A perylene imide-based porous material, a preparation method and applications thereof

Abstract

The application discloses a kind of porous materials based on perylene imide, preparation method and application thereof, its method includes the following steps: step one: perylene imide monomer and amine monomer are added to reaction vessel, reaction solvent is added, uniformly mixed, and perylene imide intermediate 1 is obtained;Step two: intermediate 1 obtained in step one and second structural unit are added to reaction vessel, reaction solvent is added, uniformly mixed, and intermediate 2 is obtained by Suzuki coupling reaction;Step three: intermediate 2 obtained in step two is added to reaction vessel, anhydrous catalyst is added, uniformly mixed, and then room temperature reaction is carried out, and porous material POP-1 is obtained by soxhlet extraction and vacuum drying;Synthesis method is simple, reaction material is easy to obtain, better thermal stability, efficient adsorption performance and photocatalytic degradation capacity are shown in the removal of dye and pesticide, and it has good application prospect in actual wastewater treatment field.

Description

Technical Field

[0001] This invention belongs to the field of porous material preparation and wastewater treatment technology, specifically relating to a method for preparing porous materials based on perylene imide and its application in adsorbing and photocatalytically degrading persistent organic micropollutants. Background Technology

[0002] The composition of dyeing and printing wastewater is complex and its treatment is difficult. Traditional treatment methods cannot meet current needs, requiring new materials to provide an effective solution. The widespread use of pesticides poses threats and risks to environmental safety and human health, making pesticide removal a crucial research objective. Due to the non-renewable nature of traditional fossil fuels and the severe environmental pollution generated during their combustion, energy shortages and environmental pollution are increasingly serious problems worldwide. To address these challenges, researchers have turned their attention to the application of semiconductor materials in photocatalytic degradation. Semiconductor photocatalytic materials have been extensively studied due to their environmental friendliness, high efficiency, and economic benefits. In 1972, Honda and Fujishima discovered that water could be photoelectrochemically decomposed into H2 and O2 on a TiO2 electrode, ushering in a new era of photocatalysis research. Currently, photocatalytic materials mainly include inorganic semiconductor materials (TiO2, SnO2, Cds, Bi2WO6, etc.) and organic semiconductor materials. This invention uses dyes, pesticides, and phenolic pollutants as model research objects. Perylene imide monomers are used as porous material substrates. Perylene imide and its derivatives are among the best n-type semiconductors currently available, and perylene imide supramolecular photocatalysts can independently complete the entire photocatalytic process from light absorption and carrier separation to the catalytic reaction. In conclusion, the application of perylene imide in photocatalytic degradation warrants further investigation. Summary of the Invention

[0003] The main technical problem solved by this invention is to provide a porous material based on perylene imide, its preparation method and its application.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0005] A method for preparing a porous material based on perylene imide includes the following steps:

[0006] Step 1: Add perylene imide monomer and amine monomer to the reaction vessel, add reaction solvent, mix well to obtain perylene imide intermediate 1;

[0007] Step 2: Add intermediate 1 and the second structural unit obtained in Step 1 into a reaction vessel, add reaction solvent, mix well, and obtain intermediate 2 through Suzuki coupling reaction;

[0008] Step 3: Add intermediate 2 obtained in step 2 into the reaction vessel, add anhydrous catalyst, mix evenly, and then react at room temperature. After Soxhlet extraction and vacuum drying, the porous material POP-1 is obtained.

[0009] Preferably, the perylene imide monomer comprises at least one of the following structural formulas;

[0010]

[0011] Preferably, the amine monomer comprises at least one of the following structural formulas;

[0012]

[0013] Preferably, the second structural unit includes at least one of the following structural formulas;

[0014]

[0015] Furthermore, the molar ratio of the perylene imide monomer to the amine monomer is 1:(2-5), and the molar ratio of the perylene imide intermediate 1 to the second structural unit is 1:(2-6).

[0016] Preferably, the reaction solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, acetic anhydride, o-dichlorobenzene, acetonitrile, chloroform, 1,2-dichloroethane, or n-butanol.

[0017] Preferably, the catalyst is one or more of palladium catalyst, anhydrous FeCl3, AlCl3, boron trifluoride or niobium pentachloride.

[0018] Preferably, the solvent used for the Soxhlet extraction is one or more of dichloromethane, methanol, ethanol or acetone.

[0019] After adding the catalyst, the temperature is controlled at 30-80℃.

[0020] The specific requirements for vacuum drying in step three are: vacuum drying at 60–120℃ for 1–2 days.

