Porphyrin-fluoroborate-based porous organic polymers and methods of preparation and photocatalytic applications
The synthesis of porphyrin-fluorinated boron fluorescent porous organic polymers via Sonogashira coupling reaction solved the problem of low degradation efficiency of high-concentration bisphenol A and achieved a highly efficient photocatalytic degradation effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHANGZHOU UNIV
- Filing Date
- 2023-07-21
- Publication Date
- 2026-05-05
AI Technical Summary
Existing photocatalysts are inefficient in the degradation of high concentrations of bisphenol A (BPA), and traditional porous organic polymers (POPs) have limited water solubility and adsorption capacity, making it difficult to effectively treat high concentrations of organic pollutants.
A porphyrin-fluoroboron fluorescent porous organic polymer was synthesized via a Sonogashira coupling reaction. The fluoroboron fluorescent derivative and the porphyrin unit were used to form a DA structure, which enhanced the adsorption driving force and improved the photocatalytic degradation efficiency.
It achieved complete degradation of high-concentration bisphenol A (100 ppm) within 30 minutes, and degradation of other dyes to 50-100 ppm concentration within a short time (15-45 minutes), demonstrating excellent photocatalytic performance.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of photocatalytic materials technology, specifically relating to a method for preparing a class of porous organic polymers based on porphyrin-fluorine-boron-fluorine and their photocatalytic applications. Background Technology
[0002] The release of persistent organic pollutants (POPs) into the environment is a global concern. These chemicals remain stable over long periods, accumulating in many plants and animals and ultimately threatening human health and safety. Traditional treatment methods include biodegradation, non-biodegradation, direct degradation, ultrasonic catalytic degradation, and photocatalytic degradation. However, these methods are characterized by incomplete removal and high costs.
[0003] Photocatalysis, with its advantages such as high efficiency, relatively low cost, and eco-friendliness, has become one of the most promising technologies in the 20th century due to its ability to effectively degrade and completely mineralize persistent organic pollutants. The efficiency of photocatalysis depends on the photocatalyst, and improving the adsorption performance and catalytic degradation efficiency of photocatalysts remains a key technical bottleneck in this research field. Porous organic polymers (POPs), as recyclable heterogeneous catalysts, are widely used to improve the adsorption and degradation performance of photocatalysts due to their tunable microporous structures. The key to this research is to combine the strong adsorption of physical adsorption methods with the thorough degradation of organic pollutants by photocatalytic oxidation into a single photocatalyst, developing a photocatalyst with high selective adsorption, high adsorption capacity, and high photocatalytic activity.
[0004] Porphyrins have been studied for their application in the degradation of organic matter for some time, and porphyrin-based POPs have exhibited higher catalytic efficiency than traditional inorganic photocatalysts. A common method to improve catalytic efficiency is to construct DA structures to promote the formation of built-in electric fields, thereby improving the separation and transport efficiency of photogenerated carriers. However, porphyrins, as large π structures with 18 electrons, have poor water solubility, resulting in limited adsorption capacity for pollutants, thus limiting further improvements in catalytic efficiency. Furthermore, current photocatalyst research focuses on the degradation of low-concentration BPA (10-20 ppm), mainly because high-concentration BPA easily causes catalyst pore blockage and deactivation. Therefore, molecular design and material performance improvements need to consider the practical application environment. Recently, Lu et al. developed a method of modifying POPs by introducing hydrophilic groups to improve hydrophilicity and enhance the efficiency of photodegradation of bisphenol A. The resulting polymer can achieve complete photodegradation of 50 ppm BPA solution in 30 minutes. However, this work still fails to address the degradation of higher concentrations of BPA, such as 100 ppm.
[0005] In summary, this invention utilizes multiple molecular bond forces (hydrogen bonds, π-π interactions, and host-guest interactions) to a certain extent to enhance the adsorption driving force, obtain adsorption-photodegradation equilibrium, and improve the overall photocatalytic degradation efficiency. It provides a D-π-A type conjugated porous organic polymer with dual photosensitive centers for degrading BPA and dyes (MO, MB, RhB) and its preparation method. Summary of the Invention
[0006] The purpose of this invention is to provide a method for preparing a porous organic polymer based on porphyrin-fluorine-boron-fluorine, and its application in photocatalytic degradation of organic pollutants and photocatalytic oxidation reactions. The porous organic polymer synthesized by this invention has the characteristics of large porosity, simple operation, and tunable structure. It can adsorb and degrade organic pollutants and can selectively and rapidly photocatalytically oxidize benzyl sulfide to methyl phenyl sulfoxide, exhibiting excellent photocatalytic performance.
