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

Abstract

The invention discloses a preparation method of a boron-dipyrrolyl porous organic polymer and application of the boron-dipyrrolyl porous organic polymer in photocatalytic production of hydrogen peroxide. The boron-dipyrrolyl porous organic polymer is a cyano-containing boron-dipyrrolyl porous organic polymer. The preparation method comprises the following steps: carrying out a Sonogashira coupling reaction on an electron acceptor boron dipyrromethene derivative and an electron donor compound to prepare a boron dipyrromethene-based porous organic polymer containing acetylenic bonds; and carrying out free radical reaction modification on the BODIPY porous organic polymer containing the acetylenic bond to prepare the BODIPY porous organic polymer containing the cyano group. The preparation method comprises the following steps: polymerizing an electron acceptor boron dipyrromethene and different electron donors by utilizing a Sonogashira coupling reaction to obtain a boron dipyrromethene-based porous organic polymer containing an acetylenic bond, and carrying out post-modification on the acetylenic bond through a free radical reaction to obtain the boron dipyrromethene-based porous organic polymer containing cyano groups with good photocatalytic performance. The polymer can be used for photocatalytic production of hydrogen peroxide in water.

Description

Technical Field

[0001] The invention belongs to the technical field of photocatalytic materials, and particularly relates to a preparation method of a fluoroboron dipyrrol-based porous organic polymer and its application in photocatalytic production of hydrogen peroxide. Background Art

[0002] Hydrogen peroxide is a high-value chemical widely used in chemical synthesis, medical disinfection, environment and other fields. At the same time, it is also used in fuel cells as a new type of green energy storage material. The broad application prospects have prompted people to continuously seek efficient and environmentally friendly hydrogen peroxide production processes. So far, people have made considerable efforts to develop synthetic methods for producing hydrogen peroxide. Traditional hydrogen peroxide production mainly adopts the anthraquinone method. However, the production of hydrogen peroxide by the anthraquinone method usually 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 runs counter to the current demand for low-carbon and environmentally friendly chemical production processes. In addition to the anthraquinone method, the direct combination of H2 and O2 catalyzed by precious metals to synthesize hydrogen peroxide is also one of the important methods, but this method faces challenges such as high cost, few product choices, and the risk of direct explosion of H2 / O2 mixtures. In contrast, the synthesis of hydrogen peroxide using solar-driven photocatalysts uses O2 and H2O as raw materials, has mild reaction conditions, simple and controllable operation, and no secondary pollution. It is a green and sustainable production method.

[0003] Porous organic polymers (POPs) are good photocatalysts for producing hydrogen peroxide due to their porosity, high crystallinity, designable building blocks, and high hydrogen peroxide selectivity. By designing a donor-acceptor (DA) system to construct a spatially separated redox center, excellent charge carrier dynamics and long carrier lifetime can be achieved in POPs, thereby effectively producing hydrogen peroxide. In addition, fluoroboranedipyrrole is a class of photosensitizers with excellent performance. Its planar rigid conjugated structure consists of two pyrrole rings and a boron nitrogen six-membered heterocycle connected together, and has good chemical stability and photophysical properties. Therefore, fluoroboranedipyrrole is introduced as a photosensitive unit in POPs, and the specific surface area, photoelectric properties, and photocatalytic activity of POPs are adjusted by adjusting the ratio of polymerized monomers, thereby optimizing the preparation process with the best carrier transfer efficiency and obtaining the best-performing POPs photocatalyst. However, although the rigid conjugated structure is beneficial to improving the photoelectric performance, it also brings about the problem of hydrophobicity in the application process, and the hydrophobicity of POPs will hinder the transfer of O2 and H +The interfacial mass transfer at the catalyst-H2O interface reduces the efficiency of photocatalytic hydrogen peroxide production. Therefore, combined with the mass transfer effect of the actual photocatalytic application process, further functional post-modification is performed to improve the hydrophilicity, stability and utilization rate of sunlight of POPs, and to increase the carrier transmission channel and O2 adsorption sites, so as to obtain efficient and stable POPs photocatalysts to promote the industrial application of photocatalytic technology in the production of hydrogen peroxide. Summary of the invention