[0021] A method for preparing perylene imide ionic porous materials.

[0022] One approach is to use perylene imide ionic porous materials for the adsorption or photocatalytic degradation of pollutants in water.

[0023] The beneficial technical effects of this invention are:

[0024] I. The present invention provides a novel porous material for adsorbing and photocatalytically degrading organic micropollutants, which can effectively improve the treatment of dyeing and printing wastewater and organic pesticides, and improve wastewater treatment methods.

[0025] II. The perylene imide-based porous material preparation method of the present invention utilizes a simple synthesis method to synthesize a highly efficient porous material. The porous material developed by the present invention has the following characteristics: simple synthesis method, readily available reaction materials, good thermal stability, and exhibits highly efficient adsorption performance and photocatalytic degradation ability in the removal of dyes and pesticides, showing good application prospects in the field of practical wastewater treatment. Attached Figure Description

[0026] Figure 1 The attached diagram shows the N2 adsorption and desorption of POP-1.

[0027] Figure 2 This is a thermogravimetric analysis (TGA) of POP-1 under N2 atmosphere;

[0028] Figure 3 This is the ultraviolet diffuse reflectance spectrum of POP-1 in air at room temperature;

[0029] Figure 4 This is a graph showing the adsorption performance of POP-1 on methyl orange (UV absorption spectra of methyl orange residue at different times);

[0030] Figure 5 This is a graph showing the adsorption performance of POP-1 on 2,4-D (UV absorption spectra of 2,4-D residues at different times);

[0031] Figure 6 This is a graph showing the adsorption performance of POP-1 on bisphenol A (UV absorption spectra of residual bisphenol A at different times);

[0032] Figure 7 This is a graph showing the photocatalytic degradation performance of POP-1 on methyl orange (the concentration ratio of residual methyl orange at different times);

[0033] Figure 8 This is a comparison chart of the dark adsorption and photocatalytic degradation performance of POP-1 for bisphenol A (the concentration ratio of residual bisphenol A at different times). Detailed Implementation

[0034] In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0035] In the description of this invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "front", "rear", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0036] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "configuration" should be interpreted broadly. For example, they can refer to a fixed connection or configuration, a detachable connection or configuration, or an integral connection or configuration. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0037] Example 1

[0038] 1,7-Dibromo-3,4,9,10-perylenetetracarboxylic dianhydride (5 g, 9.1 mmol) and N,N-dimethylpropanediamine (2.32 g, 22.75 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (85 mL) and 1,4-dioxane (55 mL) were added, and the mixture was refluxed at 55 °C for 3–4 h. After the reaction was complete, the mixture was cooled to room temperature, then added dropwise to ice water and filtered. The filter cake was washed with water and dried in a vacuum oven at 60 °C for 24 h to give 4.7 g of a red product (intermediate 1), with a yield of 70%.

[0039] Intermediate 1 (3 g, 4 mmol) and 4-(9-carbazolyl)phenylboronic acid (3.4 g, 12 mmol) were added to a 500 mL Shrek tube, followed by tetrahydrofuran (150 mL). Then, 2MK2CO3 aqueous solution (6 mL) was added under a nitrogen atmosphere, and tetra(triphenylphosphine)palladium (250 mg, 0.2 mmol) was added. The mixture was refluxed at 75 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and subjected to silica gel column chromatography (dichloromethane:methanol = 20:1) to obtain the target product. The product was dried in a vacuum oven at 60 °C to give 3.5 g of a dark purple product (intermediate 2), with a yield of 65%.

[0040] Intermediate 2 (3 g, 2.87 mmol) was added to a 500 mL Shrek tube, followed by the addition of 75 mL of dry chloroform under a nitrogen atmosphere, and then anhydrous FeCl3 (2.7 g, 15.5 mmol) was added in portions. The mixture was refluxed at room temperature for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 3.1 g of the dark purple product (POP-1).

[0041] The POP-1 reaction process is as follows:

[0042]

[0043] Example 2

[0044] 1,7-Dibromo-3,4,9,10-perylenetetracarboxylic dianhydride (2 g, 3.65 mmol) and 2-ethylhexylamine (1.18 g, 9.12 mmol) were added to a 250 mL Shrek flask. Glacial acetic acid (20 mL) and N-methylpyrrolidone (40 mL) were added under a nitrogen atmosphere, and the mixture was refluxed at 120 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, then added dropwise to ice water and filtered. The filter cake was washed with water and dried in a vacuum oven at 60 °C to give 1.2 g of a deep red product, with a yield of 62%.