[0007] The present invention is specifically achieved through the following technical solution: it is prepared by a Sonogashira coupling reaction of fluorine-boron fluorescent derivatives and porphyrin units.
[0008] The structures of fluorine-boron-fluorescent derivatives are as follows:
[0009] ;
[0010] R1 = Me, Et, , , , , , ;
[0011] Monomers containing porphyrin groups are selected from the following structural formulas:
[0012]
[0013] Where, R2= , , , .
[0014] This invention provides a method for preparing a class of porphyrin-fluorine-boron-fluorescent porous organic polymers, comprising the following steps:
[0015] 1) Add the fluoroboron fluorescent derivative parent compound and porphyrin unit, organic base, and solvent sequentially to the reaction flask, and mix by sonication; wherein the molar ratio of the functional groups of the fluoroboron fluorescent derivative parent compound and porphyrin unit is 2:1 to 5:1; the organic base is triethylamine, diisopropylethylamine or diisopropylamine; the solvent is tetrahydrofuran; the volume ratio of organic base to tetrahydrofuran solvent is 1:1 to 1:2.
[0016] 2) Replace the reaction system in step 1) with nitrogen three times, add cuprous iodide and tetra(triphenylphosphine)palladium in sequence, continue to purge with nitrogen for 5-10 min, heat and reflux for 3-5 days, cool to room temperature after reaction, and filter to obtain solid product.
[0017] The amount of cuprous iodide added is 2-4 mol of the functional group (reaction site); the amount of tetrakis(triphenylphosphine)palladium added is 2-4 mol of the functional group (reaction site).
[0018] 3) After washing and drying the solid product obtained in step 2), wash it with a solvent, and finally perform Soxhlet extraction with a solvent. The solid is subjected to 40-60 minutes of solvent extraction. o After vacuum drying at C, the porphyrin-fluorinated boron fluorescent porous organic polymer BPOP is obtained. The solvents used are dichloromethane, tetrahydrofuran, and methanol. N , N -Dimethylformamide and one or more of the following.
[0019] The porphyrin-fluorine-boron-fluorescent porous organic polymer prepared by the method described in this invention can be used for photocatalytic degradation of organic pollutants and photocatalytic oxidation of small organic molecules.
[0020] The organic pollutants are one or more of the following: phenolic pollutants, methyl orange, Congo red, methylene blue, and rhodamine B.
[0021] Furthermore, the photocatalysis uses an Xe lamp as the light source, and the porphyrin-fluorine-boron fluorescent porous organic polymer can degrade phenolic pollutants, the dye methyl orange, and photocatalytically convert benzyl sulfide to methyl phenyl sulfoxide.
[0022] Furthermore, the concentration of bisphenol A is 10–200 ppm, and the amount of the porphyrin-fluoroboron fluorescent porous organic polymer is 0.1–1 mg / mL.
[0023] Furthermore, the concentration of organic dyes such as methyl orange is 10–200 ppm, and the amount of the porphyrin-fluoroboron fluorescent porous organic polymer is 0.1–1 mg / mL.
[0024] Furthermore, based on the amount of anisole sulfide, the amount of the porphyrin-fluoroboron fluorescent porous organic polymer is 0.1–10 mol%.
[0025] Compared with the prior art, the beneficial effects of the present invention are:
[0026] This invention develops a synthetic route for a porphyrin-fluorine-boron-fluorescent porous organic polymer photocatalyst for organic pollutants: a method for preparing porous organic polymers based on fluorine-boron-fluorescent derivatives, characterized in that the porous organic polymer is prepared by a Sonogashira coupling reaction of fluorine-boron-fluorescent derivatives and porphyrin linking groups. The porphyrin-fluorine-boron-fluorescent porous organic polymer prepared by this method is applied to photocatalytic degradation of organic pollutants and photocatalytic oxidation reactions. The degradation efficiency for high concentrations of 100 ppm bisphenol A is currently the highest known, achieving complete degradation within 30 minutes. Degradation of other dyes at concentrations of 50-100 ppm can also be achieved in a short time (15-45 minutes). Attached Figure Description
[0027] Figure 1 This is a schematic diagram of the preparation process of BPOP-1, a porphyrin-fluorine-boron-fluorescent porous organic polymer.