[0004] The main technical problem solved by the present invention is to provide a preparation method of a fluoroboron dipyrrol-based porous organic polymer and its application in photocatalytic production of hydrogen peroxide. The electron acceptor fluoroboron dipyrrol is polymerized with different electron donors by Sonogashira coupling reaction to obtain an acetylene-containing fluoroboron dipyrrol-based porous organic polymer, and the acetylene bond is post-modified by free radical reaction to obtain a cyanide-containing fluoroboron dipyrrol-based porous organic polymer with good photocatalytic performance. The polymer can photocatalytically produce hydrogen peroxide in water.

[0005] In order to solve the above technical problems, a technical solution adopted by the present invention is: a method for preparing a fluoroboron dipyrrol-based porous organic polymer, wherein the fluoroboron dipyrrol-based porous organic polymer is a fluoroboron dipyrrol-based porous organic polymer containing a cyano group, and the preparation method comprises the following steps:

[0006] Step 1: polymerizing an electron acceptor fluoroborane dipyrrole derivative and an electron donor compound through a Sonogashira coupling reaction to obtain an acetylenic bond-containing fluoroborane dipyrrole-based porous organic polymer;

[0007] Step 2: The fluoroboron dipyrrol-based porous organic polymer containing cyano groups is prepared by modifying the fluoroboron dipyrrol-based porous organic polymer containing acetylenic bonds through free radical reaction.

[0008] Furthermore, preferably, the electron acceptor fluoroborane dipyrrole derivative is any one of the following structures:

[0009]

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

[0011] Further, 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-tetraynylpyrene, 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] compounds, and its structural unit is as follows:

[0012] Formula 1, 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole: Formula 2, 1,1,2,2-tetrakis(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 method for preparing the fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond comprises the following steps:

[0014] S1: dissolving the electron acceptor fluoroboranedipyrrole derivative and the electron donor compound in a solvent;

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

[0016] S3: After the reaction is completed, the filter is filtered and the filter cake is washed with a solvent;

[0017] S4: The solid obtained in step S3 is eluted with a Soxhlet extractor and vacuum dried to obtain a fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond.

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

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

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

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

[0022] The protective atmosphere is nitrogen or argon;

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

[0024] Furthermore, the solvent for washing the filter cake in step S3 is at least one of 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 fluoroborane dipyrrol-based porous organic polymer is a fluoroborane dipyrrol-based porous organic polymer containing a cyano group, and comprises the following steps:

[0028] S1: dispersing the prepared fluoroborane dipyrrol-based porous organic polymer containing an alkyne bond in a solvent;

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

[0030] S3: After the reaction is completed, the mixed solution in step S2 is filtered, and the filter cake is washed with a solvent;

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

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

[0033] In step S2, the molar ratio of the fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond to 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 to 100° C., and the reaction time is 12 to 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 dipyrrol-based porous organic polymer to produce hydrogen peroxide by photocatalysis, wherein the fluoroboron dipyrrol-based porous organic polymer containing a cyanide group is applied to produce hydrogen peroxide by photocatalysis;

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

[0041] The dosage of the cyano-containing fluoroboron dipyrrol-based porous organic polymer is 0.1-1 mg / mL.

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

[0043] The invention utilizes Sonogashira coupling reaction to polymerize electron acceptor fluoroboron dipyrrole with different electron donors to obtain fluoroboron dipyrrole-based porous organic polymer containing alkyne bonds, and post-modifies the alkyne bonds through free radical reaction to obtain cyano-containing fluoroboron dipyrrole-based porous organic polymer with good photocatalytic performance. The polymer can photocatalytically produce hydrogen peroxide in water. The invention provides a simple and feasible method and idea for the design and development of photocatalysts based on porous organic polymers, performance improvement, and green and clean production of hydrogen peroxide. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is a water contact angle diagram of the alkyne-bonded fluoroboron dipyrrol-based porous organic polymer BDP-CZ prepared in Example 1;

[0045] Figure 2 This is a water contact angle diagram of the cyano-containing fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ prepared in Example 1;