[0045] The above-mentioned deep red product (0.9 g, 1.1 mmol) and 4-(9-carbazolyl)phenylboronic acid (0.92 g, 3.3 mmol) were added to a 100 mL Shrek tube, followed by 60 mL of tetrahydrofuran. Then, 6 mL of 2MK₂CO₃ aqueous solution was added under a nitrogen atmosphere, followed by tetra(triphenylphosphine)palladium (136 mg, 0.1 mmol). The mixture was refluxed at 65 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and subjected to silica gel column chromatography (dichloromethane:methanol = 30:1) to obtain the target product. The product was dried in a vacuum oven at 60 °C to obtain 0.9 g of black product, with a yield of 80%.

[0046] The above-mentioned black product (0.9 g, 0.81 mmol) was added to a 100 mL Shrek tube, and dry chloroform (50 mL) was added under a nitrogen atmosphere. Then, anhydrous FeCl3 (1 g, 6.3 mmol) was added in portions, and the mixture was refluxed at 45 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1 g of black product.

[0047] Example 3

[0048] 2.5 g (9.1 mmol) of 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride and 2 g (18 mmol) of N,N-dimethylpropanediamine were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, 80 mL of N,N-dimethylformamide and 40 mL of 1,4-dioxane were added, and the mixture was refluxed at 65 °C for 5–6 h. After the reaction was complete, the mixture was cooled to room temperature, then added dropwise to ice water and filtered. The filter cake was washed with water and dried in a vacuum oven at 60 °C to give 3.8 g of a red product, with a yield of 55%.

[0049] The above-mentioned red product (3 g, 4 mmol) and 4-pyridineboronic acid (0.98 g, 8 mmol) were added to a 200 mL Shrek tube, followed by 120 mL of tetrahydrofuran. Then, 6 mL of 2MK₂CO₃ aqueous solution was added under a nitrogen atmosphere, followed by tetra(triphenylphosphine)palladium (115 mg, 0.1 mmol). The mixture was refluxed at 65 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, diluted with dichloromethane, and subjected to column chromatography (dichloromethane:methanol = 25:1) to obtain the target product. The product was dried in a vacuum oven at 60 °C to give 2 g of a dark purple product, with a yield of 70%.

[0050] The above-mentioned dark purple product (2 g, 2.8 mmol) was added to a 250 mL Shrek tube, and anhydrous chloroform (100 mL) was added under a nitrogen atmosphere. Then, anhydrous AlCl3 (2.7 g, 22.4 mmol) was added in portions, and the mixture was refluxed at room temperature for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 2.2 g of dark purple product.

[0051] Example 4

[0052] 1,7-Dibromo-3,4,9,10-perylenetetracarboxylic dianhydride (5 g, 9.1 mmol), N,N-dimethylpropanediamine (1.1 g, 9.1 mmol), and 2-ethylhexylamine (1.2 g, 9.1 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (70 mL) and 1,4-dioxane (50 mL) were added, and the mixture was refluxed at 65 °C for 3–4 h. After the reaction was complete, the mixture was cooled to room temperature, then added dropwise to ice water and filtered. The filter cake was washed with water and dried in a vacuum oven at 60 °C to give 4.7 g of a red product, with a yield of 70%.

[0053] The above-mentioned red product (3 g, 4 mmol) and 4-(diphenylamino)phenylboronic acid triphenylamine-4-boronic acid (3.4 g, 12 mmol) were added to a 500 mL Shrek tube, followed by tetrahydrofuran (150 mL), and then 2MK2CO3 aqueous solution (6 mL) under a nitrogen atmosphere. Tetra(triphenylphosphine)palladium (250 mg, 0.2 mmol) was added, and the mixture was refluxed at 75 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, diluted with dichloromethane, and subjected to column chromatography (dichloromethane:methanol = 25:1) to obtain the target product. The product was dried in a vacuum oven at 60 °C to obtain 3.5 g of black product, with a yield of 65%.

[0054] The above-mentioned black product (3 g, 2.87 mmol) was added to a 500 mL Shrek tube, and dry chloroform (100 mL) was added under a nitrogen atmosphere. Then, anhydrous FeCl3 (2.7 g, 15.5 mmol) was added in portions, and the mixture was refluxed at 35 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 2.95 g of black product.

