Method for preparing fluorine-boron dipyrrin-based porous organic polymer and application of the polymer in photocatalytic hydrogen peroxide production

Abstract

The application discloses a preparation method of a fluorobodipyrrin-based porous organic polymer and application of the fluorobodipyrrin-based porous organic polymer in photocatalytic production of hydrogen peroxide. The fluorobodipyrrin-based porous organic polymer is a fluorobodipyrrin-based porous organic polymer containing a cyano group, and the preparation method comprises the following steps: polymerizing an electron acceptor fluorobodipyrrin derivative and an electron donor compound through a Sonogashira coupling reaction to obtain a fluorobodipyrrin-based porous organic polymer containing an alkyne bond; and modifying the fluorobodipyrrin-based porous organic polymer containing the alkyne bond through a free radical reaction to obtain the fluorobodipyrrin-based porous organic polymer containing the cyano group. The electron acceptor fluorobodipyrrin is polymerized with different electron donors through the Sonogashira coupling reaction to obtain the fluorobodipyrrin-based porous organic polymer containing the alkyne bond, and the alkyne bond is post-modified through the free radical reaction to obtain the fluorobodipyrrin-based porous organic polymer containing the cyano group, which has good photocatalytic performance and can be used for photocatalytic production of hydrogen peroxide in water.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic materials technology, and in particular relates to a method for preparing a fluoroboron dipyrrole-based porous organic polymer and its application in photocatalytic hydrogen peroxide production. Background Technology

[0002] Hydrogen peroxide is a high-value chemical widely used in chemical synthesis, medical disinfection, and environmental applications. It is also used as a novel green energy storage material in fuel cells. This broad application prospect has prompted continuous efforts to develop efficient and environmentally friendly hydrogen peroxide production processes. To date, considerable efforts have been made to develop synthetic methods for hydrogen peroxide production. Traditional hydrogen peroxide production mainly uses the anthraquinone process; however, the anthraquinone process typically involves the use of toxic reagents (such as heavy aromatics and trioctyl phosphate) and the emission of toxic byproducts (such as carbon monoxide and hydrogen sulfide), which contradicts the current demand for low-carbon and environmentally friendly chemical production processes. Besides the anthraquinone process, the direct combination of H2 and O2 catalyzed by noble metals to synthesize hydrogen peroxide is also an important method, but this method faces challenges such as high cost, limited product selection, and the risk of direct explosion of H2 / O2 mixtures. In contrast, the synthesis of hydrogen peroxide using solar-driven photocatalysts with O2 and H2O as raw materials offers mild reaction conditions, simple and controllable operation, and no secondary pollution, making it a green and sustainable production method.

[0003] Porous organic polymers (POPs) possess advantages such as porosity, high crystallinity, designable building blocks, and high selectivity for hydrogen peroxide, making them excellent photocatalysts for hydrogen peroxide production. By designing a donor-acceptor (DA) system to construct a spatially separated redox center, excellent charge carrier kinetics and a long carrier lifetime can be achieved in POPs, thus efficiently generating hydrogen peroxide. Furthermore, fluoroboron dipyrrole is a high-performance photosensitizer. Its planar rigid conjugated structure consists of two pyrrole rings connected to a boron-nitrogen six-membered heterocycle, exhibiting good chemical stability and photophysical properties. Therefore, introducing fluoroboron dipyrrole as a photosensitizing unit into POPs allows for the adjustment of the specific surface area, photoelectric properties, and photocatalytic activity of POPs by regulating the ratio of polymerizable monomers. This optimizes the preparation process to achieve the best carrier transport efficiency, resulting in a POPs photocatalyst with optimal performance. However, while the rigid conjugated structure is beneficial for improving photoelectric performance, it also introduces hydrophobicity issues during application. The hydrophobicity of POPs can hinder the reaction of O2 and H2. +Interfacial mass transfer at the catalyst-H2O interface reduces the efficiency of photocatalytic hydrogen peroxide production. Therefore, considering the impact of mass transfer in practical photocatalytic applications, further functional modifications can be made to improve the hydrophilicity, stability, and solar energy utilization of POPs, as well as increase carrier transport channels and O2 adsorption sites. This is expected to yield highly efficient and stable POPs photocatalysts, thereby promoting the industrial application of photocatalysis in hydrogen peroxide production. Summary of the Invention

[0004] The main technical problem solved by this invention is to provide a method for preparing a fluoroboron dipyrrole-based porous organic polymer and its application in photocatalytic hydrogen peroxide production. The method utilizes the Sonogashira coupling reaction to polymerize electron acceptor fluoroboron dipyrrole with different electron donors to obtain a fluoroboron dipyrrole-based porous organic polymer containing alkyne bonds. The alkyne bonds are then post-modified via a free radical reaction to obtain a cyano-containing fluoroboron dipyrrole-based porous organic polymer with good photocatalytic performance. This polymer can photocatalytically produce hydrogen peroxide in water.

