A hydrophilic porous organic polymer and a preparation method and application thereof

Abstract

The application discloses a kind of hydrophilic porous organic polymer and its preparation method and application.The preparation method of the application includes the following steps: compound III and compound II are dissolved in first solvent;After solid in step (1) is dissolved sufficiently, catalyst is added, and reaction is carried out under the protection of inert atmosphere;After reaction is finished, filtration is carried out, and filter cake is washed with second solvent;After washing, filter cake is eluted, dried, and hydrophilic porous organic polymer is obtained.The application polymerizes BODIPY monomer and dibenzothiophene derivative by using Sonogashira coupling reaction to prepare a kind of hydrophilic porous organic polymer by molecular engineering regulation and control monomer structure.The porous organic polymer is a good photocatalyst, and can directly synthesize hydrogen peroxide by water and oxygen under light, which provides a simple and easy new method and new idea for design and development, performance improvement and practical application of photocatalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of photocatalytic material and its preparation method and application, especially to a kind of hydrophilic porous organic polymer containing boron photosensitizer and its preparation method and application in photocatalytic preparation hydrogen peroxide. BACKGROUND

[0002] At present, anthraquinone (AQ) method process dominates the large-scale production of hydrogen peroxide in industry, accounting for more than 95%. However, the anthraquinone method for producing hydrogen peroxide involves four steps of hydrogenation, oxidation, extraction and purification, with huge energy input, noble metal catalysts involved in the reaction and a large amount of toxic by-products. Therefore, it is urgent to develop a green and energy-efficient hydrogen peroxide production technology. Semiconductor-based photocatalytic technology opens up an economically viable way to utilize solar energy, which converts solar energy into chemical energy by simulating natural photosynthesis. It is considered that the photocatalytic technology driven by sunlight to produce hydrogen peroxide is a feasible strategy to replace the anthraquinone method for producing hydrogen peroxide in the future.

[0003] Various semiconductor materials have been explored for photocatalytic production of hydrogen peroxide. For example, metal oxides (titanium dioxide, BiVO4), g-C3N4, metal-organic frameworks (MOFs), porous organic polymers (POPs), covalent triazine frameworks (CTFs), covalent organic frameworks (COFs) and polymer semiconductors. Among them, POPs have outstanding advantages compared to other materials: 1) low backbone density; 2) abundant polymer monomers, various organic reaction types, easy functionalization; 3) linked by covalent bonds, stable physical and chemical properties; 4) mainly rigid aromatic building blocks, conducive to obtaining permanent pore structure. These characteristics make it a popular material for light-driven hydrogen peroxide production. However, the performance of the current photocatalytic hydrogen peroxide production still needs to be improved, mainly in the range of several mmol h -1 g -1 This is not conducive to the purification of hydrogen peroxide, so it is necessary to develop more efficient POPs photocatalysts.

[0004] The main preparation strategies of POPs are pre-design and post-modification. The introduction of BODIPY as a photosensitive center into POPs not only obtains the porosity of the material itself, but also inherits the photosensitive properties and oxygen active species generating ability of BODIPY, ensuring excellent photocatalytic hydrogen peroxide production performance of the material. At the same time, through molecular engineering, the specific surface area, planar rigidity, conjugation degree, hydrophilicity and photoelectric performance of the material can be further adjusted to obtain better photocatalytic performance, making the material have better practicality. SUMMARY

[0005] The application aims to provide a hydrophilic porous organic polymer, solve the problem of low performance of existing photocatalytic materials in catalyzing preparation of hydrogen peroxide, and provide a preparation method of the hydrophilic porous organic polymer, solve the problem of how to prepare an organic porous polymer which can inherit the photosensitive characteristics and oxygen active species generating capacity of BODIPY, and provide the application of the hydrophilic porous organic polymer in photocatalytic preparation of hydrogen peroxide, solve the problem of how to efficiently prepare hydrogen peroxide by using the hydrophilic porous organic polymer.

[0006] The application provides a hydrophilic porous organic polymer, which comprises a structural unit shown in formula (I).

[0007]

[0008] Y is S or sulfonyl.

[0009] In order to obtain the hydrophilic porous organic polymer, the application discloses a preparation method of the polymer, which comprises the following steps.

[0010]

[0011] X is halogen, and Y is S or sulfonyl.

[0012] The application adopts a BODIPY derivative and a diphenylthiophene derivative to prepare a porous organic polymer based on BODIPY through a Sonogashira coupling reaction, and the polymer has excellent hydrophilicity and photocatalytic performance, and can efficiently produce hydrogen peroxide in water.