[0055] Example 5

[0056] 0.5 g (0.5 mmol) of 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride, 0.5 g (0.7 mmol) of 1,6-dichloro-3,4,9,10-perylenetetracarboxylic dianhydride, and 0.618 g (6.0 mmol) of diethylenetriamine were added to a 250 mL Shrek flask. Under a nitrogen atmosphere, 70 mL of N,N-dimethylformamide and 50 mL of 1,4-dioxane were added, and the mixture was refluxed at 65 °C for 3–4 h. After the reaction was complete, the mixture was cooled to room temperature, then added dropwise to ice water and filtered. The filter cake was washed with water and dried in a vacuum oven at 60 °C to obtain 1.2 g of a red solid powder, with a yield of 62%.

[0057] The above-mentioned red solid powder (1 g, 1.1 mmol) and 4-(diphenylamino)phenylboronic acid triphenylamine-4-boronic acid (1.84 g, 6.6 mmol) were added to a 200 mL Shrek tube, followed by tetrahydrofuran (70 mL), and then 4MK2CO3 aqueous solution (6 mL) under a nitrogen atmosphere. Then, bis(triphenylphosphine)palladium dichloride (140 mg, 0.2 mmol) was added, and the mixture was refluxed at 85 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, diluted with dichloromethane, and subjected to column chromatography (dichloromethane:methanol = 25:1) to obtain the target product. The product was dried in a vacuum oven at 60 °C to obtain 0.9 g of black product, with a yield of 75%.

[0058] The above-mentioned black product (0.9 g, 0.81 mmol) was added to a 100 mL Shrek tube, and dry chloroform (30 mL) was added under a nitrogen atmosphere. Then, anhydrous FeCl3 (1 g, 6.3 mmol) was added in portions, and the mixture was refluxed at 55 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1 g of black product.

[0059] Example 6

[0060] 1,6-Dichloro-3,4,9,10-perylenetetracarboxylic dianhydride (3 g, 4.23 mmol), N,N-dimethylpropanediamine (0.86 g, 8.46 mmol), and 2-ethylhexylamine (1.1 g, 8.5 mmol) were added to a 250 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (80 mL) and 1,4-dioxane (60 mL) were added, and the mixture was refluxed at 55 °C for 5–6 h. After the reaction was complete, the mixture was cooled to room temperature, then added dropwise to ice water and filtered. The filter cake was washed with water and dried in a vacuum oven at 60 °C to obtain 2.5 g of a pale red solid powder, with a yield of 65%.

[0061] The above-mentioned red solid powder (2 g, 2.2 mmol) and 4-(9-carbazolyl)phenylboronic acid (3.68 g, 13.2 mmol) were added to a 250 mL Shrek tube, followed by 1,4-dioxane (100 mL). Then, under a nitrogen atmosphere, 6 mL of 2MK2CO3 aqueous solution was added, followed by bis(triphenylphosphine)palladium dichloride (250 mg, 0.4 mmol). The mixture was refluxed at 85 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, diluted with dichloromethane, and subjected to column chromatography (dichloromethane:methanol = 30:1) to obtain the target product. The product was dried in a vacuum oven at 60 °C to obtain 1.8 g of purple solid powder, with a yield of 75%.

[0062] The above-mentioned purple solid powder (1.8 g, 1.92 mmol) was added to a 100 mL Shrek tube, and dry chloroform (80 mL) was added under a nitrogen atmosphere. Then, anhydrous FeCl3 (2 g, 12.6 mmol) was added in portions, and the mixture was refluxed at 35 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.6 g of black product.

[0063] Table 1

[0064]

[0065] Application Example 1

[0066] Adsorption experiment of methyl orange (MO) ionic dye:

[0067] The porous materials obtained in Examples 1 and 2 were subjected to MO adsorption studies.

[0068] Test samples: Porous materials obtained in Examples 1 and 2;

[0069] Preparation of MO dye solution: Prepare a MO dye solution with a concentration of 50 ppm.

[0070] Experimental Method: 5 mg of the test sample and 10 mL of the prepared MO dye solution were added to a flat-bottomed beaker. The beaker was placed on a magnetic stirrer for adsorption experiments. The solution was removed at 30 s, 60 s, 90 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s, and solid-liquid separation was performed using a filter with a pore size of 0.22 μm. The concentration of the MO dye solution was measured using a UV-Vis spectrophotometer, and the adsorption rate of the MO dye solution on the porous material was calculated. Figure 4 This is a graph showing the change in the UV absorption spectrum of the residual MO dye after adsorption by the porous material obtained in Example 1 over time. According to the UV spectrophotometer, within 5 seconds of dark adsorption, POP-1 adsorbs approximately 60% of the 50 ppm MO, and the adsorption is completed within 60 seconds.