[0005] To solve the above-mentioned technical problems, one technical solution adopted by the present invention is: a method for preparing a fluoroboron dipyrrole-based porous organic polymer, wherein the fluoroboron dipyrrole-based porous organic polymer is a cyano-containing fluoroboron dipyrrole-based porous organic polymer, and the preparation method includes the following steps:

[0006] Step 1: Electron acceptor fluoroboron dipyrrole derivatives and electron donor compounds are polymerized via Sonogashira coupling reaction to obtain fluoroboron dipyrrole-based porous organic polymers containing alkyne bonds.

[0007] Step 2: The cyano-containing fluoroboron dipyrrole porous organic polymer is prepared by free radical modification of the fluoroboron dipyrrole porous organic polymer containing alkyne bonds.

[0008] Furthermore, preferably, the electron acceptor fluoroboron dipyrrole derivative has any of the following structures:

[0009]

[0010] Where R is any one of -H, -NO3, -SO4, -CN, -CH3, and -OCH3.

[0011] Furthermore, the electron donor compound is any one of 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole, 1,1,2,2-tetra(p-ethynylphenyl)ethylene, 1,3,6,8-tetraethynylpyrene, and 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] compounds, whose structural units are as follows:

[0012] Formula 1, 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole: Formula 2, 1,1,2,2-Tetra(p-ethynylphenyl)ethylene: Formula 3, 1,3,6,8-tetraynylpyrene: Formula 4, 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole]:

[0013] Furthermore, the preparation method of the fluoroboron dipyrrole-containing porous organic polymer containing alkyne bonds includes the following steps;

[0014] S1: Dissolve electron acceptor fluoroboron dipyrrole derivatives and electron donor compounds in a solvent;

[0015] S2: After the solid in step S1 has been fully dissolved, the catalyst is added, and the fully dispersed solution is reacted under a protective atmosphere.

[0016] S3: After the reaction is complete, filter the mixture and wash the filter cake with solvent.

[0017] S4: The solid obtained in step S3 is eluted using a Soxhlet extractor and dried under vacuum to obtain a porous organic polymer containing alkyne bonds and fluoroboron dipyrrole groups.

[0018] Furthermore, the molar ratio of the electron acceptor fluoroboron dipyrrole derivative and the electron donor compound in step S1 is 0.5:1 to 5:1;

[0019] The solvent is at least one selected from N,N-dimethylformamide, N,N-diisopropylethylamine, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

[0020] Furthermore, the molar ratio of the fluoroboron dipyrrole derivative and the catalyst in step S2 is 1:0.05 to 1:1;

[0021] The catalyst is at least one of tetrakis(triphenylphosphine)palladium, dichlorodi(triphenylphosphine)palladium, cuprous iodide, triphenylphosphine, and 1,10-phenanthroline;

[0022] The protective atmosphere is nitrogen or argon;

[0023] The reaction temperature is 25–100°C, and the reaction time is 12–72 hours.

[0024] Furthermore, the solvent for washing the filter cake in step S3 is at least one of diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, water, and methanol;

[0025] The eluent in step S4 is at least one of water, dichloromethane, tetrahydrofuran, acetonitrile, and methanol;

[0026] The elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100°C, and the vacuum drying time is 12 to 24 hours.

[0027] Furthermore, the fluoroboron dipyrrole-based porous organic polymer is a cyano-containing fluoroboron dipyrrole-based porous organic polymer, comprising the following steps:

[0028] S1: The prepared fluoroboron dipyrrole-containing porous organic polymer containing alkyne bonds is dispersed in a solvent;

[0029] S2: After the porous polymer in step S1 is fully dispersed, add the free radical reaction reagent, and react the mixed solution under a protective atmosphere;

[0030] S3: After the reaction is complete, filter the mixture from step S2 and wash the filter cake with solvent;

[0031] S4: The solid obtained in step S2 is eluted using a Soxhlet extractor and vacuum dried to obtain a cyano-containing fluoroboron dipyrrole porous organic polymer.

