Preparation method of bodipy-based functional coupling type porous organic polymer photocatalyst and application of the photocatalyst in photocatalytic hydrogen peroxide production

Abstract

The application discloses a preparation method of a BODIPY-based functional coupling type porous organic polymer photocatalyst and application of the photocatalyst in photocatalytic production of hydrogen peroxide, and utilizes Suzuki or Sonogashira coupling reaction to regulate the photoelectric performance and catalytic performance of the polymer by adjusting the polarity of polymerization monomers. The obtained polymer is a good photocatalyst, can directly synthesize hydrogen peroxide from water and oxygen under light, and provides a simple and feasible new method and new idea for design and development, performance improvement and practical application of the photocatalyst.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic materials technology, and in particular to a method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY and its application in the photocatalytic production of hydrogen peroxide. Background Technology

[0002] Hydrogen peroxide, as an important chemical reagent and green oxidant, plays a crucial role in many fields such as chemical industry, pharmaceuticals, textiles, water treatment, energy conversion, electronics, and liquid fuels. Industrially, over 95% of hydrogen peroxide is produced using the anthraquinone process. However, the anthraquinone process for producing hydrogen peroxide involves four steps: hydrogenation, oxidation, extraction, and purification. It requires significant energy input, uses precious metal catalysts, and generates large amounts of toxic byproducts. Currently, the synthesis of hydrogen peroxide using water and oxygen as raw materials through artificial photosynthesis has attracted widespread attention and holds promise as a replacement for the traditional industrial anthraquinone process.

[0003] Currently, many semiconductor materials exhibit the ability to photocatalyze the production of hydrogen peroxide, such as metal oxides, g-C3N4, metal-organic frameworks (MOFs), porous organic polymers (POPs), and covalent organic frameworks (COFs). Among them, POPs, due to their regular porous structure and easily tunable characteristics, are beneficial for efficient mass transport and light capture, and have become a popular type of photocatalyst. Introducing BODIPY as a photosensitizing center into POPs can combine porosity and photosensitivity, especially the ability to generate oxygen-active species, which can provide key species for the photocatalytic production of hydrogen peroxide. By changing the monomer structure, the specific surface area, planar rigidity, conjugation degree, hydrophilicity, and photoelectric properties of the material can be further adjusted to obtain more efficient photocatalytic performance.

[0004] Currently, the concentration of hydrogen peroxide produced by photocatalysis using POPs (particulate organic polymers) needs to be improved (typically at the μM level), limiting its application in industrial production. Therefore, there is an urgent need to develop efficient POPs photocatalysts and photocatalytic technologies to advance the photocatalytic production of hydrogen peroxide suitable for industrial-scale production. Recently, a two-phase system of benzyl alcohol and water has been used to produce high-concentration hydrogen peroxide under illumination, reaching up to 47.25 μM (Chemical Engineering Journal 2022, 438, 135664), equivalent to a 1% (w / w) hydrogen peroxide concentration, close to the commonly used concentration (3%–5%) for medical disinfection. However, benzyl alcohol is easily oxidized to benzaldehyde and benzoic acid, producing byproducts that hinder hydrogen peroxide purification, and benzyl alcohol is also difficult to recycle. Therefore, developing efficient and recyclable functionally coupled porous organic polymer photocatalysts, using a small amount of benzyl alcohol as a co-catalyst, to achieve high-concentration and efficient photocatalytic hydrogen peroxide production close to practical / industrial production levels is of great significance. Summary of the Invention

[0005] The main technical problem solved by this invention is to provide a method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY and its application in the photocatalytic production of hydrogen peroxide. The functionally coupled porous organic polymer photocatalyst based on BODIPY prepared by this invention can photocatalytically produce a high concentration of hydrogen peroxide (3% by mass), which can be used for medical disinfection and exhibits excellent photocatalytic performance.

[0006] Therefore, the present invention provides the following technical solution:

[0007] A method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY, comprising a one-step synthesis of BODIPY and a carbonyl-containing derivative via a Suzuki or Sonogashira coupling reaction. The synthetic route is as follows:

[0008]

[0009] The structural formula of the BODIPY is shown in formula (Ⅰ), wherein X is selected from any one of halogen or C≡CH. When X is a halogen, the Suzuki reaction is carried out; when X is C≡CH, the Sonogashira reaction is carried out.