[0013] Preferably, the catalyst is a palladium catalyst and / or cuprous iodide, and the palladium catalyst is tetrakis(triphenylphosphine)palladium and / or 1,1-bis(diphenylphosphino)ferrocene palladium dichloride.

[0014] Preferably, the molar ratio of the compound III to the compound II is 1:1-3.

[0015] Preferably, the preparation method comprises the following steps.

[0016] (1) dissolving the compound III and the compound II in a first solvent;

[0017] (2) after the solid in step (1) is fully dissolved, adding a catalyst and reacting under protection of an inert atmosphere;

[0018] (3) after the reaction is completed, performing filtration, and washing the filter cake with a second solvent;

[0019] (4) eluting the washed filter cake, drying, and obtaining the hydrophilic porous organic polymer.

[0020] Preferably, in step (1), the first solvent is one or more of N,N-dimethylformamide, dichloromethane, trichloromethane, diisopropylamine, acetone, tetrahydrofuran, acetonitrile, toluene, ethanol and methanol; in step (3), the second solvent is one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, methanol.

[0021] Preferably, in step (2), the method of reaction under inert atmosphere protection is reaction under nitrogen or argon atmosphere at 20-120℃ for 24-72h; in step (4), the method of elution is elution with one or more of dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, methanol as eluent for 24-72h using a Soxhlet extractor; and the drying condition is 60-100℃, vacuum drying for 24-48h.

[0022] The present application further applies the above-mentioned hydrophilic porous organic polymer in the photocatalytic preparation of hydrogen peroxide.

[0023] The method for photocatalytic preparation of hydrogen peroxide using the hydrophilic porous organic polymer comprises any one of the following:

[0024] Method one: the hydrophilic porous organic polymer is added into water to obtain a reaction solution, at least one of air, oxygen or nitrogen is continuously introduced into the reaction solution, the reaction solution is stirred in the dark, and then light irradiation is performed for at least 10 minutes, and the light irradiation is simultaneously accompanied by continuous introduction of at least one of air, oxygen or nitrogen;

[0025] Method two: water and an alcohol reagent are added to the hydrophilic porous organic polymer to obtain a reaction solution, the reaction solution is stirred in the dark, and then light irradiation is performed for at least 10 minutes, and the light irradiation is simultaneously accompanied by continuous introduction of at least one of air, oxygen or nitrogen;

[0026] Method three: the hydrophilic porous organic polymer is added into water to obtain a reaction solution, the reaction solution is stirred in the dark, and then light irradiation is performed for at least 1 hour, and the light irradiation is simultaneously accompanied by continuous introduction of at least one of air, oxygen or nitrogen.

[0027] Preferably, the ratio of the hydrophilic porous organic polymer to water is 3-7mg: 15-25mL, preferably 5mg: 18-20mL.

[0028] In method two, the alcohol reagent is at least one of ethanol, methanol or isopropyl alcohol, and the volume ratio of water to alcohol reagent is 8-12:1, preferably 9-10:1.

[0029] Beneficial effects: Compared with the prior art, the present application has the following remarkable advantages: the present application prepares a porous organic polymer based on BODIPY, which inherits the photosensitive properties of BODIPY and can efficiently photocatalyze the production of hydrogen peroxide, and under appropriate catalytic conditions, the hydrogen peroxide yield can reach 5.81 mmol g -1 The present application 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 DRAWINGS

[0030] Figure 1 A 200nm scanning electron microscope image of the porous organic polymer BMSO based on BODIPY prepared in Example 1;

[0031] Figure 2 The water contact angle of the porous organic polymer BMSO based on BODIPY prepared in Example 1;

[0032] Figure 3 The infrared spectrum of the porous organic polymer BMSO based on BODIPY prepared in Example 1;

[0033] Figure 4 The X-ray diffraction pattern of the porous organic polymer BMSO based on BODIPY prepared in Example 1;

[0034] Figure 5 The nitrogen adsorption and desorption curve of the porous organic polymer BMSO based on BODIPY prepared in Example 1;

[0035] Figure 6 The rate comparison chart of the photocatalytic production of hydrogen peroxide of the porous organic polymer based on BODIPY prepared in Example 1 under different gas atmospheres;

[0036] Figure 7 The rate comparison chart of the photocatalytic production of hydrogen peroxide of the porous organic polymer BMSO based on BODIPY prepared in Example 1 under different sacrificial agent conditions;

[0037] Figure 8 The rate chart of the photocatalytic oxidation production of hydrogen peroxide of the porous organic polymer BMSO based on BODIPY prepared in Example 1 under long time. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be further described below in combination with the drawings.