[0032] Furthermore, the solvent mentioned in step S1 is at least one selected from N,N-dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol;

[0033] In step S2, the molar ratio of the alkyne-containing fluoroboron dipyrrole porous organic polymer and the free radical reaction reagent is 1:0.1 to 1:5;

[0034] The free radical reaction reagent is tetracyanoethylene;

[0035] The protective atmosphere is nitrogen or argon;

[0036] The reaction temperature is 25–100°C, and the reaction time is 12–72 hours;

[0037] The solvent for washing the filter cake in step S3 is at least one of diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0038] The eluent in step S4 is at least one of dichloromethane, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100°C; and the vacuum drying time is 12 to 24 hours.

[0039] Furthermore, the present invention also provides an application of a fluoroboron dipyrrole porous organic polymer for photocatalytic hydrogen peroxide production, wherein the cyano-containing fluoroboron dipyrrole porous organic polymer is used for photocatalytic hydrogen peroxide production;

[0040] The light source for the photocatalytic production of hydrogen peroxide is a xenon lamp;

[0041] The amount of the cyano-containing fluoroboron dipyrrole-based porous organic polymer used is 0.1–1 mg / mL.

[0042] The beneficial effects of the present invention include at least the following:

[0043] This invention utilizes the Sonogashira coupling reaction to polymerize electron acceptor fluoroboron dipyrrole with different electron donors to obtain fluoroboron dipyrrole-based porous organic polymers containing alkyne bonds. Further modification of the alkyne bonds via free radical reactions yields cyano-containing fluoroboron dipyrrole-based porous organic polymers with excellent photocatalytic performance. This polymer can photocatalytically produce hydrogen peroxide in water. This invention provides a simple and feasible method and approach for the design, development, performance improvement, and green and clean production of hydrogen peroxide based on porous organic polymer photocatalysts. Attached Figure Description

[0044] Figure 1 Water contact angle diagram of BDP-CZ, a fluoroboron dipyrrole porous organic polymer containing alkyne bonds prepared in Example 1;

[0045] Figure 2 Water contact angle diagram of the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-CZ prepared in Example 1;

[0046] Figure 3 Thermogravimetric diagrams of BDP-CZ, a fluoroboron dipyrrole porous organic polymer containing alkyne bonds, and 4CN-BDP-CZ, a fluoroboron dipyrrole porous organic polymer containing cyano groups, are shown in Example 1.

[0047] Figure 4 The solid UV images are of the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-CZ and the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-CZ from Example 1.

[0048] Figure 5 Scanning electron microscope image of 4CN-BDP-CZ, a cyano-based fluoroboron dipyrrole-based porous organic polymer prepared in Example 1;

[0049] Figure 6 The image shows a comparison of the photocatalytic hydrogen peroxide production performance of the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-CZ and the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-CZ prepared in Example 1. Detailed Implementation

[0050] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby providing a clearer and more explicit definition of the scope of protection of the present invention.

[0051] Example: A method for preparing a fluoroboron dipyrrole-based porous organic polymer, wherein the fluoroboron dipyrrole-based porous organic polymer is a cyano-containing fluoroboron dipyrrole-based porous organic polymer, and the preparation method includes the following steps:

[0052] Step 1: Electron acceptor fluoroboron dipyrrole derivatives and electron donor compounds are polymerized via Sonogashira coupling reaction to obtain fluoroboron dipyrrole-based porous organic polymers containing alkyne bonds.

[0053] Step 2: The cyano-containing fluoroboron dipyrrole porous organic polymer is prepared by free radical modification of the fluoroboron dipyrrole porous organic polymer containing alkyne bonds.

[0054] Preferably, the electron acceptor fluoroboron dipyrrole derivative has any one of the following structures:

[0055]

[0056] Where R is any one of -H, -NO3, -SO4, -CN, -CH3, and -OCH3.

[0057] The electron donor compound is any one of 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole, 1,1,2,2-tetra(p-ethynylphenyl)ethylene, 1,3,6,8-tetraethynylpyrene, and 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] compounds, with the following structural unit:

[0058] Formula 1, 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole: Formula 2, 1,1,2,2-Tetra(p-ethynylphenyl)ethylene: Formula 3, 1,3,6,8-tetraynylpyrene: Formula 4, 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole]:

[0059] The method for preparing the alkyne-containing fluoroboron dipyrrole-based porous organic polymer includes the following steps;

[0060] S1: Dissolve electron acceptor fluoroboron dipyrrole derivatives and electron donor compounds in a solvent;

[0061] S2: After the solid in step S1 has been fully dissolved, the catalyst is added, and the fully dispersed solution is reacted under a protective atmosphere.