[0028] Figure 2 This is the Fourier transform infrared spectrum of BPOP-1, a porphyrin-fluorine-boron-fluorescent porous organic polymer.
[0029] Figure 3 This is a TEM image of BPOP-1, a porphyrin-fluorine-boron-fluorescent porous organic polymer.
[0030] Figure 4 This is the N2 adsorption-desorption isotherm diagram of BPOP-1, a porphyrin-fluorine-boron-fluorescent porous organic polymer.
[0031] Figure 5 This is a TGA image of BPOP-1, a porphyrin-fluorine-boron-fluorescent porous organic polymer.
[0032] Figure 6 This is the UV-Vis diffuse reflectance spectrum of BPOP-1, a porphyrin-fluorine-boron-fluorescent porous organic polymer.
[0033] Figure 7 It is a porphyrin-fluorine-boron-fluorescent porous organic polymer BPOP-1 that photocatalytically degrades bisphenol A.
[0034] Figure 8 It is a porphyrin-fluorine-boron-fluorescent porous organic polymer BPOP-1 that photocatalytically degrades methyl orange.
[0035] Figure 9 It is a porphyrin-fluorine-boron-fluorescent porous organic polymer BPOP-1 that photocatalytically oxidizes anisole. Detailed Implementation
[0036] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.
[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.
[0038] The monomer compositions of porphyrin-fluorine-boron-fluorescent porous organic polymers BPOP-1 to BPOP-10 are as follows:
[0039] BPOP-1:
[0040]
[0041] Example 1
[0042] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-1:
[0043] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4-bromophenyl)porphyrin (1.80 g, 2.00 mmol), and 2,8-diethynyl-5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.50 g, 4.00 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0044] Nitrogen gas was introduced into the Shrek flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 mg, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , NThe product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-1 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 99%.
[0045] The infrared spectrum of the BPOP-1 polymer obtained by sonogashira coupling contains approximately 2200 cm⁻¹. -1 and 3200 cm -1 The tensile vibrations attributable to the alkyne linker and terminal alkyne demonstrate the successful synthesis of the polymer, 3300 cm. -1 The nearby peaks belong to the NH vibration of porphyrins, indicating that the main structure remains unchanged. TEM images of BPOP-1 show its clustered morphology. N2 adsorption-desorption isotherms of BPOP-1 show that it exhibits type IV adsorption characteristics with adsorption / desorption hysteresis, indicating the presence of mesopores. TGA images of BPOP-1 show that it has good thermal stability at 800°C. o At C, there is less than 30% mass loss. The solid-state UV spectrum of BPOP-1 also shows that it has a broad absorption range.
[0046] Example 2
[0047] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-2:
[0048] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4-bromophenyl)porphyrin (1.80 g, 2.00 mmol), and 2,8-diethynyl-10-(4-ethynylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexylborane (1.05 g, 2.67 mmol), stirred for 20 min to allow the mixture to disperse evenly;
[0049] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 mg, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o After reacting in an oil bath for 3 days and cooling to room temperature, the product was obtained by filtration; N , NThe product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-2 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 98%.
[0050] Example 3
[0051] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-3:
[0052] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4-bromophenyl)porphyrin (1.80 g, 2.00 mmol), and 2,8-diethynyl-10-(2,4,6-trimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexylborane (1.66 g, 4.00 mmol), stirred for 20 min to allow the mixture to disperse evenly;
[0053] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-3 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 95%.
[0054] Example 4
[0055] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-4:
[0056] Add 100 mL to the Shlenk flask sequentially. N ,N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4-bromophenyl)porphyrin (1.80 g, 2.00 mmol), and 2,8-diethynyl-10-(4-methylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.54 g, 4 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0057] Nitrogen gas was introduced into the Shrek flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by vacuum filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-4 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 98%.