[0039] Example 1: A porous organic polymer BMSO based on BODIPY, the structural unit of which is as follows:

[0040]

[0041] The preparation method of BMSO is as follows:

[0042]

[0043] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine (388 mg, 1 mmol), 3,7-dibromodibenzo[b,d]thiophene-5,5-dioxide (550 mg, 1.5 mmol), 40 mL of diisopropylamine and 80 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask, and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0044] (2) After the solution of step (1) was thoroughly mixed, tetrakis(triphenylphosphine)palladium (104 mg, 0.09 mmol), cuprous iodide (35 mg, 0.18 mmol) were sequentially added to the above reaction solution, and after being thoroughly dispersed, the mixed solution was heated to reflux at 120°C for 36 hours under a nitrogen atmosphere;

[0045] (3) After the reaction was completed, the reaction solution was cooled to room temperature and filtered, and the filter cake obtained by filtration was sequentially washed with water, methanol, tetrahydrofuran, N,N-dimethylformamide, diethyl ether and dichloromethane;

[0046] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and sequentially eluted with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours, and the eluted filter cake was transferred to a vacuum drying oven, and dried at 60°C for 24 hours under vacuum to obtain the porous organic polymer BMSO based on BODIPY, with a yield of 90%. The microstructure of BMSO is shown in Figure 1 , the hydrophilicity test results are shown in Figure 2 , the chemical structure test results are shown in Figure 3 and Figure 4 , in Figure 3 , BDP-3A is the above compound III, and BTDO is 3,7-dibromodibenzo thiophene sulfone. The nitrogen adsorption and desorption of BMSO was further tested, and the results are shown in Figure 5 .

[0047] Example 2: A porous organic polymer BPSO based on BODIPY, the structural unit of which is as follows:

[0048]

[0049] The preparation method of BPSO is as follows:

[0050]

[0051] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine (388 mg, 1 mmol), 2,8-dibromodibenzo[b,d]thiophene-5,5-dioxide (550 mg, 1.5 mmol), 40 mL diisopropylamine and 80 mL N,N-dimethylformamide were added into a 500 mL Schlenk flask, and stirred thoroughly for 30 minutes under nitrogen atmosphere;

[0052] (2) After the solution of step (1) was mixed thoroughly, tetrakis(triphenylphosphine)palladium (104 mg, 0.09 mmol), cuprous iodide (35 mg, 0.18 mmol) were sequentially added into the above reaction solution, and after being dispersed thoroughly, the mixed solution was heated to reflux at 120°C for 36 hours under nitrogen atmosphere;

[0053] (3) After the reaction was completed, the reaction solution was cooled to room temperature and filtered, and the obtained filter cake was sequentially washed with water, methanol, tetrahydrofuran, N,N-dimethylformamide, diethyl ether and dichloromethane;

[0054] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor, and eluted with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours, and the eluted filter cake was transferred to a vacuum drying oven, and dried at 60°C for 24 hours under vacuum to obtain a BODIPY-based porous organic polymer BPSO with a yield of 86%.

[0055] Example 3: A BODIPY-based porous organic polymer BMS, the structural unit of which is as follows:

[0056]

[0057] The preparation method of BMS is as follows:

[0058]

[0059] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrrolo[1,2-c:2',1'-f][1,3,2]diazaborocine (388 mg, 1 mmol), 3,7-dibromodibenzo[b,d]thiophene (513 mg, 1.5 mmol), 40 mL of diisopropylamine and 80 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask, and stirred sufficiently for 30 minutes under a nitrogen atmosphere;

[0060] (2) After the solution of step (1) was mixed sufficiently, tetrakis(triphenylphosphine)palladium (104 mg, 0.09 mmol), cuprous iodide (35 mg, 0.18 mmol) were sequentially added to the above reaction solution, and after being dispersed sufficiently, the mixed solution was heated to reflux at 120°C for 36 hours under a nitrogen atmosphere;

[0061] (3) After the reaction was completed, the reaction solution was cooled to room temperature and filtered, and the filter cake obtained by the filtration was sequentially washed with water, methanol, tetrahydrofuran, N,N-dimethylformamide, diethyl ether, dichloromethane;

[0062] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor, and eluted with dichloromethane, acetone, tetrahydrofuran, methanol for 36 hours, and the eluted filter cake was transferred to a vacuum drying oven, and dried at 60°C for 24 hours under vacuum to obtain a BODIPY-based porous organic polymer BMS at a yield of 81%.