[0062] S3: After the reaction is complete, filter the mixture and wash the filter cake with solvent.

[0063] S4: The solid obtained in step S3 is eluted using a Soxhlet extractor and dried under vacuum to obtain a porous organic polymer containing alkyne bonds and fluoroboron dipyrrole groups.

[0064] The molar ratio of the electron acceptor fluoroboron dipyrrole derivative and the electron donor compound in step S1 is 0.5:1 to 5:1;

[0065] The solvent is at least one selected from N,N-dimethylformamide, N,N-diisopropylethylamine, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

[0066] In step S2, the molar ratio of the fluoroboron dipyrrole derivative to the catalyst is 1:0.05 to 1:1;

[0067] The catalyst is at least one of tetrakis(triphenylphosphine)palladium, dichlorodi(triphenylphosphine)palladium, cuprous iodide, triphenylphosphine, and 1,10-phenanthroline;

[0068] The protective atmosphere is nitrogen or argon;

[0069] The reaction temperature is 25–100°C, and the reaction time is 12–72 hours.

[0070] The solvent for washing the filter cake in step S3 is at least one of diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, water, and methanol.

[0071] The eluent in step S4 is at least one of water, dichloromethane, tetrahydrofuran, acetonitrile, and methanol;

[0072] The elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100°C, and the vacuum drying time is 12 to 24 hours.

[0073] The fluoroboron dipyrrole-based porous organic polymer is a cyano-containing fluoroboron dipyrrole-based porous organic polymer, comprising the following steps:

[0074] S1: The prepared fluoroboron dipyrrole-containing porous organic polymer containing alkyne bonds is dispersed in a solvent;

[0075] S2: After the porous polymer in step S1 is fully dispersed, add the free radical reaction reagent, and react the mixed solution under a protective atmosphere;

[0076] S3: After the reaction is complete, filter the mixture from step S2 and wash the filter cake with solvent;

[0077] S4: The solid obtained in step S2 is eluted using a Soxhlet extractor and vacuum dried to obtain a cyano-containing fluoroboron dipyrrole porous organic polymer.

[0078] The solvent mentioned in step S1 is at least one selected from N,N-dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

[0079] In step S2, the molar ratio of the alkyne-containing fluoroboron dipyrrole porous organic polymer and the free radical reaction reagent is 1:0.1 to 1:5;

[0080] The free radical reaction reagent is tetracyanoethylene;

[0081] The protective atmosphere is nitrogen or argon;

[0082] The reaction temperature is 25–100°C, and the reaction time is 12–72 hours;

[0083] The solvent for washing the filter cake in step S3 is at least one of diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0084] The eluent in step S4 is at least one of dichloromethane, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100°C; and the vacuum drying time is 12 to 24 hours.

[0085] This invention also provides an application of a fluoroboron dipyrrole-based porous organic polymer for photocatalytic hydrogen peroxide production, wherein the cyano-containing fluoroboron dipyrrole-based porous organic polymer is used for photocatalytic hydrogen peroxide production;

[0086] The light source for the photocatalytic production of hydrogen peroxide is a xenon lamp;

[0087] The amount of the cyano-containing fluoroboron dipyrrole-based porous organic polymer used is 0.1–1 mg / mL.

[0088] In specific implementation, the preparation method of the fluoroboron dipyrrole-based porous organic polymer of the present invention is shown in Examples 1-4;

[0089] Example 1, according to the following synthetic route ( Figure 3 Thermogravimetric diagrams of BDP-CZ, a fluoroboron dipyrrole porous organic polymer containing alkyne bonds, and 4CN-BDP-CZ, a fluoroboron dipyrrole porous organic polymer containing cyano groups. Figure 4Solid UV images of BDP-CZ, a porous organic polymer with alkyne bonds and 4CN-BDP-CZ, a porous organic polymer with cyano groups:

[0090] (1) 5,5-difluoro-2,8-diiodo-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexylborane (3.20 g, 5.60 mmol), 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole (1.20 g, 2.80 mmol), 150 mL N,N-dimethylformamide (DMF), and 5 mL N,N-diisopropylethylamine (DIEA) were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0091] (2) After the solution in step (1) is fully mixed, copper iodide (0.11 g, 0.56 mmol) and tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol) are added to the above reaction solution. After being fully dispersed, the mixture is heated to 100°C and reacted for 72 hours under a nitrogen atmosphere.