[0071] Application Example 2

[0072] Adsorption experiment of 2,4-dichlorophenoxyacetic acid (2,4-D) ion pesticides:

[0073] The porous materials obtained in Examples 1 and 2 were used to study the adsorption of 2,4-D pesticides.

[0074] Test samples: Porous materials obtained in Examples 1 and 2;

[0075] Preparation of 2,4-D solution: Prepare a 2,4-D solution with a concentration of 50 ppm.

[0076] Experimental Method: 5 mg of the test sample and 10 mL of the prepared solution were added to a flat-bottomed beaker, and the beaker was placed on a shaker for adsorption experiments. The solution was removed at 30 s, 60 s, 90 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s, and solid-liquid separation was performed using a filter with a pore size of 0.22 μm. The concentration of the 2,4-D solution was measured using a UV-Vis spectrophotometer, and the adsorption rate of the 2,4-D pesticide solution by the porous material was calculated. Figure 5 This is a graph showing the changes in the UV absorption spectra of the porous material obtained in Example 1, including the adsorption of 2,4-D and the residual 2,4-D, over time. According to the UV spectrophotometer, within 5 seconds of dark adsorption, POP-1 adsorbed approximately 98% of 50 ppm 2,4-D, and the adsorption was completed within 10 seconds.

[0077] Application Example 3

[0078] Bisphenol A adsorption experiment:

[0079] The porous materials obtained in Examples 1, 2 and 3 were subjected to adsorption studies of bisphenol A solution.

[0080] Test samples: Porous materials obtained in Examples 1 and 2;

[0081] Preparation of bisphenol A solution: Prepare a bisphenol A solution with a concentration of 50 ppm.

[0082] Experimental Method: 5 mg of the test sample and 10 mL of the prepared solution were added to a flat-bottomed beaker, and the mixture was placed in an ultrasonic apparatus for adsorption experiments. The solution was removed at 30 s, 60 s, 90 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s, and solid-liquid separation was performed using a filter with a pore size of 0.22 μm. Bisphenol A was developed using the phenol colorimetric method, and the concentration of the bisphenol A solution was measured using a UV-Vis spectrophotometer. The adsorption rate of the porous material for the bisphenol A solution was calculated. Figure 6 This is a graph showing the change in the UV absorption spectrum of residual bisphenol A over time after the porous material obtained in Example 1 adsorbs bisphenol A. According to the UV spectrophotometer, within 5 seconds of dark adsorption, POP-1 adsorbs approximately 80% of 50 ppm bisphenol A, and the adsorption is completed within 30 seconds.

[0083] Application Example 4

[0084] Adsorption capacity experiment of MO dye:

[0085] The MO adsorption capacity of the porous material obtained in Example 1 was studied.

[0086] Test sample: The porous material obtained in Example 1;

[0087] Preparation of MO dye solution: Prepare MO dye solution with a concentration of 80–800 ppm.

[0088] Experimental method: Add 5 mg of the test sample to the sample bottle, and add 10 mL of the prepared MO dye solution. Keep the room temperature constant and place the bottle on a magnetic stirrer to carry out the adsorption capacity experiment. After adsorption for 48 h, measure the concentration of the MO dye solution using a UV-Vis spectrophotometer and calculate the adsorption capacity of the porous material for MO dye solutions of different concentrations.

[0089] Application Example 5

[0090] Photocatalytic degradation experiment of MO dyes:

[0091] The porous materials obtained in Examples 1 and 2 were studied for MO photocatalytic degradation.

[0092] Test samples: Porous materials obtained in Examples 1 and 2;

[0093] Preparation of MO dye solution: Prepare a MO dye solution with a concentration of 150 ppm;

[0094] Experimental method: 10 mg of the test sample was added to a flat-bottomed beaker, followed by 20 mL of the prepared MO solution. A dark adsorption experiment was first conducted for 1 hour, then the beaker was placed under illumination with a 300 W xenon lamp (420 nm filter). The solution was removed at 0.5 min, 2 min, 5 min, 10 min, 20 min, 30 min, 40 min, and 50 min, and solid-liquid separation was performed using a filter with a pore size of 0.22 μm. The concentration of the MO solution was measured using a UV-Vis spectrophotometer, confirming that the porous material obtained in Example 1 has photocatalytic degradation ability for MO. Figure 7 The graph shows the residual concentration of MO at different times. It can be seen that under dark adsorption conditions, when POP-1 reaches adsorption equilibrium for 150 ppm MO, about 20% remains. After 40-50 minutes of light irradiation, only about 5% of MO remains, which shows that POP-1 has a good photodegradation ability for MO.