[0010] Preferably, X is selected from Br, I, Cl, Any one of them.

[0011] The basic structural formula of the carbonyl derivative is shown in formula (II), where Y is selected from any one of halogen, B(OH)2, or Bpin, and the carbonyl derivative is extended as follows:

[0012]

[0013] Any one of them.

[0014] The specific preparation steps are as follows:

[0015] 1) Add BODIPY and carbonyl derivative sequentially to the solvent and sonicate until homogeneous;

[0016] 2) After the solid in step 1) has completely dissolved, add the catalyst and carry out the reaction under a protective atmosphere;

[0017] 3) After the reaction is complete, filter and wash the filter cake, and then vacuum dry the resulting filter cake.

[0018] 4) The filter cake obtained in step 3) is eluted using a Soxhlet extractor and vacuum dried to obtain a functionally coupled porous organic polymer photocatalyst based on BODIPY.

[0019] Preferably, in step (1): the molar ratio of BODIPY to the carbonyl derivative is 1:1 to 1:5, and the solvent is one or a combination of several of N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, toluene, chloroform, and water.

[0020] Preferably, in step (2): the catalyst is one or a combination of several of tetra(triphenylphosphine)palladium, 1,1-(bis(diphenylphosphine)ferrocene palladium dichloride, and cuprous iodide; the protective atmosphere is nitrogen or argon; the reaction temperature is 20-120°C; and the reaction time is 24-72 hours.

[0021] Preferably, in step (3): the solvent for washing the filter cake is one or a combination of several of the following: N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, toluene, chloroform, and water; the vacuum drying temperature is 60-100°C, and the vacuum drying time is 24-48 hours.

[0022] Application of the functionally coupled porous organic polymer photocatalyst based on BODIPY prepared by the above method: production of hydrogen peroxide via photocatalysis.

[0023] Preferably, the light source used in photocatalysis is a xenon lamp.

[0024] Preferably, the amount of hydrogen peroxide used in the production is 0.1-1 mg / mL.

[0025] The beneficial technical effects of this invention are:

[0026] This invention discloses a method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY. The photocatalyst is prepared in one step by coupling BODIPY with a carbonyl derivative via a Suzuki or Sonogashira coupling reaction. By controlling the connection mode and changing the carbonyl derivative, a variety of porous organic polymers with excellent photocatalytic performance are obtained, which can efficiently produce hydrogen peroxide in water.

[0027] This invention provides a functionally coupled porous organic polymer photocatalyst based on BODIPY for the photocatalytic production of hydrogen peroxide. It has good application prospects and potential value in the field of photocatalysis, and provides a simple and easy new method and idea for the design, development, performance improvement and practical application of photocatalysts. Attached Figure Description

[0028] Figure 1The 1H NMR spectrum of 2,8-dieethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-tetrafluoro-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoborene is shown.

[0029] Figure 2 A 200 nm scanning electron microscope image of BDP-AAQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY, prepared in Example 1.

[0030] Figure 3 The water contact angle of the functionally coupled porous organic polymer photocatalyst BDP-AAQ based on BODIPY prepared in Example 1;

[0031] Figure 4 The infrared spectrum of BDP-AAQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY, prepared in Example 1;

[0032] Figure 5 X-ray diffraction pattern of BDP-AAQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY prepared in Example 1;

[0033] Figure 6 The solid-state UV image of BDP-AAQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY prepared in Example 1;

[0034] Figure 7 The nitrogen adsorption-desorption curve of BDP-AAQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY prepared in Example 1, is shown.

[0035] Figure 8 A comparison chart showing the rate of photocatalytic production of hydrogen peroxide using the functionally coupled porous organic polymer photocatalyst based on BODIPY prepared in Example 1 under different gas atmospheres;

[0036] Figure 9 A comparison of the photocatalytic production rate of hydrogen peroxide by the functionally coupled porous organic polymer photocatalyst BDP-AAQ based on BODIPY prepared in Example 1 under different cocatalyst conditions.