[0058] Example 5
[0059] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-5:
[0060] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4-bromophenyl)porphyrin (1.80 g, 2.00 mmol), and 2,8-diethynyl-10-(perfluorophenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.85 g, 4 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0061] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-5 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 95%.
[0062] Example 6
[0063] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-6:
[0064] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4-bromophenyl)porphyrin (1.80 g, 2.00 mmol), and 2,8-diethynyl-10-(4-hydroxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.55 g, 4.00 mmol), stirred for 20 min to allow the mixture to disperse evenly;
[0065] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-6 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 95%.
[0066] Example 7
[0067] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-7:
[0068] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(4'-bromo-[1,1'-biphenyl]-4-yl)porphyrin (2.47 g, 2.00 mmol), and 2,8-diethynyl-5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.50 g, 4.00 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0069] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-7 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 95%.
[0070] Example 8
[0071] Preparation of BPOP-8, a porphyrin-fluorine boron fluorescent porous organic polymer:
[0072] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(5-bromo-[1,1'-biphenyl]-3-yl)porphyrin (2.47 g, 2.00 mmol), and 2,8-diethynyl-5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.50 g, 4.00 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0073] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-8 was obtained by drying in a vacuum oven at C for 12 hours, with a yield of 95%.
[0074] Example 9
[0075] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-9:
[0076] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetrakis(4,4'-dibromo-[1,1'-:3'-,1'-triphenyl]-5'-yl)porphyrin (1.85 g, 1.00 mmol), and 2,8-diethynyl-5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.50 g, 4.00 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0077] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately...N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-9 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 95%.
[0078] Example 10
[0079] Preparation of porphyrin-fluorine boron fluorescent porous organic polymer BPOP-10:
[0080] Add 100 mL to the Shlenk flask sequentially. N , N A mixed solution of dimethylformamide and 100 mL of diisopropylamine, 5,10,15,20-tetra(10-bromoanthracene-9-yl)porphyrin (2.66 g, 2.00 mmol), and 2,8-diethynyl-5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5 H -4 5 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaborane (1.50 g, 4.00 mmol), stirred for 20 min to ensure uniform dispersion of the mixture;
[0081] Nitrogen gas was bubbled through the Shlenk flask, and cuprous iodide (0.12 g, 1.40 mmol) and tetrakis(triphenylphosphine)palladium (0.41 g, 0.34 mmol) were added sequentially under nitrogen atmosphere. The mixture was then heated to 100 °C. o The reaction was carried out in an oil bath for 3 days, and after cooling to room temperature, the product was obtained by filtration. N , N The product was washed repeatedly with dimethylformamide, tetrahydrofuran, and methanol, and then separately... N , N The product was subjected to Soxhlet extraction for two days using dimethylformamide, tetrahydrofuran, and dichloromethane as solvents, and the resulting solid product was then cooled at 40-60°C. o The porphyrin-fluorine-boron-fluorine porous organic polymer BPOP-10 was obtained by drying in a vacuum drying oven at C for 12 hours, with a yield of 95%.
[0082] Application Example 1
[0083] Study on photodegradation of organic pollutant bisphenol A:
[0084] The porous organic polymers obtained in Examples 1-10 were subjected to photodegradation studies of phenolic organic compounds.
[0085] Test sample: The porous organic polymers obtained in Examples 1-10;
[0086] Preparation of phenolic organic compound solution: Prepare a bisphenol A solution with a concentration of 200 ppm.
[0087] Experimental method: 5 mg of the porous organic polymer obtained in Examples 1-10 was added to a sample vial, along with 10 ml of the prepared bisphenol A solution. The vial was placed in a constant-temperature reactor and stirred for photodegradation experiments (300W xenon lamp, simulating sunlight). Samples were taken at 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, and 60 min, respectively. The concentration of the bisphenol A solution was measured using liquid chromatography, and the photodegradation ability of the porous organic polymer to the bisphenol A solution was calculated. Example 1 ( Figure 7 As shown), Examples 2, 3, 4, 5, 6, 7, 8, 9 and 10 can achieve 99% degradation of 100 ppm bisphenol A in 30 min, 30 min, 50 min, 60 min, 90 min, 70 min, 40 min, 50 min, 60 min and 60 min respectively.