[0092] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0093] (4) The filter cake obtained after washing in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, tetrahydrofuran, and methanol for 36 hours. The eluted solid was then transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain the fluoroboron dipyrrole-containing porous organic polymer BDP-CZ with an alkyne bond, yielding 90%. Figure 1 (Water contact angle diagram of the prepared alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-CZ).

[0094] (5) Place the fluoroboron dipyrrole porous organic polymer BDP-CZ (1.20 g, 1.60 mmol) containing alkyne bonds obtained in step (4) and 100 mL of chloroform into a 250 mL Schlenk flask and stir and disperse for 30 minutes under a nitrogen atmosphere.

[0095] (6) After the mixture in step (5) is fully dispersed, tetracyanoethylene (0.20 g, 1.60 mmol) is added in batches. The reaction solution is stirred for 30 minutes and then heated to 65°C for 72 hours.

[0096] (7) After the reaction is completed, the reaction solution is cooled to room temperature and then filtered. The filter cake obtained by filtration is washed with methanol, N,N-dimethylformamide, diethyl ether and dichloromethane in sequence.

[0097] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, tetrahydrofuran, and methanol for 36 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain a cyano-containing fluoroboron dipyrrole-based porous organic polymer 4CN-BDP-CZ with a yield of 91%. Figure 2 The water contact angle diagram for the prepared cyano-containing fluoroboron dipyrrole-based porous organic polymer 4CN-BDP-CZ is shown. Figure 5 Scanning electron microscope image of 4CN-BDP-CZ, a cyano-based fluoroboron dipyrrole-based porous organic polymer.

[0098]

[0099] Example 2, according to the following synthetic route:

[0100] (1) 5,5-difluoro-2,8-diiodo-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexylborane (3.20 g, 5.60 mmol), 1,1,2,2-tetra(p-ethynylphenyl)ethylene (1.22 g, 2.80 mmol), 150 mL DMF, and 5 mL DIEA 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, copper iodide (0.11 g, 0.56 mmol) and tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol) are added to the above reaction solution. After being fully dispersed, the mixture is heated to 100°C and reacted for 72 hours under a nitrogen atmosphere.

[0102] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0103] (4) The filter cake obtained after washing in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, tetrahydrofuran and methanol as eluents for 36 hours in sequence. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain the fluoroboron dipyrrole porous organic polymer BDP-TPE containing alkyne bonds, with a yield of 93%.

[0104] (5) Place the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-TPE (1.27 g, 1.60 mmol) obtained in step (4) and 100 mL of chloroform into a 250 mL Schlenk flask and stir and disperse for 30 minutes under a nitrogen atmosphere.

[0105] (6) After the mixture in step (5) is fully dispersed, tetracyanoethylene (0.20 g, 1.60 mmol) is added in batches. The reaction solution is stirred for 30 minutes and then heated to 65°C for 72 hours.

[0106] (7) After the reaction is completed, the reaction solution is cooled to room temperature and then filtered. The filter cake obtained by filtration is washed with methanol, N,N-dimethylformamide, diethyl ether and dichloromethane in sequence.

[0107] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, tetrahydrofuran and methanol for 36 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-TPE with a yield of 94%.

[0108]

[0109] Example 3, according to the following synthetic route:

[0110] (1) 5,5-difluoro-2,8-diiodo-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexylborane (3.20 g, 5.60 mmol), 1,3,6,8-tetraynylpyrene (0.84 g, 2.80 mmol), 150 mL DMF, and 5 mL DIEA were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0111] (2) After the solution in step (1) is fully mixed, copper iodide (0.11 g, 0.56 mmol) and tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol) are added to the above reaction solution. After being fully dispersed, the mixture is heated to 100°C and reacted for 72 hours under a nitrogen atmosphere.

[0112] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0113] (4) The filter cake obtained after washing in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, tetrahydrofuran and methanol as eluents for 36 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain the fluoroboron dipyrrole porous organic polymer BDP-Py containing alkyne bonds, with a yield of 93%.

[0114] (5) Place the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-Py (1.06 g, 1.6 mmol) obtained in step (4) and 100 mL of chloroform into a 250 mL Schlenk flask and stir and disperse for 30 minutes under a nitrogen atmosphere.

[0115] (6) After the mixture in step (5) is fully dispersed, tetracyanoethylene (0.20 g, 1.6 mmol) is added in batches. The reaction solution is stirred for 30 minutes and then heated to 65°C for 72 hours.

[0116] (7) After the reaction is completed, the reaction solution is cooled to room temperature and then filtered. The filter cake obtained by filtration is washed with methanol, N,N-dimethylformamide, diethyl ether and dichloromethane in sequence.