[0037] Figure 10 The graph shows the rate and concentration of hydrogen peroxide produced by the photocatalytic oxidation of the functionally coupled porous organic polymer photocatalyst BDP-AAQ based on BODIPY prepared in Example 1 at different benzyl alcohol contents. Detailed Implementation

[0038] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The use of "attribute" in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and" as used herein includes any and all combinations of one or more of the associated listed items.

[0040] Example 1

[0041] Following the synthetic route:

[0042]

[0043] Preparation steps:

[0044] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-tetrafluoro-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoborene (700 mg, 1.77 mmol), 2,6-dibromoanthraquinone (971 mg, 2.65 mmol), 70 mL of diisopropylamine and 140 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0045] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (183mg, 0.16mmol) and cuprous iodide (60mg, 0.32mmol) are added to the above reaction solution in sequence. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120°C and refluxed for 72 hours.

[0046] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0047] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain a functionally coupled porous organic polymer photocatalyst based on BODIPY with a yield of 95%.

[0048] Example 2

[0049] Following the synthetic route:

[0050]

[0051] Preparation steps:

[0052] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-tetrafluoro-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoborene (700 mg, 1.77 mmol), 2,7-dibromofluorenone (897 mg, 2.65 mmol), 70 mL of diisopropylamine and 140 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0053] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (183mg, 0.16mmol) and cuprous iodide (60mg, 0.32mmol) are added to the above reaction solution in sequence. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120°C and refluxed for 72 hours.

[0054] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0055] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain BDP-AFO, a functionally coupled porous organic polymer photocatalyst based on BODIPY, with a yield of 89%.

[0056] Example 3

[0057] Following the synthetic route:

[0058]

[0059] Preparation steps:

[0060] (1) Add 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoboronine (702 mg, 1 mmol), 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)anthraquinone-9,10-dione (690 mg, 1.5 mmol), potassium carbonate (1380 mg, 10 mmol) and 120 mL of N,N-dimethylformamide to a 500 mL Schlenk flask and stir thoroughly for 15 minutes under a nitrogen atmosphere;

[0061] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (92 mg, 0.08 mmol) is added to the above reaction solution. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120 °C and refluxed for 72 hours.

[0062] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0063] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain BDP-AQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY, with a yield of 88%.

[0064] Example 4

[0065] Following the synthetic route:

[0066]

[0067] Preparation steps:

[0068] (1) Add 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoboronine (702 mg, 1 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)-9H-fluorene-9-one (648 mg, 1.5 mmol), potassium carbonate (1380 mg, 10 mmol) and 120 mL of N,N-dimethylformamide to a 500 mL Schlenk flask and stir thoroughly for 15 minutes under a nitrogen atmosphere;

[0069] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (92 mg, 0.08 mmol) is added to the above reaction solution. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120 °C and refluxed for 72 hours.

[0070] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0071] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain BDP-FO, a functionally coupled porous organic polymer photocatalyst based on BODIPY, with a yield of 91%.

[0072] Example 5

[0073] Following the synthetic route:

[0074]

[0075] Preparation steps:

[0076] (1) Add 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoboronine (702 mg, 1 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenanthrene-9,10-dione (690 mg, 1.5 mmol), potassium carbonate (1380 mg, 10 mmol) and 120 mL of N,N-dimethylformamide to a 500 mL Schlenk flask and stir thoroughly for 15 minutes under a nitrogen atmosphere;

[0077] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (92 mg, 0.08 mmol) is added to the above reaction solution. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120 °C and refluxed for 72 hours.

[0078] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0079] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain BDP-FQ, a functionally coupled porous organic polymer photocatalyst based on BODIPY, with a yield of 83%.