[0088] Application Example 2
[0089] Photodegradation study of methyl orange dye:
[0090] The porous organic polymers obtained in Examples 1-10 were subjected to photodegradation studies of methyl orange dye.
[0091] Test sample: The porous organic polymers obtained in Examples 1-10;
[0092] Preparation of methyl orange dye solution: Prepare a methyl orange dye solution with a concentration of 100 ppm.
[0093] Experimental Method: 5 mg of the porous organic polymer obtained in Examples 1-10 was added to a sample vial, along with 10 ml of the prepared methyl orange dye solution. The vial was placed in a constant-temperature reactor and stirred for photodegradation experiments (300W xenon lamp, simulating sunlight). Samples were taken at 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, and 60 min, respectively. The concentration of the methyl orange dye solution was measured using a UV-Vis spectrophotometer, and the photodegradation ability of the porous organic polymer to the methyl orange dye solution was calculated. Example 1 ( Figure 8As shown), Examples 2, 3, 4, 5, 6, 7, 8, 9 and 10 can achieve 100% degradation of methyl orange in 10 min, 20 min, 30 min, 35 min, 50 min, 25 min, 15 min, 30 min, 40 min and 80 min respectively.
[0094] Application Example 3
[0095] Photodegradation of Congo Red dye:
[0096] The porous organic polymers obtained in Examples 1-10 were subjected to photodegradation studies of Congo red dye.
[0097] Test sample: The porous organic polymers obtained in Examples 1-10;
[0098] Preparation of Congo Red dye solution: Prepare a Congo Red dye solution with a concentration of 100 ppm.
[0099] Experimental Method: 5 mg of the porous organic polymer obtained in Examples 1-10 was added to the sample bottle, along with 10 ml of the prepared Congo red dye solution. The bottle was placed in a constant-temperature reactor and stirred for photodegradation experiments (300W xenon lamp, simulating sunlight). Samples were taken at 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, and 60 min, respectively. The concentration of the Congo red dye solution was measured using a UV-Vis spectrophotometer, and the photodegradation ability of the porous organic polymer to the Congo red dye solution was calculated. Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 showed that 100% degradation of Congo red was achieved within 40 min, 70 min, 40 min, 50 min, 55 min, 60 min, 50 min, 70 min, 100 min, and 130 min, respectively.
[0100] Application Example 4
[0101] Photodegradation study of methylene blue dye:
[0102] The porous organic polymers obtained in Examples 1-10 were subjected to methylene blue light degradation studies.
[0103] Test sample: Porous organic polymers obtained in Examples 1-10;
[0104] Preparation of methylene blue dye solution: Prepare a methylene blue dye solution with a concentration of 100 ppm.
[0105] Experimental Method: 5 mg of the porous organic polymer obtained in Examples 1-10 was added to a sample vial, along with 10 ml of the prepared methylene blue dye solution. The vial was placed in a constant-temperature reactor and stirred for photodegradation experiments (using a 300W xenon lamp to simulate sunlight). Samples were taken at 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, and 60 min, respectively. The concentration of the methylene blue dye solution was measured using a UV-Vis spectrophotometer, and the photodegradation ability of the porous organic polymer to the methylene blue dye solution was calculated. Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 showed 100% degradation of methylene blue within 30 min, 50 min, 70 min, 40 min, 50 min, 55 min, 60 min, 50 min, 70 min, and 90 min, respectively.
[0106] Application Example 5
[0107] Photodegradation study of Rhodamine B dye:
[0108] The porous organic polymers obtained in Examples 1-10 were subjected to photodegradation studies of Rhodamine B dye.
[0109] Test sample: Porous organic polymers obtained in Examples 1-10;
[0110] Preparation of Rhodamine B dye solution: Prepare a Rhodamine B dye solution with a concentration of 100 ppm.