[0046] Figure 3 The thermogravimetric diagrams of the fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an alkyne bond and the fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ containing a cyano group in Example 1;

[0047] Figure 4 The solid UV images of the alkyne-containing fluoroboron dipyrrol-based porous organic polymer BDP-CZ and the cyano-containing fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ in Example 1;

[0048] Figure 5 This is a scanning electron microscope image of the cyano-based fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ prepared in Example 1;

[0049] Figure 6 This is a comparison chart of the photocatalytic hydrogen peroxide production performance of the alkyne-containing fluoroboron dipyrrol-based porous organic polymer BDP-CZ and the cyano-containing fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ prepared in Example 1. DETAILED DESCRIPTION

[0050] The preferred embodiments of the present invention are described in detail below in conjunction with 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 making a clearer and more definite definition of the protection scope of the present invention.

[0051] Embodiment: A method for preparing a fluoroboron dipyrrol-based porous organic polymer, wherein the fluoroboron dipyrrol-based porous organic polymer is a fluoroboron dipyrrol-based porous organic polymer containing a cyano group, and the preparation method comprises the following steps:

[0052] Step 1: polymerizing an electron acceptor fluoroborane dipyrrole derivative and an electron donor compound through a Sonogashira coupling reaction to obtain an acetylenic bond-containing fluoroborane dipyrrole-based porous organic polymer;

[0053] Step 2: The fluoroboron dipyrrol-based porous organic polymer containing cyano groups is prepared by modifying the fluoroboron dipyrrol-based porous organic polymer containing acetylenic bonds through free radical reaction.

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

[0055]

[0056] Wherein: R is any one of -H, -NO3, -SO4, -CN, -CH3, -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-tetraynylpyrene, and 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] compounds, and its structural unit is as follows:

[0058] Formula 1, 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole: Formula 2, 1,1,2,2-tetrakis(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 fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond comprises the following steps:

[0060] S1: dissolving the electron acceptor fluoroboranedipyrrole derivative and the electron donor compound in a solvent;

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

[0062] S3: After the reaction is completed, the filter is filtered and the filter cake is washed with a solvent;

[0063] S4: The solid obtained in step S3 is eluted with a Soxhlet extractor and vacuum dried to obtain a fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond.

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

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

[0066] The molar ratio of the fluoroborane dipyrrole derivative to the catalyst in step S2 is 1:0.05 to 1:1;

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

[0068] The protective atmosphere is nitrogen or argon;

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

[0070] The solvent for washing the filter cake in step S3 is at least one of 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 dipyrrol-based porous organic polymer is a fluoroboron dipyrrol-based porous organic polymer containing a cyano group, and the method comprises the following steps:

[0074] S1: dispersing the prepared fluoroborane dipyrrol-based porous organic polymer containing an alkyne bond in a solvent;

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

[0076] S3: After the reaction is completed, the mixed solution in step S2 is filtered, and the filter cake is washed with a solvent;

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

[0078] The solvent in step S1 is at least one of N,N-dimethylformamide, ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene and methanol;

[0079] In step S2, the molar ratio of the fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond to 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 to 100° C., and the reaction time is 12 to 72 hours;

[0083] The solvent for washing the filter cake in step S3 is at least one of 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] The present invention also provides an application of a fluorine boron dipyrrol-based porous organic polymer to produce hydrogen peroxide by photocatalysis, wherein the fluorine boron dipyrrol-based porous organic polymer containing a cyanide group is applied to produce hydrogen peroxide by photocatalysis;

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

[0087] The dosage of the cyano-containing fluoroboron dipyrrol-based porous organic polymer is 0.1-1 mg / mL.