[0080] Example 6

[0081] Following the synthetic route:

[0082]

[0083] Preparation steps:

[0084] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-tetrafluoro-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoborene (700 mg, 1.77 mmol), 4,7-bromonaphthalene-1,2-dione (901 mg, 2.65 mmol), 70 mL of diisopropylamine and 140 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0085] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (183mg, 0.16mmol) and cuprous iodide (60mg, 0.32mmol) are added to the above reaction solution in sequence. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120°C and refluxed for 72 hours.

[0086] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0087] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain a functionally coupled porous organic polymer photocatalyst based on BODIPY with a yield of 82%.

[0088] Example 7

[0089] Following the synthetic route:

[0090]

[0091] Preparation steps:

[0092] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-tetrafluoro-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoborene (700 mg, 1.77 mmol), 4,7-bromonaphthalene-1,2-dione (768 mg, 1.33 mmol), 70 mL of diisopropylamine and 140 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0093] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (183mg, 0.16mmol) and cuprous iodide (60mg, 0.32mmol) are added to the above reaction solution in sequence. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120°C and refluxed for 72 hours.

[0094] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0095] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain a functionally coupled porous organic polymer photocatalyst based on BODIPY with a yield of 85%.

[0096] Example 8

[0097] Following the synthetic route:

[0098]

[0099] Preparation steps:

[0100] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-tetrafluoro-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazoborene (700 mg, 1.77 mmol), 4,7-bromonaphthalene-1,2-dione (768 mg, 1.33 mmol), 70 mL of diisopropylamine and 140 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0101] (2) After the solution in step (1) is fully mixed, tetra(triphenylphosphine)palladium (183mg, 0.16mmol) and cuprous iodide (60mg, 0.32mmol) are added to the above reaction solution in sequence. After being fully dispersed under a nitrogen atmosphere, the mixed solution is heated to 120°C and refluxed for 72 hours.

[0102] (3) After the reaction is complete, cool the mixture to room temperature and pour it into water. Collect the precipitate by filtration, and wash the filter cake obtained by filtration successively with water, tetrahydrofuran, methanol and dichloromethane.

[0103] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with tetrahydrofuran, methanol and dichloromethane for 48 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 65°C for 24 hours to obtain a functionally coupled porous organic polymer photocatalyst based on BODIPY with a yield of 91%.

[0104] The results obtained in Examples 1-8 are summarized in Table 1:

[0105] Table 1

[0106]

[0107]

[0108] Application Example 1

[0109] Research on photocatalytic oxidation of hydrogen peroxide to produce hydrogen peroxide under different atmospheres using different photocatalysts:

[0110] The functionally coupled porous organic polymer photocatalysts based on BODIPY obtained in Examples 1, 2, 3, 4, and 5 were used to study the photocatalytic oxidation of hydrogen peroxide in air, oxygen, and nitrogen atmospheres.

[0111] Test samples: BODIPY-based functionally coupled porous organic polymer photocatalysts obtained in Examples 1, 2, 3, and 4;

[0112] Experimental Method: 5 mg of the test sample was added to the photoreactor, followed by 20 mL of pure water. Before the photocatalytic test, air, oxygen, or nitrogen was continuously bubbled into the reaction solution, and the mixture was stirred in the dark for 30 minutes. Then, the reactor was irradiated with a 300 watt xenon lamp while continuously bubbling in air, oxygen, or nitrogen. After one hour, 2 mL of the reaction solution was taken and filtered using a 0.22 μm filter. 1.5 mL of the filtered solution was added to a 5 mL centrifuge tube, followed by 1 mL of a 1 mol L⁻¹ potassium titanium oxalate aqueous solution. After mixing and reacting for 5 minutes, the absorbance was measured using a UV-Vis spectrophotometer. The hydrogen peroxide concentration was determined according to the standard curve, as shown in Tables 2 and 3.

[0113] Table 2

[0114]

[0115] Table 3

[0116]

[0117]

[0118] Application Example 2

[0119] Study on photocatalytic oxidation of hydrogen peroxide in Example 1 with different co-catalysts:

[0120] The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1 was added to different cocatalysts and then used for photocatalytic oxidation to produce hydrogen peroxide in an oxygen atmosphere.