[0095] Application Example 6

[0096] Comparative experiment on dark adsorption and photocatalytic degradation of bisphenol A:

[0097] The porous material obtained in Example 1 was studied for the photocatalytic degradation of bisphenol A.

[0098] Test sample: The porous material obtained in Example 1;

[0099] Preparation of bisphenol A dye solution: Prepare a bisphenol A solution with a concentration of 105 ppm;

[0100] Experimental Method: 5 mg of the test sample was added to a flat-bottomed beaker, followed by 15 mL of prepared bisphenol A solution. Dark adsorption experiments were conducted, with the solution removed at 0.5 min, 2 min, 5 min, 10 min, 20 min, 40 min, 60 min, 90 min, 180 min, and 210 min for solid-liquid separation using a 0.22 μm pore size filter. The photocatalytic degradation experiment conditions were the same as the dark adsorption experiment, except that the mixed solution was placed in a reaction vessel with circulating water and illuminated by a 300W xenon lamp (420 nm filter). The solution was removed at 0.5 min, 2 min, 5 min, 10 min, 20 min, 40 min, 60 min, 90 min, 120 min, 150 min, 180 min, and 210 min for solid-liquid separation using a 0.22 μm pore size filter. The concentration of residual bisphenol A solution in both samples was measured using high performance liquid chromatography (HPLC). The dark adsorption and photocatalytic degradation capabilities of the porous material for bisphenol A solution were calculated and compared to demonstrate the photocatalytic degradation capability of the porous material. Figure 8 The graph shows the residual concentration of bisphenol A at 105 ppm at different times, based on... Figure 8It can be seen that the porous material obtained in Example 1 basically completed the degradation of 105 ppm BPA within 210 minutes, and it can be seen that the photocatalytic degradation ability is about twice that of dark adsorption and has sustainability.

[0101] In summary, as can be seen from Examples 1-6 and Application Examples 1-6, the present invention obtains porous material POP-1 by coupling perylene imide monomer, amine monomer, and second structural unit through Suzuki coupling reaction, followed by Soxhlet extraction and vacuum drying. POP-1 exhibits high adsorption performance and photocatalytic degradation capability in the photocatalytic degradation of methyl orange, Congo red, diquat, 2,4-dichlorophenoxyacetic acid, and bisphenol A, and has good application prospects in the field of practical wastewater treatment.

[0102] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing porous materials based on perylene imide, characterized in that: Includes the following steps: Step 1: Add perylene imide monomer and amine monomer to the reaction vessel, add reaction solvent, mix well to obtain perylene imide intermediate 1; Step 2: Add intermediate 1 and the second structural unit obtained in Step 1 into a reaction vessel, add reaction solvent, mix well, and obtain intermediate 2 through Suzuki coupling reaction; Step 3: Add intermediate 2 obtained in step 2 to the reaction vessel, add anhydrous catalyst, mix well and react at room temperature. After Soxhlet extraction and vacuum drying, the porous material POP-1 is obtained. The perylene imide monomer includes at least one of the following structural formulas; ； The amine monomer includes at least one of the following structural formulas; ； The second structural unit includes at least one of the following structural formulas; ； The molar ratio of the perylene imide monomer to the amine monomer is 1:(2~5), and the molar ratio of perylene imide intermediate 1 to the second structural unit is 1:(2~6).

2. The preparation method of perylene imide-based ionic porous materials according to claim 1, characterized in that, The reaction solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, acetic anhydride, o-dichlorobenzene, acetonitrile, chloroform, 1,2-dichloroethane, or n-butanol.

3. The preparation method of perylene imide-based ionic porous materials according to claim 1, characterized in that, The catalyst is one or more of palladium catalyst, anhydrous FeCl3, AlCl3, boron trifluoride, or niobium pentachloride.

4. The method for preparing perylene imide-based ionic porous materials according to claim 1, characterized in that, The solvent used for Soxhlet extraction is one or more of dichloromethane, methanol, ethanol, or acetone.

5. A perylene imide ionic porous material prepared by the method for preparing perylene imide ionic porous materials as described in any one of claims 1-4.

6. A perylene imide ionic porous material as described in claim 5, used for the adsorption or photocatalytic degradation of pollutants in water.

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