[0063] Example 4: A BODIPY-based porous organic polymer BPS, the structural unit of which is as follows:

[0064]

[0065] A method for preparing BPS is as follows:

[0066]

[0067] (1) 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrrolo[1,2-c:2',1'-f][1,3,2]diazaborocine (388 mg, 1 mmol), 2,8-dibromodibenzo[b,d]thiophene (513 mg, 1.5 mmol), 40 mL of diisopropylamine and 80 mL of N,N-dimethylformamide were added to a 500 mL Schlenk flask, and stirred sufficiently for 30 minutes under a nitrogen atmosphere;

[0068] (2) After the solution of step (1) is mixed thoroughly, add tetrakis(triphenylphosphine)palladium (104 mg, 0.09 mmol) and cuprous iodide (35 mg, 0.18 mmol) to the above reaction solution in sequence, and after being dispersed thoroughly, heat the mixed solution to reflux at 120°C for 36 hours under a nitrogen atmosphere;

[0069] (3) After the reaction is completed, cool the reaction solution to room temperature and filter it. The filter cake obtained by filtration is washed with water, methanol, tetrahydrofuran, N,N-dimethylformamide, diethyl ether, and dichloromethane in sequence;

[0070] (4) Place the filter cake obtained in step (3) in a Soxhlet extractor, and elute it with dichloromethane, acetone, tetrahydrofuran, and methanol in sequence for 36 hours. After elution, transfer the filter cake to a vacuum drying oven, and dry it at 60°C for 24 hours under vacuum to obtain the porous organic polymer BMS based on BODIPY, with a yield of 72%.

[0071] Example 5: The rest is the same as Example 1, except that:

[0072] In step (1), the molar ratio of 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine to 3,7-dibromodibenzo[b,d]thiophene-5,5-dioxide is 1:1;

[0073] The catalyst is 1,1-bis(diphenylphosphino)ferrocene palladium dichloride and cuprous iodide.

[0074] In step (2), heat the mixed solution to reflux at 20°C for 72 hours under a nitrogen atmosphere;

[0075] In step (4), the elution time is 72 hours, and vacuum drying is performed at 100°C for 48 hours.

[0076] Example 6: The rest is the same as Example 1, except that:

[0077] In step (1), the molar ratio of 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine to 3,7-dibromodibenzo[b,d]thiophene-5,5-dioxide is 1:3;

[0078] In step (2), heat the mixed solution to reflux at 120°C for 24 hours under a nitrogen atmosphere;

[0079] In step (4), the elution time is 24 h, and the vacuum drying is performed at 80°C for 36 h.

[0080] Example 7: The BODIPY-based porous organic polymers obtained in Example 1, Example 2, Example 3 and Example 4 were used to produce hydrogen peroxide by photocatalytic oxidation in air, oxygen and nitrogen atmosphere, in the following way:

[0081] Test sample: the BODIPY-based porous organic polymers obtained in Example 1, Example 2, Example 3 and Example 4;

[0082] Test method: 5 mg of the test sample was added to a constant-temperature reactor, 20 mL of pure water was added, and air, oxygen or nitrogen was continuously introduced into the reaction solution before photocatalytic test. After stirring in the dark for 30 minutes, the reactor was irradiated with a 300-watt xenon lamp while continuously introducing air, oxygen or nitrogen. 2 mL of the reaction solution was taken at 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes and 60 minutes, respectively, and filtered with a 0.22-μm filter. 1.5 mL of the filtered solution was taken and added to a 5-mL centrifuge tube, 1 mL of 1-mol / L titanium potassium oxalate aqueous solution was added, and the mixture was reacted for 5 minutes. The absorbance was measured by ultraviolet-visible spectrophotometry, and the concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 1 and Figure 6

[0083] Table 1 Hydrogen peroxide yield of different porous organic polymers in different gas atmospheres

[0084]

[0085] Example 8: The BODIPY-based porous organic polymer obtained in Example 1 was used to produce hydrogen peroxide by photocatalytic oxidation in oxygen atmosphere after adding different cocatalysts, in the following way:

[0086] Test sample: the BODIPY-based porous organic polymer obtained in Example 1;

[0087] Test method: 5 mg of the test sample was added to a constant-temperature reactor, 18 mL of pure water was added, and 2 mL of one of ethanol, methanol or isopropanol was added. After stirring in the dark for 30 minutes, the reactor was irradiated with a 300-watt xenon lamp while continuously introducing oxygen. 2 mL of the reaction solution was taken at 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes and 60 minutes, respectively, and filtered with a 0.22-μm filter. 1.5 mL of the filtered solution was taken and added to a 5-mL centrifuge tube, 1 mL of 1-mol / L titanium potassium oxalate aqueous solution was added, and the mixture was reacted for 5 minutes. The absorbance was measured by ultraviolet-visible spectrophotometry, and the concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 2 and​Figure 7 as shown.

