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

Abstract

The invention discloses a preparation method of a BODIPY-based functional coupling type porous organic polymer photocatalyst and application of the BODIPY-based functional coupling type porous organic polymer photocatalyst in photocatalytic production of hydrogen peroxide. Suzuki or Sonogashira coupling reaction is utilized, and the photoelectric property and catalytic performance of a polymer are regulated and controlled by adjusting the polarity of a polymeric monomer. The obtained polymer is a good photocatalyst, hydrogen peroxide can be directly synthesized through water and oxygen under illumination, and a simple and feasible new method and a new idea are provided for design and development, performance improvement and practical application of the photocatalyst.

Description

Technical Field

[0001] The invention relates to the technical field of photocatalytic materials, and in particular to a preparation method of a functional coupling porous organic polymer photocatalyst based on BODIPY and its application in photocatalytic production of hydrogen peroxide. Background Art

[0002] As an important chemical reagent and green oxidant, hydrogen peroxide plays a vital role in many fields such as chemical industry, medicine, textile, water treatment, energy conversion, electronics and liquid fuel. More than 95% of hydrogen peroxide in industry is prepared by the anthraquinone method. However, the production of hydrogen peroxide by the anthraquinone method involves four steps: hydrogenation, oxidation, extraction and purification. It requires huge energy input, uses precious metal catalysts and produces a large number of toxic by-products. At present, the use of artificial photosynthesis to synthesize hydrogen peroxide using water and oxygen as raw materials has attracted widespread attention and is expected to replace the traditional industrial anthraquinone method.

[0003] At present, many semiconductor materials have shown the ability to produce hydrogen peroxide through photocatalysis, such as metal oxides, g-C3N4, metal organic frameworks (MOFs), porous organic polymers (POPs) and covalent organic frameworks (COFs). Among them, POPs have become a popular catalyst type for photocatalysis due to their regular porous structure and easy-to-adjust properties, which are conducive to efficient mass transfer and light capture. Introducing BODIPY as a photosensitive center into POPs can combine porosity and photosensitivity, especially the ability to produce oxygen-active species, and the production of oxygen-active species can provide key species for the photocatalytic production of hydrogen peroxide. By changing the monomer structure, the specific surface area, planar rigidity, degree of conjugation, hydrophilicity and photoelectric properties of the material can be further adjusted to obtain more efficient photocatalytic performance.

[0004] At present, the concentration of hydrogen peroxide produced by photocatalysis of POPs needs to be improved (usually at the μM level), which limits its application in industrial production. Therefore, it is urgent to develop efficient POPs photocatalysts and photocatalytic technologies to promote the photocatalytic production of hydrogen peroxide suitable for industrial-scale production. Recently, a two-phase system of benzyl alcohol and water can be used to produce high-concentration hydrogen peroxide under light, up to 47.25 μM (Chemical Engineering Journal 2022, 438, 135664), which is equivalent to a mass fraction of 1% hydrogen peroxide, close to the commonly used concentration for medical disinfection (3% to 5%). However, benzyl alcohol is easily oxidized to benzaldehyde and benzoic acid, thereby producing by-products, which is not conducive to the purification of hydrogen peroxide, and benzyl alcohol is also difficult to recycle. Therefore, it is of great significance to develop 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 the actual / industrial production level. Summary of the invention

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

[0006] To this end, the present invention provides the following technical solutions:

[0007] A method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY, wherein BODIPY and a carbonyl-containing derivative are reacted by Suzuki or Sonogashira coupling reaction to obtain the photocatalyst.

[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 halogen, Suzuki reaction is carried out; when X is C≡CH, Sonogashira reaction is carried out.

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

[0011] The basic structural formula of the carbonyl-containing derivative is shown in formula (II), wherein Y is selected from any one of halogen, B(OH)2 or Bpin, and the carbonyl-containing derivative is expanded to:

[0012]

[0013] Any one of .