[0121] Test sample: The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1;

[0122] Experimental Method: Add 5 mg of the test sample, 18 mL of pure water, and 2 mL of one of the following: ethanol, methanol, isopropanol, or benzyl alcohol, to the photoreactor. After stirring in the dark for 30 minutes, irradiate the reactor with a 300 watt xenon lamp while continuously introducing oxygen. After one hour, take 2 mL of the reaction solution and filter it using a 0.22 μm filter. Add 1.5 mL of the filtered solution to a 5 mL centrifuge tube, then add 1 mL of a 1 mol L⁻¹ potassium titanium oxalate aqueous solution. After mixing and reacting for 5 minutes, measure the absorbance using a UV-Vis spectrophotometer. Determine the concentration of hydrogen peroxide according to the standard curve, as shown in Table 4.

[0123] Table 4

[0124]

[0125] Application Example 3

[0126] Research on the photocatalytic oxidation of hydrogen peroxide using benzyl alcohol at different concentrations as a co-catalyst:

[0127] The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1 was added to different benzyl alcohols and then used for photocatalytic oxidation to produce hydrogen peroxide in an oxygen atmosphere.

[0128] Test sample: The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1;

[0129] Experimental Method: 5 mg of the test sample was added to the photoreactor, followed by 20 mL of a mixed solution of pure water and benzyl alcohol at a volume ratio of 18:1, 9:1, 5:1, 4:1, 3:1, 2:1, or 1:1. After stirring in the dark for 30 minutes, the reactor was irradiated with a 300 watt xenon lamp while continuously introducing oxygen. After one hour, 2 mL of the reaction solution was taken and filtered through a 0.22 μm filter. 1.5 mL of the filtered solution was added to a 5 mL centrifuge tube, followed by 1 mL of a 1 mol L⁻¹ potassium titanium oxalate aqueous solution. After mixing and reacting for 5 minutes, the absorbance was measured using a UV-Vis spectrophotometer. The concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 5.

[0130] Table 5

[0131]

[0132] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY, characterized in that, It is prepared in one step by coupling BODIPY with carbonyl-containing derivatives via Suzuki or Sonogashira reaction; The structural formula of the BODIPY is shown in formula (Ⅰ): ； Wherein, X is selected from halogens or C≡CH; The basic structural formula of the carbonyl derivative is shown in formula (II): ； Y is selected from any one of halogen, B(OH)2, or Bpin.

2. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 1, characterized in that: When X is a halogen, the Suzuki reaction occurs; when X is C≡CH, the Sonogashira reaction occurs.

3. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 1, characterized in that, The synthesis route is as follows: ； Wherein, X and Y are the same as in claim 1.

4. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 3, characterized in that, The specific preparation steps are as follows: 1) Dissolve the BODIPY and the carbonyl derivative of claim 1 in a solvent; 2) After the solid in step 1) has completely dissolved, add the catalyst and carry out the reaction under a protective atmosphere; 3) After the reaction is complete, filter and wash the filter cake, and then vacuum dry the resulting filter cake. 4) The filter cake obtained in step 3) is eluted using a Soxhlet extractor and vacuum dried to obtain a functionally coupled porous organic polymer photocatalyst based on BODIPY.

5. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 4, characterized in that, In step 1): the molar ratio of BODIPY to the carbonyl-containing derivative is 1:1 to 1:5, and the solvent is... N , N - One or a combination of dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, toluene, chloroform, and water.

6. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 4, characterized in that, In step 2): the catalyst is one or a combination of several of tetra(triphenylphosphine)palladium, 1,1-(bis(diphenylphosphine)ferrocene palladium dichloride, and cuprous iodide; the protective atmosphere is nitrogen or argon; the reaction temperature is 20–120 °C; and the reaction time is 24–72 hours.

7. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 4, characterized in that, In step 4): the solvent for washing the filter cake is N , N - One or a combination of dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, toluene, chloroform, and water; vacuum drying temperature is 60–100 °C, and vacuum drying time is 24–48 hours.

8. The application of the functionally coupled porous organic polymer photocatalyst based on BODIPY prepared by the preparation method according to any one of claims 2-7 in the photocatalytic production of hydrogen peroxide.

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