1, characterized in that: The conjugated microporous polymer is synthesized in one step by a Sonogashira coupling reaction of a biscarbazole derivative and aromatic monomers with different nitrogen contents.

3. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 2, characterized in that: The specific steps are: (1) adding a biscarbazole monomer and a nitrogen-containing aromatic monomer into an organic solvent and stirring to dissolve them to obtain a reaction solution 1; (2) adding a catalyst to the reaction solution, heating the reaction solution under a protective gas atmosphere, and obtaining a reaction solution 2; (3) After the reaction is completed, the reaction solution 2 is filtered to obtain a solid, and the obtained solid is washed with solvents in sequence to obtain a solid powder; (4) The obtained solid powder was eluted in a Soxhlet extractor and vacuum dried to obtain the base Conjugated microporous polymers based on biscarbazole structure.

4. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 3, characterized in that: In the step (1), the organic solvent is one or a combination of chloroform, N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, triethylamine, N,N-diisopropylethylamine, 1,4-dioxane and acetonitrile.

5. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 3, characterized in that: In the step (2), the catalyst is one or a combination of cuprous iodide, tetrakis(triphenylphosphine)palladium, 1,1-(bis(diphenylphosphine)) and ferrocenepalladium dichloride.

6. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 3, characterized in that: In the step (2), the protective gas is argon or nitrogen.

7. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 3, characterized in that: In the step (2), the reaction conditions are a temperature of 100 to 130° C. and a reaction time of 24 to 96 hours.

8. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 3, characterized in that: In the step (3), the solvent for washing the filter cake is one or a combination of dichloromethane, methanol, tetrahydrofuran, water, dilute hydrochloric acid, acetone, ether, and N,N-dimethylformamide.

9. The method for preparing a conjugated microporous polymer based on a biscarbazole structure according to claim 3, characterized in that: In the step (4), the elution solvent is one or a combination of dichloromethane, methanol, tetrahydrofuran, acetone, and ether; the elution time is 12 to 48 hours; and the vacuum drying temperature is 60 to 80°C.

10. An application of the conjugated microporous polymer based on a biscarbazole structure as claimed in claim 1, characterized in that: Conjugated microporous polymers based on biscarbazole structures are used for photocatalytic production of hydrogen peroxide.

Images