[0117] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, tetrahydrofuran and methanol for 36 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-Py with a yield of 92%.

[0118]

[0119] Example 4, following the synthetic route:

[0120] (1) 5,5-difluoro-2,8-diiodo-1,3,7,9-tetramethyl-10-phenyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexylborane (3.20 g, 5.60 mmol), 9,9′-(1,4-phenylene)bis[3,6-dieethynyl-9H-carbazole] (1.32 g, 2.80 mmol), 150 mL DMF, and 5 mL DIEA were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0121] (2) After the solution in step (1) is fully mixed, copper iodide (0.11 g, 0.56 mmol) and tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol) are added to the above reaction solution. After being fully dispersed, the mixture is heated to 100°C and reacted for 72 hours under a nitrogen atmosphere.

[0122] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0123] (4) The filter cake obtained after washing in step (3) was placed in a Soxhlet extractor and eluted with dichloromethane, tetrahydrofuran and methanol as eluents for 36 hours in sequence. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain a fluoroboron dipyrrole porous organic polymer BDP-TPA containing alkyne bonds, with a yield of 92%.

[0124] (5) Place the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-TPA (1.32 g, 1.6 mmol) obtained in step (4) and 100 mL of chloroform into a 250 mL Schlenk flask and stir and disperse for 30 minutes under a nitrogen atmosphere.

[0125] (6) After the mixture in step (5) is fully dispersed, tetracyanoethylene (0.20 g, 1.6 mmol) is added in batches. The reaction solution is stirred for 30 minutes and then heated to 65°C for 72 hours.

[0126] (7) After the reaction is completed, the reaction solution is cooled to room temperature and then filtered. The filter cake obtained by filtration is washed with methanol, N,N-dimethylformamide, diethyl ether and dichloromethane in sequence.

[0127] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, tetrahydrofuran and methanol for 36 hours. The eluted solid was transferred to a vacuum drying oven and dried under vacuum at 70°C for 24 hours to obtain cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-TPA with a yield of 93%.

[0128]

[0129] The yields of each stage in Examples 1-4 above are shown in Table 1 below:

[0130] Table 1

[0131]

[0132] The fluoroboron dipyrrole-based porous organic polymers containing alkyne bonds and cyano groups obtained in Examples 1-4 were subjected to photocatalytic hydrogen peroxide production, resulting in Application Examples 1-4. The peroxide yields are shown in Table 2 below.

[0133] Application Example 1

[0134] The photocatalytic hydrogen peroxide production performance of the fluoroboron dipyrrole-based porous organic polymer containing alkyne and cyano groups obtained in Example 1 was studied. Figure 6 Comparison of photocatalytic hydrogen peroxide production performance between BDP-CZ, a porous organic polymer with alkyne bonds and 4CN-BDP-CZ, a porous organic polymer with cyano groups;

[0135] Test samples: the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-CZ and the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-CZ obtained in Example 1;

[0136] Hydrogen peroxide detection method: Prepare a 5mM potassium titanium oxalate (IV) solution;

[0137] Experimental Method: 5 mg of BDP-CZ and 4 CN-BDP-CZ were added to a quartz catalytic reactor, followed by 20 mL of deionized water and stirring thoroughly for 30 minutes to reach adsorption-desorption equilibrium. Finally, a photocatalytic hydrogen peroxide production experiment was conducted using a 300W xenon lamp to simulate sunlight at room temperature for 1 hour. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The hydrogen peroxide concentration of the filtrate was determined using the potassium titanium oxalate method: 1.5 mL of the solution was mixed with 1 mL of a 5 mM potassium titanium oxalate (IV) solution. Due to the formation of titanium peroxide, the solution changed from transparent to yellow. The concentration of hydrogen peroxide was calculated by measuring the absorbance at 400 nm using a UV-Vis spectrometer, as shown in Table 2.

[0138] Application Example 2

[0139] The photocatalytic hydrogen peroxide production performance of the fluoroboron dipyrrole-based porous organic polymer containing alkyne bonds and cyano groups obtained in Example 2 was studied.