[0111] Experimental Method: 5 mg of the porous organic polymer obtained in Examples 1-10 was added to a sample vial, along with 10 ml of the prepared Rhodamine B dye solution. The vial was placed in a constant-temperature reactor and stirred for photodegradation experiments (using a 300W xenon lamp to simulate sunlight). Samples were taken at 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, and 60 min, respectively. The concentration of the Rhodamine B dye solution was measured using a UV-Vis spectrophotometer to evaluate the photodegradation ability of the porous organic polymer on the Rhodamine B dye solution. Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 showed 99% degradation of Rhodamine B within 20 min, 40 min, 50 min, 70 min, 40 min, 50 min, 30 min, 35 min, 50 min, and 80 min, respectively.
[0112] Application Example 6
[0113] Study on the photo-oxidation reaction of anisole:
[0114] The porous organic polymers obtained in Examples 1-10 were subjected to photo-oxidation reaction of anisole.
[0115] Test sample: Porous organic polymers obtained in Examples 1-10;
[0116] Preparation of anisole solution: Prepare anisole methanol solution with a concentration of 1 mol / L;
[0117] Experimental Method: 5 mg of the porous organic polymer obtained in Examples 1-10 was added to the sample vial, along with 5 ml of the prepared anisole methanol solution. The vials were placed in a constant-temperature reactor and stirred for photodegradation experiments (300W xenon lamp, simulating sunlight). Samples were taken at 30 min, 60 min, 90 min, 120 min, and 150 min, and the concentration of the anisole methanol solution was measured using gas chromatography to evaluate the conversion ability of the porous organic polymer to anisole. Example 1 ( Figure 9 As shown), Examples 2, 3, 4, 5, 6, 7, 8, 9 and 10 can completely convert anisole to methyl phenyl sulfoxide in 30 min, 60 min, 70 min, 240 min, 90 min, 120 min, 210 min, 90 min, 150 min and 180 min respectively.
[0118] Table 1 compares the degradation efficiency of BPA by different catalysts in existing documents.
[0119] Table 1 Comparison of BPA degradation efficiency for different catalysts
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[0154] In summary, the porphyrin-fluoroboron fluorescent porous organic polymer (BPOP) prepared by the method of this invention exhibits highly efficient photocatalytic degradation of organic pollutants (such as bisphenol A, RhB, MB, and MO), and can rapidly photocatalytically oxidize anisole to methyl phenyl sulfoxide, demonstrating high selectivity and a good oxidation rate. As a highly efficient photocatalyst in heterogeneous media, BPOP rapidly generates oxygen-active species under illumination, photocatalytically degrading organic pollutants and catalyzing the conversion of sulfides to sulfoxides. It can complete the rapid degradation of 100 ppm BPA and the oxidation of anisole within 60 minutes. The photocatalyst was constructed using pure organic components without metal photocatalytic centers or photosensitizer molecules. Through detailed structural analysis, the catalytic performance of porous organic polymer BPOP with different linking units was systematically studied, revealing the relationship between the structure and performance of BPOP, as well as the differences and key roles of the linking units in photocatalytic performance.
[0155] The embodiments described above are merely preferred embodiments of the present invention, and while the descriptions are specific and detailed, they are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the concept and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. An application of a class of porous organic polymers based on porphyrin-fluorine-boron-fluorescein, characterized in that, The porous organic polymer is used for photocatalytic degradation of organic pollutants; the organic pollutant is bisphenol A. The porous organic polymer was prepared by a Sonogashira coupling reaction of fluoroboron fluorescent derivatives and monomers containing porphyrin groups. The structures of fluorine-boron-fluorescent derivatives are as follows: ； R1= Me, Et, , , , , , ; The structures of monomers containing porphyrin groups are as follows: ； Where, R2= , , , .
2. The application according to claim 1, characterized in that, The molar ratio of the fluorinated boron fluorescent derivative to the porphyrin-containing monomer is 2:1 to 5:
1.
3. The application according to claim 1 or 2, characterized in that, A polymer was prepared by reflux reaction of fluoroboron fluorescent derivatives and porphyrin-containing monomers in the presence of a catalyst and an organic base, using tetrahydrofuran as a solvent; the catalysts were cuprous iodide and tetra(triphenylphosphine)palladium.
4. The application according to claim 3, characterized in that, The organic base is triethylamine, diisopropylethylamine, or diisopropylamine; the volume ratio of organic base to solvent is 1:1 to 1:2.