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

[0089] Example 1, according to the following synthetic route ( Figure 3 The thermogravimetric diagrams of the fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an alkyne bond and the fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ containing a cyano group are shown in Figure 1. Figure 4Solid UV images of fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an acetylenic bond and fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ containing a cyano group):

[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]diazaborolane (3.20 g, 5.60 mmol), 3,3',6,6'-tetraethynyl-9,9'-biscarbazole (1.20 g, 2.80 mmol), 150 mL of N,N-dimethylformamide (DMF), and 5 mL of N,N-diisopropylethylamine (DIEA) were added into a 500 mL Schlenk bottle and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0091] (2) After the solution in step (1) is fully mixed, cuprous 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. under a nitrogen atmosphere and reacted for 72 hours;

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

[0093] (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, and the eluted solid was transferred to a vacuum drying oven and vacuum dried at 70° C. for 24 hours to obtain a fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an acetylenic bond with a yield of 90% ( Figure 1 (Figure 3) is the water contact angle diagram of the prepared fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an alkyne bond.

[0094] (5) The alkyne-bonded fluoroborane dipyrrol-based porous organic polymer BDP-CZ (1.20 g, 1.60 mmol) obtained in step (4) and 100 mL of chloroform were placed in a 250 mL Schlenk bottle and stirred and dispersed under a nitrogen atmosphere for 30 minutes;

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

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

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

[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]diazaborolane (3.20 g, 5.60 mmol), 1,1,2,2-tetrakis(p-ethynylphenyl)ethylene (1.22 g, 2.80 mmol), 150 mL of DMF, and 5 mL of DIEA 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, cuprous 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. under a nitrogen atmosphere and reacted for 72 hours;

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

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

[0104] (5) The fluoroboron dipyrrol-based porous organic polymer BDP-TPE (1.27 g, 1.60 mmol) obtained in step (4) and 100 mL of chloroform were placed in a 250 mL Schlenk bottle and stirred and dispersed under a nitrogen atmosphere for 30 minutes;

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

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

[0107] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted with dichloromethane, tetrahydrofuran and methanol for 36 hours in sequence. The eluted solid was transferred to a vacuum drying oven and vacuum dried at 70° C. for 24 hours to obtain a cyano-containing fluoroboron dipyrrol-based 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]diazaborolane (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 bottle and stirred thoroughly for 30 minutes under a nitrogen atmosphere;

[0111] (2) After the solution in step (1) is fully mixed, cuprous 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. under a nitrogen atmosphere and reacted for 72 hours;

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

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

[0114] (5) The alkyne-bonded fluoroboron dipyrrol-based porous organic polymer BDP-Py (1.06 g, 1.6 mmol) obtained in step (4) and 100 mL of chloroform were placed in a 250 mL Schlenk bottle and stirred and dispersed under a nitrogen atmosphere for 30 minutes;

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

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

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

[0118]

[0119] Example 4, according to the following 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]diazaborolane (3.20 g, 5.60 mmol), 9,9'-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] (1.32 g, 2.80 mmol), 150 mL of DMF and 5 mL of DIEA were added into a 500 mL Schlenk bottle and stirred thoroughly for 30 min under nitrogen atmosphere;

[0121] (2) After the solution in step (1) is fully mixed, cuprous 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. under a nitrogen atmosphere and reacted for 72 hours;

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

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

[0124] (5) The alkyne-bonded fluoroboron dipyrrol-based porous organic polymer BDP-TPA (1.32 g, 1.6 mmol) obtained in step (4) and 100 mL of chloroform were placed in a 250 mL Schlenk bottle and stirred and dispersed under a nitrogen atmosphere for 30 minutes;

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

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

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

[0128]

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

[0130] Table 1

[0131]

[0132] The fluoroboron dipyrrol-based porous organic polymers containing acetylenic bonds and cyano groups obtained in Examples 1 to 4 were subjected to photocatalysis to produce hydrogen peroxide, and Application Examples 1 to 4 were obtained respectively. The yield of peroxide is shown in Table 2 below.