[0140] Test samples: the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-TPE and the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-TPE obtained in Example 2;

[0141] Hydrogen peroxide detection method: Prepare a 5mM potassium titanium oxalate (IV) solution;

[0142] Experimental Method: 5 mg of BDP-TPE and 4 CN-BDP-TPE were added to a quartz catalytic reactor, followed by 20 mL of deionized water and stirring thoroughly for 30 minutes to reach adsorption-desorption equilibrium. Finally, a photocatalytic hydrogen peroxide production experiment was conducted using a 300W xenon lamp to simulate sunlight at room temperature for 1 hour. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The hydrogen peroxide concentration of the filtrate was determined using the potassium titanium oxalate method: 1.5 mL of the solution was mixed with 1 mL of a 5 mM potassium titanium oxalate (IV) solution. Due to the formation of titanium peroxide, the solution changed from transparent to yellow. The concentration of hydrogen peroxide was calculated by measuring the absorbance at 400 nm using a UV-Vis spectrometer, as shown in Table 2.

[0143] Application Example 3

[0144] The photocatalytic hydrogen peroxide production performance of the fluoroboron dipyrrole-based porous organic polymer containing alkyne bonds and cyano groups obtained in Example 3 was studied.

[0145] Test samples: the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-Py and the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-Py obtained in Example 3;

[0146] Hydrogen peroxide detection method: Prepare a 5mM potassium titanium oxalate (IV) solution;

[0147] Experimental Method: 5 mg of BDP-Py and 4 CN-BDP-Py were added to a quartz catalytic reactor, followed by 20 mL of deionized water and stirring thoroughly for 30 minutes to reach adsorption-desorption equilibrium. Finally, a photocatalytic hydrogen peroxide production experiment was conducted using a 300W xenon lamp to simulate sunlight at room temperature for 1 hour. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The hydrogen peroxide concentration of the filtrate was determined using the potassium titanium oxalate method: 1.5 mL of the solution was mixed with 1 mL of a 5 mM potassium titanium oxalate (IV) solution. Due to the formation of titanium peroxide, the solution changed from transparent to yellow. The concentration of hydrogen peroxide was calculated by measuring the absorbance at 400 nm using a UV-Vis spectrometer, as shown in Table 2.

[0148] Application Example 4

[0149] The photocatalytic hydrogen peroxide production performance of the fluoroboron dipyrrole-based porous organic polymer containing alkyne bonds and cyano groups obtained in Example 4 was studied.

[0150] Test samples: the alkyne-containing fluoroboron dipyrrole porous organic polymer BDP-TPA and the cyano-containing fluoroboron dipyrrole porous organic polymer 4CN-BDP-TPA obtained in Example 3;

[0151] Hydrogen peroxide detection method: Prepare a 5mM potassium titanium oxalate (IV) solution;

[0152] Experimental Method: 5 mg of BDP-TPA and 4 CN-BDP-TPA were added to a quartz catalytic reactor, followed by 20 mL of deionized water and stirring thoroughly for 30 minutes to reach adsorption-desorption equilibrium. Finally, a photocatalytic hydrogen peroxide production experiment was conducted using a 300W xenon lamp to simulate sunlight at room temperature for 1 hour. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The hydrogen peroxide concentration of the filtrate was determined using the potassium titanium oxalate method: 1.5 mL of the solution was mixed with 1 mL of a 5 mM potassium titanium oxalate (IV) solution. Due to the formation of titanium peroxide, the solution changed from transparent to yellow. The concentration of hydrogen peroxide was calculated by measuring the absorbance at 400 nm using a UV-Vis spectrometer, as shown in Table 2.

[0153] The results of the above application examples are summarized in Table 2:

[0154] Table 2

[0155]

[0156] It is evident that by using the Sonogashira coupling reaction to polymerize electron acceptor fluoroboron dipyrrole with different electron donors, alkyne-containing fluoroboron dipyrrole-based porous organic polymers can be obtained. Furthermore, by post-modifying the alkyne bonds through a free radical reaction, cyano-containing fluoroboron dipyrrole-based porous organic polymers with good photocatalytic performance can be obtained. This catalyst can significantly improve the yield of hydrogen peroxide.