[0088] Table 2 Hydrogen peroxide yield of porous organic polymer under different cocatalyst conditions

[0089]

[0090] Example 9: The BODIPY-based porous organic polymer obtained in Example 1 was subjected to long-time accumulated photocatalytic oxidation to produce hydrogen peroxide under an oxygen atmosphere, in the following manner:

[0091] Test sample: the BODIPY-based porous organic polymer obtained in Example 1;

[0092] Test method: 5 mg of the test sample was added to a constant-temperature reactor, 20 mL of pure water was added, and after stirring in the dark for 30 minutes, the reactor was irradiated using a 300-watt xenon lamp while continuously bubbling oxygen. 2 mL of the reaction solution was taken at 1 hour, 2 hours, 3 hours, and 5 hours, and filtered using a 0.22-μm filter. 1.5 mL of the filtered solution was taken and added to a 5-mL centrifuge tube, 1 mL of 1-mol / L titanium potassium oxalate aqueous solution was added, and after mixing for 5 minutes, the absorbance was measured by ultraviolet-visible spectrophotometry, and the concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 3 and Figure 8 as shown.

[0093] Table 3 Yield of hydrogen peroxide produced by accumulated photocatalytic oxidation at different times

[0094]

[0095] As can be seen from the results in Table 3, after 2 hours, the accumulated yield of the porous organic polymer increased by a relatively small amount.

Claims

1. A hydrophilic porous organic polymer, characterized by, comprising a structural unit represented by formula (I): wherein Y is S or sulfonyl.

2. The method for producing a hydrophilic porous organic polymer according to claim 1, wherein comprising the following steps: wherein X is halogen and Y is S or sulfonyl.

3. The method for producing a hydrophilic porous organic polymer according to claim 2, wherein The catalyst is palladium catalyst and / or cuprous iodide, and the palladium catalyst is tetrakis(triphenylphosphine)palladium and / or 1,1-bis(diphenylphosphino)ferrocene palladium dichloride.

4. The method for producing a hydrophilic porous organic polymer according to claim 3, wherein The molar ratio of the compound III to the compound II is 1:1-3.

5. The method for preparing a hydrophilic porous organic polymer according to claim 2, wherein comprising the following steps: (1) dissolving the compound III and the compound II in a first solvent; (2) after the solid in step (1) is fully dissolved, adding a catalyst and reacting under the protection of an inert atmosphere; (3) after the reaction is completed, filtering, and washing the filter cake with a second solvent; (4) eluting, drying the washed filter cake, and obtaining the hydrophilic porous organic polymer.

6. The method for producing a hydrophilic porous organic polymer according to claim 5, wherein In step (1), the first solvent is one or more of N,N-dimethylformamide, dichloromethane, trichloromethane, diisopropylamine, acetone, tetrahydrofuran, acetonitrile, toluene, ethanol, and methanol; in step (3), the second solvent is one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, and methanol.

7. The method for preparing a hydrophilic porous organic polymer according to claim 5, wherein In step (2), the method of reacting under the protection of an inert atmosphere is reacting at 20-120℃ for 24-72h in a nitrogen or argon atmosphere; in step (4), the method of eluting is eluting for 24-72h with one or more of dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, and methanol as the eluent using a Soxhlet extractor; and the drying condition is vacuum drying at 60-100℃ for 24-48h.

8. The hydrophilic porous organic polymer according to claim 1 is used in the photocatalytic preparation of hydrogen peroxide.

9. Use according to claim 8, characterized in that, comprising any one of the following methods: Method one: adding the hydrophilic porous organic polymer into water to obtain a reaction solution, continuously bubbling at least one of air, oxygen, or nitrogen into the reaction solution, stirring the reaction solution in the dark, and then performing a light reaction for at least 10min, and continuously bubbling at least one of air, oxygen, or nitrogen during the light reaction; Method two: adding the hydrophilic porous organic polymer into water and an alcohol reagent to obtain a reaction solution, stirring the reaction solution in the dark, and then performing a light reaction for at least 10min, and continuously bubbling at least one of air, oxygen, or nitrogen during the light reaction; Method three: adding the hydrophilic porous organic polymer into water to obtain a reaction solution, stirring the reaction solution in the dark, and then performing a light reaction for at least 1h, and continuously bubbling at least one of air, oxygen, or nitrogen during the light reaction.

10. Use according to claim 9, characterized in that, The ratio of the hydrophilic porous organic polymer to water is 3-7mg:15-25mL; in method two, the alcohol reagent is at least one of ethanol, methanol, or isopropyl alcohol, and the volume ratio of water to the alcohol reagent is 8-12:1.

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