[0133] Application Example 1

[0134] The photocatalytic performance of the porous organic polymer containing fluoroborane dipyrrol and acetylene bonds obtained in Example 1 to produce hydrogen peroxide was studied ( Figure 6 A comparison chart of the photocatalytic hydrogen peroxide production performance of fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an alkyne bond and fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ containing a cyano group);

[0135] Test samples: the fluoroboron dipyrrol-based porous organic polymer BDP-CZ containing an acetylenic bond and the fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-CZ containing a cyano group obtained in Example 1;

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

[0137] Experimental method: 5 mg BDP-CZ and 4CN-BDP-CZ were added to the quartz catalytic reactor, followed by 20 mL deionized water and stirred for 30 minutes to reach adsorption-desorption equilibrium. Finally, a 300W xenon lamp was used to simulate sunlight and react at room temperature for 1 hour to carry out a photocatalytic hydrogen peroxide production experiment. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The filtrate was used to determine the hydrogen peroxide concentration by 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 turned from transparent to yellow. The solution was measured using a UV-visible spectrometer, and the absorbance at 400 nm was measured to calculate the concentration of hydrogen peroxide, as shown in Table 2.

[0138] Application Example 2

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

[0140] Test samples: the fluoroboron dipyrrol-based porous organic polymer BDP-TPE containing an acetylenic bond and the fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-TPE containing a cyano group obtained in Example 2;

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

[0142] Experimental method: 5 mg of BDP-TPE and 4CN-BDP-TPE were added to the quartz catalytic reactor, followed by 20 mL of deionized water and stirred for 30 minutes to achieve adsorption-desorption equilibrium. Finally, a 300W xenon lamp was used to simulate sunlight and react at room temperature for 1 hour to carry out a photocatalytic hydrogen peroxide production experiment. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The filtrate was used to determine the hydrogen peroxide concentration by 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 turned from transparent to yellow. The solution was measured using a UV-visible spectrometer, and the absorbance at 400 nm was measured to calculate the concentration of hydrogen peroxide, as shown in Table 2.

[0143] Application Example 3

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

[0145] Test samples: the fluoroboron dipyrrol-based porous organic polymer BDP-Py containing an acetylenic bond and the fluoroboron dipyrrol-based porous organic polymer 4CN-BDP-Py containing a cyano group obtained in Example 3;

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

[0147] Experimental method: 5 mg BDP-Py and 4CN-BDP-Py were added to the quartz catalytic reactor, followed by 20 mL deionized water and stirred for 30 minutes to reach adsorption-desorption equilibrium. Finally, a 300W xenon lamp was used to simulate sunlight and react at room temperature for 1 hour to carry out a photocatalytic hydrogen peroxide production experiment. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The filtrate was used to determine the hydrogen peroxide concentration by 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 turned from transparent to yellow. The solution was measured using a UV-visible spectrometer, and the absorbance at 400 nm was measured to calculate the concentration of hydrogen peroxide, as shown in Table 2.

[0148] Application Example 4

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

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

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

[0152] Experimental method: 5 mg BDP-TPA and 4CN-BDP-TPA were added to the quartz catalytic reactor, followed by 20 mL deionized water and stirring for 30 minutes to reach adsorption-desorption equilibrium. Finally, a 300W xenon lamp was used to simulate sunlight and react at room temperature for 1 hour to carry out a photocatalytic hydrogen peroxide production experiment. During the reaction, 2 mL of the reaction solution was taken every 10 minutes and filtered using a 0.22 μm filter. The filtrate was used to determine the hydrogen peroxide concentration by 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 turned from transparent to yellow. The solution was measured using a UV-visible spectrometer, and the absorbance at 400 nm was measured to calculate the concentration of hydrogen peroxide, as shown in Table 2.

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

[0154] Table 2

[0155]

[0156] It can be seen that the electron acceptor fluoroborane dipyrrole is polymerized with different electron donors by the Sonogashira coupling reaction to obtain a fluoroborane dipyrrole-based porous organic polymer containing an alkyne bond, and the alkyne bond is post-modified by a free radical reaction to obtain a cyanide-containing fluoroborane dipyrrole-based porous organic polymer with good photocatalytic performance. This catalyst can significantly increase the production of hydrogen peroxide.

[0157] The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention's specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a fluoroborane dipyrrol-based porous organic polymer, characterized in that: The fluoroboron dipyrrol-based porous organic polymer is a fluoroboron dipyrrol-based porous organic polymer containing a cyano group, and the preparation method thereof comprises the following steps: Step 1: polymerizing an electron acceptor fluoroborane dipyrrole derivative and an electron donor compound through a Sonogashira coupling reaction to obtain an acetylenic bond-containing fluoroborane dipyrrole-based porous organic polymer; Step 2: The fluoroboron dipyrrol-based porous organic polymer containing cyano groups is prepared by modifying the fluoroboron dipyrrol-based porous organic polymer containing acetylenic bonds through free radical reaction.

2. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 1, characterized in that: The electron acceptor fluoroborane dipyrrole derivative is any one of the following structures: Wherein: R is any one of -H, -NO3, -SO4, -CN, -CH3, -OCH3.

3. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 1, characterized in that: 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-tetraynylpyrene, and 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole] compounds, and its structural unit is as follows: Formula 1, 3,3′,6,6′-tetraethynyl-9,9′-biscarbazole: Formula 2, 1,1,2,2-tetrakis(p-ethynylphenyl)ethylene: Formula 3, 1,3,6,8-tetraynylpyrene: Formula 4, 9,9′-(1,4-phenylene)bis[3,6-diethynyl-9H-carbazole]:

4. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 1, characterized in that: The method for preparing the fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond comprises the following steps: S1: dissolving the electron acceptor fluoroboranedipyrrole derivative and the electron donor compound in a solvent; S2: After the solid in step S1 is fully dissolved, a catalyst is added, and the fully dispersed solution is reacted under a protective atmosphere; S3: After the reaction is completed, the filter is filtered and the filter cake is washed with a solvent; S4: The solid obtained in step S3 is eluted with a Soxhlet extractor and vacuum dried to obtain a fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond.

5. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 4, characterized in that: The molar ratio of the electron acceptor fluoroborane dipyrrole derivative to the electron donor compound in step S1 is 0.5:1 to 5:1; The solvent is at least one of N,N-dimethylformamide, N,N-diisopropylethylamine, ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene and methanol.

6. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 4, characterized in that: The molar ratio of the fluoroborane dipyrrole derivative to the catalyst in step S2 is 1:0.05 to 1:1; The catalyst is at least one of tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, cuprous iodide, triphenylphosphine, and 1,10-phenanthroline; The protective atmosphere is nitrogen or argon; The reaction temperature is 25 to 100° C., and the reaction time is 12 to 72 hours.

7. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 4, characterized in that: The solvent for washing the filter cake in step S3 is at least one of ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, water, and methanol; The eluent in step S4 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.

8. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to any one of claims 1 to 7, characterized in that: The fluoroborane dipyrrol-based porous organic polymer is a fluoroborane dipyrrol-based porous organic polymer containing a cyano group. The following steps are involved: S1: dispersing the prepared fluoroborane dipyrrol-based porous organic polymer containing an alkyne bond in a solvent; S2: After the porous polymer in step S1 is fully dispersed, a free radical reaction reagent is added, and the mixed solution reacts under a protective atmosphere; S3: After the reaction is completed, the mixed solution in step S2 is filtered, and the filter cake is washed with a solvent; S4: The solid obtained in step S2 is eluted with a Soxhlet extractor and vacuum dried to obtain a cyano-containing fluoroboron dipyrrol-based porous organic polymer.

9. The method for preparing a fluoroborane dipyrrol-based porous organic polymer according to claim 8, characterized in that: The solvent in step S1 is at least one of N,N-dimethylformamide, ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene and methanol; In step S2, the molar ratio of the fluoroboron dipyrrol-based porous organic polymer containing an acetylenic bond to the free radical reaction reagent is 1:0.1 to 1:5; The free radical reaction reagent is tetracyanoethylene; The protective atmosphere is nitrogen or argon; The reaction temperature is 25 to 100° C., and the reaction time is 12 to 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; 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.

10. The use of fluoroborane dipyrrol-based porous organic polymer for photocatalytic production of hydrogen peroxide according to claim 8, characterized in that: The cyano-containing fluoroboron dipyrrol-based porous organic polymer is used for photocatalytic production of hydrogen peroxide; The light source for photocatalytic production of hydrogen peroxide is a xenon lamp; The dosage of the cyano-containing fluoroboron dipyrrol-based porous organic polymer is 0.1-1 mg / mL.

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