[0157] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent structural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. An application of a fluoroboron dipyrrole-based porous organic polymer in photocatalytic hydrogen peroxide production, characterized in that: The fluoroboron dipyrrole-based porous organic polymer is a cyano-containing fluoroboron dipyrrole-based porous organic polymer, and its preparation method includes the following steps: Step 1: Electron acceptor fluoroboron dipyrrole derivatives and electron donor compounds are polymerized via Sonogashira coupling reaction to obtain fluoroboron dipyrrole-based porous organic polymers containing alkyne bonds. Step 2: The cyano-containing fluoroboron dipyrrole porous organic polymer is prepared by free radical modification of the fluoroboron dipyrrole porous organic polymer containing alkyne bonds; The electron donor compound is any one of 3,3ʹ,6,6ʹ-tetraethynyl-9,9ʹ-biscarbazole, 1,1,2,2-tetra(p-ethynylphenyl)ethylene, and 9,9ʹ-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] compounds, with the following structural unit: Formula 1, 3,3ʹ,6,6ʹ-tetraethynyl-9,9ʹ-biscarbazole: ; Formula 2, 1,1,2,2-Tetra(p-ethynylphenyl)ethylene: ; Formula 4, 9,9ʹ-(1,4-phenylene)bis[3,6-dieethynyl-9H-carbazole]: ; The electron acceptor fluoroboron dipyrrole derivative has any one of the following structures: ； Where R is any one of -H, -CH3, and -OCH3; The molar ratio of the electron acceptor fluoroboron dipyrrole derivative and the electron donor compound in step one is 0.5:1 to 5:1; In step two, the molar ratio of the alkyne-containing fluoroboron dipyrrole porous organic polymer and the free radical reaction reagent is 1:0.1 to 1:5; The free radical reaction reagent is tetracyanoethylene; The preparation method of the cyano-containing fluoroboron dipyrrole-based porous organic polymer includes the following steps: S1: The prepared fluoroboron dipyrrole-containing porous organic polymer containing alkyne bonds is dispersed in a solvent; S2: After the porous polymer in step S1 is fully dispersed, add the free radical reaction reagent, and react the mixed solution under a protective atmosphere; S3: After the reaction is complete, filter the mixture from step S2 and wash the filter cake with solvent; S4: The solid obtained in step S2 is eluted with a Soxhlet extractor and vacuum dried to obtain a cyano-containing fluoroboron dipyrrole porous organic polymer. The cyano-containing fluoroboron dipyrrole porous organic polymer is used in the photocatalytic production of hydrogen peroxide; The light source for the photocatalytic production of hydrogen peroxide is a xenon lamp; The amount of the cyano-containing fluoroboron dipyrrole-based porous organic polymer used is 0.1–1 mg / mL.

2. The application of the fluoroboron dipyrrole-based porous organic polymer for photocatalytic hydrogen peroxide production according to claim 1, characterized in that: The method for preparing the alkyne-containing fluoroboron dipyrrole-based porous organic polymer includes the following steps; A1: Dissolve electron acceptor fluoroboron dipyrrole derivatives and electron donor compounds in a solvent; A2: After the solid in step A1 has been fully dissolved, the catalyst is added, and the fully dispersed solution is reacted under a protective atmosphere; A3: After the reaction is complete, filter the mixture and wash the filter cake with solvent; A4: The solid obtained in step A3 was eluted using a Soxhlet extractor and vacuum dried to obtain a porous organic polymer containing alkyne bonds and fluoroboron dipyrrole groups.

3. The application of the photocatalytic hydrogen peroxide production of a fluoroboron dipyrrole-based porous organic polymer according to claim 2, characterized in that: The solvent mentioned in step A1 is at least one selected from N,N-dimethylformamide, N,N-diisopropylethylamine, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

4. The application of the fluoroboron dipyrrole-based porous organic polymer for photocatalytic hydrogen peroxide production according to claim 2, characterized in that: The molar ratio of the fluoroboron dipyrrole derivative and the catalyst in step A2 is 1:0.05 to 1:1; The catalyst is at least one of tetrakis(triphenylphosphine)palladium, dichlorodi(triphenylphosphine)palladium, cuprous iodide, triphenylphosphine, and 1,10-phenanthroline; The protective atmosphere is nitrogen or argon; The reaction temperature is 25–100°C, and the reaction time is 12–72 hours.

5. The application of the fluoroboron dipyrrole-based porous organic polymer for photocatalytic hydrogen peroxide production according to claim 2, characterized in that: The solvent for washing the filter cake in step A3 is at least one of diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, water, and methanol. In step A4, the eluent is at least one of water, dichloromethane, tetrahydrofuran, acetonitrile, and methanol; The elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100°C, and the vacuum drying time is 12 to 24 hours.

6. The application of the fluoroboron dipyrrole-based porous organic polymer for photocatalytic hydrogen peroxide production according to claim 1, characterized in that: The solvent mentioned in step S1 is at least one selected from N,N-dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol. The protective atmosphere is nitrogen or argon; The reaction temperature is 25–100°C, and the reaction time is 12–72 hours; The solvent for washing the filter cake in step S3 is at least one of diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol. In step S4, the eluent is at least one of dichloromethane, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100°C; and the vacuum drying time is 12 to 24 hours.

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