[0014] The specific preparation steps are:

[0015] 1) Add BODIPY and carbonyl-containing derivatives to the solvent in sequence and mix them evenly with ultrasound;

[0016] 2) After the solid in step 1) is completely dissolved, a catalyst is added and the reaction is carried out under a protective atmosphere;

[0017] 3) After the reaction is completed, the filter cake is filtered and washed, and vacuum dried;

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

[0019] Preferably, in step (1), the molar ratio of BODIPY to the carbonyl-containing derivative is 1:1 to 1:5, and the solvent is one or a combination 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 tetrakis(triphenylphosphine)palladium, 1,1-(bis(diphenylphosphino)ferrocenepalladium dichloride, cuprous iodide; the protective atmosphere is nitrogen or argon; the reaction temperature is 20 to 120° C.; and the reaction time is 24 to 72 hours.

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

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

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

[0024] Preferably, the amount used to produce hydrogen peroxide is 0.1-1 mg / mL.

[0025] The beneficial technical effects of the present invention are:

[0026] The present invention discloses a method for preparing a functional coupling porous organic polymer photocatalyst based on BODIPY, which is prepared in one step by Suzuki or Sonogashira coupling reaction of BODIPY and a carbonyl-containing derivative, and by regulating the connection mode and changing the carbonyl-containing derivative, a variety of porous organic polymers with excellent photocatalytic performance are obtained, and hydrogen peroxide can be efficiently produced in water.

[0027] The present invention provides a BODIPY-based functional coupling porous organic polymer photocatalyst for photocatalytic production of hydrogen peroxide, which has good application prospects and potential application value in the field of photocatalysis, and provides a simple and easy new method and new idea for the design and development, performance improvement and practical application of photocatalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1The hydrogen nuclear magnetic resonance spectrum of 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]diazaborene;

[0029] Figure 2 This is a 200nm scanning electron microscope image of the BODIPY-based functional coupling porous organic polymer photocatalyst BDP-AAQ prepared in Example 1;

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

[0031] Figure 4 This is the infrared spectrum of the BODIPY-based functional coupling porous organic polymer photocatalyst BDP-AAQ prepared in Example 1;

[0032] Figure 5 This is an X-ray diffraction pattern of the BODIPY-based functional coupling porous organic polymer photocatalyst BDP-AAQ prepared in Example 1;

[0033] Figure 6 This is a solid UV image of the BODIPY-based functional coupling porous organic polymer photocatalyst BDP-AAQ prepared in Example 1;

[0034] Figure 7 This is a nitrogen adsorption-desorption curve of the BODIPY-based functional coupling porous organic polymer photocatalyst BDP-AAQ prepared in Example 1;

[0035] Figure 8 This is a comparison chart of the rate of photocatalytic production of hydrogen peroxide by the BODIPY-based functionally coupled porous organic polymer photocatalyst prepared in Example 1 under different gas atmospheres;

[0036] Fig. 9 This is a comparison chart of the rate of photocatalytic production of hydrogen peroxide by the BODIPY-based functionally coupled porous organic polymer photocatalyst BDP-AAQ prepared in Example 1 under different co-catalyst conditions;

[0037] Fig.10 This is a graph showing the rate and concentration of hydrogen peroxide produced by photocatalytic oxidation of the BODIPY-based functionally coupled porous organic polymer photocatalyst BDP-AAQ prepared in Example 1 at different benzyl alcohol contents. DETAILED DESCRIPTION

[0038] 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.

[0039] 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.

[0040] Example 1

[0041] According to the following 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]diazaborolene (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 bottle and stirred for 30 minutes under a nitrogen atmosphere;

[0045] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (183 mg, 0.16 mmol) and cuprous iodide (60 mg, 0.32 mmol) are added to the above reaction solution in sequence, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

[0047] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted solid was transferred to a vacuum drying oven and vacuum dried 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] According to the following 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]diazaborolene (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 bottle and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0053] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (183 mg, 0.16 mmol) and cuprous iodide (60 mg, 0.32 mmol) are added to the above reaction solution in sequence, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

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

[0056] Example 3

[0057] According to the following synthetic route:

[0058]

[0059] Preparation steps:

[0060] (1) 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine (702 mg, 1 mmol), 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anthraquinone-9,10-dione (690 mg, 1.5 mmol), potassium carbonate (1380 mg, 10 mmol) and 120 mL of N,N-dimethylformamide were added to a 500 mL Schlenk bottle and stirred thoroughly for 15 minutes under a nitrogen atmosphere;

[0061] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (92 mg, 0.08 mmol) is added to the above reaction solution, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

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

[0064] Example 4

[0065] According to the following synthetic route:

[0066]

[0067] Preparation steps:

[0068] (1) Add 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine (702 mg, 1 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-9-one (648 mg, 1.5 mmol), potassium carbonate (1380 mg, 10 mmol) and 120 mL of N,N-dimethylformamide into a 500 mL Schlenk bottle and stir well for 15 minutes under nitrogen atmosphere;

[0069] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (92 mg, 0.08 mmol) is added to the above reaction solution, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

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

[0072] Example 5

[0073] According to the following synthetic route:

[0074]

[0075] Preparation steps:

[0076] (1) 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine (702 mg, 1 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthrene-9,10-dione (690 mg, 1.5 mmol), potassium carbonate (1380 mg, 10 mmol) and 120 mL of N,N-dimethylformamide were added to a 500 mL Schlenk bottle and stirred thoroughly for 15 minutes under a nitrogen atmosphere;

[0077] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (92 mg, 0.08 mmol) is added to the above reaction solution, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

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

[0080] Example 6

[0081] According to the following 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]diazaborole (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 bottle and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0085] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (183 mg, 0.16 mmol) and cuprous iodide (60 mg, 0.32 mmol) are added to the above reaction solution in sequence, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

[0087] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted solid was transferred to a vacuum drying oven and vacuum dried 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] According to the following 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]diazaborolene (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 bottle and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0093] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (183 mg, 0.16 mmol) and cuprous iodide (60 mg, 0.32 mmol) are added to the above reaction solution in sequence, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

[0095] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted solid was transferred to a vacuum drying oven and vacuum dried 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] According to the following 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]diazaborolene (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 bottle and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0101] (2) After the solution in step (1) is fully mixed, tetrakis(triphenylphosphine)palladium (183 mg, 0.16 mmol) and cuprous iodide (60 mg, 0.32 mmol) are added to the above reaction solution in sequence, and 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 completed, the mixture is cooled to room temperature and poured into water. The precipitate is collected by filtration, and the filter cake obtained by filtration is washed with water, tetrahydrofuran, methanol and dichloromethane in sequence.

[0103] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted solid was transferred to a vacuum drying oven and vacuum dried 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 as shown in Table 1:

[0105] Table 1

[0106]

[0107]

[0108] Application Example 1

[0109] Study on the production of hydrogen peroxide by photocatalytic oxidation of different photocatalysts in different atmospheres:

[0110] The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1, Example 2, Example 3, Example 4, and Example 5 was subjected to photocatalytic oxidation to produce hydrogen peroxide in air, oxygen, and nitrogen atmospheres;

[0111] Test samples: BODIPY-based functional coupling porous organic polymer photocatalysts obtained in Example 1, Example 2, Example 3, and Example 4;

[0112] Test method: Add 5 mg of the test sample to the photoreactor, add 20 mL of pure water. Before the photocatalytic test, continuously blow air, oxygen or nitrogen into the reaction solution, and stir in the dark for 30 minutes. Then, use a 300-watt xenon lamp to illuminate the reactor, and continuously blow air, oxygen or nitrogen. One hour later, take 2 mL of the reaction solution and filter it with a 0.22 μm filter. Take 1.5 mL of the filtered solution and add it to a 5 mL centrifuge tube. Then add 1 mL of 1 mol L-1 potassium titanium oxalate aqueous solution. After mixing and reacting for 5 minutes, measure the absorbance with a UV-visible spectrophotometer, and determine the concentration of hydrogen peroxide 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 the production of hydrogen peroxide by photocatalytic oxidation of Example 1 with different co-catalysts added:

[0120] The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1 was added with different co-catalysts to conduct photocatalytic oxidation to produce hydrogen peroxide in an oxygen atmosphere;

[0121] Test sample: the BODIPY-based functional coupling porous organic polymer photocatalyst obtained in Example 1;

[0122] Test method: Add 5 mg of the test sample, 18 mL of pure water, and 2 mL of ethanol, methanol, isopropanol or benzyl alcohol to the photoreactor, and stir in the dark for 30 minutes, then illuminate the reactor with a 300-watt xenon lamp while continuously blowing in oxygen. One hour later, take 2 mL of the reaction solution and filter it with a 0.22 μm filter, draw 1.5 mL of the filtered solution and add it to a 5 mL centrifuge tube, then add 1 mL of 1 mol L-1 potassium titanium oxalate aqueous solution, mix and react for 5 minutes, measure the absorbance with a UV-visible spectrophotometer, and 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] Study on the production of hydrogen peroxide by photocatalytic oxidation with different concentrations of benzyl alcohol as a co-catalyst:

[0127] The functionally coupled porous organic polymer photocatalyst based on BODIPY obtained in Example 1 was added with different benzyl alcohols to conduct photocatalytic oxidation to produce hydrogen peroxide in an oxygen atmosphere;

[0128] Test sample: the BODIPY-based functional coupling porous organic polymer photocatalyst obtained in Example 1;

[0129] Test method: Add 5 mg of the test sample to the photoreactor, add 20 mL of a mixed solution of pure water and benzyl alcohol in a volume ratio of 18:1, 9:1, 5:1, 4:1, 3:1, 2:1 or 1:1, and stir in the dark for 30 minutes. Then, illuminate the reactor with a 300-watt xenon lamp and continuously bubble in oxygen. One hour later, take 2 mL of the reaction solution and filter it with a 0.22 μm filter. Take 1.5 mL of the filtered solution and add it 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 with a UV-visible spectrophotometer. Determine the concentration of hydrogen peroxide according to the standard curve, as shown in Table 5:

[0130] Table 5

[0131]

[0132] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention 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 Suzuki or Sonogashira coupling reaction of BODIPY and carbonyl-containing derivatives.

2. The method for preparing a porous organic polymer photocatalyst based on BODIPY according to claim 1, characterized in that: The structural formula of BODIPY is shown in formula (I): Wherein, X is selected from any one of halogen or C≡CH; The basic structural formula of the carbonyl-containing derivative is shown in formula (II): Wherein, Y is selected from any one of halogen, B(OH)2 or Bpin.

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

4. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 2, characterized in that: The carbonyl-containing derivative is expanded to: Any one of .

5. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 2, characterized in that: The synthetic route is as follows: Among them, X and Y are the same as claim 2.

6. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 5, characterized in that: The specific preparation steps are: 1) dissolving the BODIPY and the carbonyl derivative according to claim 2 in a solvent; 2) After the solid in step 1) is completely dissolved, a catalyst is added and the reaction is carried out under a protective atmosphere; 3) After the reaction is completed, the filter cake is filtered and washed, and vacuum dried; 4) The filter cake obtained in step 3) is eluted using a Soxhlet extractor and vacuum dried to obtain a BODIPY-based functionally coupled porous organic polymer photocatalyst.

7. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 6, 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 one or a combination of N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, toluene, chloroform, and water.

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

9. The method for preparing a functionally coupled porous organic polymer photocatalyst based on BODIPY according to claim 6, characterized in that: In step 4), the solvent for washing the filter cake is one or a combination of N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, toluene, chloroform, and water; the vacuum drying temperature is 60 to 100° C., and the vacuum drying time is 24 to 48 hours.

10. The BODIPY-based functionally coupled porous organic polymer photocatalyst prepared by the preparation method according to any one of claims 3 to 9 is capable of photocatalytically producing hydrogen peroxide.

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