Triphenylamine imidazole porous organic polymer, preparation method thereof and application of triphenylamine imidazole porous organic polymer in proton conduction and photocatalytic antibiosis

Abstract

The invention provides a triphenylamine imidazole porous organic polymer, a preparation method thereof and application of the triphenylamine imidazole porous organic polymer in proton conduction and photocatalytic antibiosis. According to the invention, pyrene-4, 5, 9, 10-tetraone, ammonium acetate and tris (4-formylphenyl) amine are used as raw materials to synthesize the triphenylamine imidazole POPs with high crystallinity, high specific surface area, porosity and high structural stability; the POPs containing high-density triphenylamine, imidazole and pyrene groups are subjected to sulfonation modification of different degrees, and then a proton carrier is loaded after sulfonation modification to obtain a series of functionalized triphenylamine imidazole porous organic polymers. The triphenylamine imidazole porous organic polymer material disclosed by the invention shows good proton conduction capability under a wide temperature condition, and has very high use stability. Meanwhile, the triphenylamine imidazole porous organic polymer material disclosed by the invention shows an excellent photocatalytic broad-spectrum antibacterial effect and an excellent antibacterial effect under various water body conditions.

Description

Technical Field

[0001] The invention relates to a triphenylamine imidazole porous organic polymer, a preparation method thereof and application in proton conduction and photocatalytic antibacterial, and belongs to the field of new energy materials and antibacterial materials in organic functional materials. Background Art

[0002] Energy crisis and environmental pollution are important issues that human society is currently facing and urgently needs to solve. In the low-carbon future social life, proton exchange membrane fuel cells are expected to become a powerful alternative to the existing traditional fossil fuel-based power technology because of their high conversion efficiency and environmental friendliness. As one of the core technologies of fuel cells, the proton conductivity of proton exchange membranes directly affects the final performance of the entire fuel cell. At present, the commercialized material in the field of proton exchange membrane technology is a perfluorosulfonic acid-based electrolyte polymer called Nafion; however, its cumbersome synthesis steps, narrow operating temperature range and high cost have seriously restricted the application and promotion of this material.

[0003] On the other hand, bacterial contamination in water bodies has become a serious threat to public health. Antibiotics, as the current common method, often lead to a sharp decline in bactericidal effect due to bacterial resistance. Recently, photocatalytic oxidation disinfection technology has emerged as a promising alternative bactericidal technology that can effectively avoid the problem of antibiotic resistance. However, the current in-depth research on photocatalysts is mainly based on inorganic semiconductors (such as TiO 2 , CdSe and ZnO) and noble metal complexes (such as ruthenium, rhodium and palladium). The metal / dye toxicity and non-recyclability of these traditional photocatalysts severely limit their application in the field of photocatalytic disinfection, especially in water bodies.

[0004] In recent years, porous organic polymers (POPs) have attracted extensive attention for their preparation and application development due to their structural peculiarities and excellent physical and chemical properties. Their inherent organic properties endow them with chemical and functional adjustability, and therefore they have been widely and deeply studied in many fields such as gas adsorption and separation, sensing, catalysis, energy storage and conversion. Through structural design and chemical modification, high-performance functional porous polymer materials can be constructed, which is expected to become a potential method for constructing new proton-conducting materials and photocatalytic antibacterial materials. Chinese patent document CN113912845A discloses a porphyrin-based imidazole porous organic polymer, its preparation method and its application in proton-conducting materials. The invention uses pyrene-4,5,9,10-tetraketone, ammonium acetate and tetraaldehyde phenylporphyrin as raw materials to synthesize a porphyrin-based imidazole POPs with high crystallinity, high specific surface area, porosity and large pore size, and high structural stability; the POPs containing high-density porphyrin groups, porphyrin-based imidazoles and pyrene groups are sulfonated, loaded with phosphoric acid, and loaded with phosphoric acid after sulfonation to obtain a series of functionalized porphyrin-based imidazole POPs materials. The POPs material of the invention exhibits good proton conductivity under a wide range of temperature and humidity conditions, as well as under anhydrous conditions, and has high stability in use. However, its sulfonation modification uses chlorosulfonic acid as the raw material, the sulfonation conditions are relatively harsh, and the modification site has a certain uncertainty; and it does not have an antibacterial effect. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a triphenylamino imidazole porous organic polymer, a preparation method thereof, and its application in proton conduction and photocatalytic antibacterial. The present invention uses pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine as raw materials to synthesize a triphenylamino imidazole POPs with high crystallinity, high specific surface area, porosity and high structural stability; the POPs containing high-density triphenylamine, imidazole and pyrene groups are subjected to sulfonation modification to different degrees and then loaded with proton carriers after sulfonation modification to obtain a series of functionalized triphenylamino imidazole porous organic polymers. The triphenylamino imidazole porous organic polymer material of the present invention exhibits good proton conduction ability under a wide range of temperature conditions and has high stability in use. At the same time, the triphenylamino imidazole porous organic polymer material of the present invention exhibits excellent photocatalytic broad-spectrum antibacterial effect and excellent antibacterial effect under various water conditions.

[0006] The technical solution of the present invention is as follows:

[0007] A triphenylamino imidazole porous organic polymer, wherein the organic polymer is triphenylamino imidazole POPs, sulfonated triphenylamino imidazole POPs or sulfonated triphenylamino imidazole POPs loaded with a proton carrier;

[0008] The triphenylamino imidazole POPs and the sulfonated triphenylamino imidazole POPs are two-dimensional porous polymers having structural units represented by the following formulas (I) and (II), respectively;

[0009]

[0010]

[0011] Wherein, in formula (II), R 1 is the propane sulfonic acid anion group, R 2 is H or a propane sulfonic acid group.

[0012] Preferably according to the present invention, the proton carrier is phosphoric acid or imidazole.

[0013] According to the preferred embodiment of the present invention, the specific surface area of ​​the organic polymer is 150-900m 2 / g, and a pore size of 1-15nm; the organic polymer has good crystallinity.

[0014] The preparation method of the triphenylamino imidazole POPs comprises the steps of: reacting pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine in an organic solvent A, and then filtering, washing and drying to prepare the triphenylamino imidazole POPs.

[0015] According to the present invention, the pyrene-4,5,9,10-tetraketone and tris(4-formylphenyl)amine have the following structures:

[0016]

[0017] Preferably according to the present invention, the organic solvent A is a mixed solvent of mesitylene, toluene and glacial acetic acid; the volume ratio of mesitylene, toluene and glacial acetic acid is 1-10:1-10:1, preferably 4-8:2-4:1, and further preferably 8:2:1; the volume ratio of the amount of pyrene-4,5,9,10-tetraketone to the organic solvent A is 0.01-0.1 mol / L.

[0018] Preferably according to the present invention, the molar ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine is (1.2-2):(1-5):1; preferably, the molar ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine is (1.2-1.8):(2.5-3.5):1; further preferably, the molar ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine is 1.5:2.9:1.

[0019] Preferably according to the present invention, the reaction temperature of pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine is 80-150°C, and the reaction time is 2 days to 8 days; most preferably, the reaction temperature is 150°C, and the reaction time is 5 days.

[0020] Preferably according to the present invention, one to three freeze-pump-thaw cycles are required before the reaction of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine to keep the reaction system in a vacuum state to ensure that the reaction is carried out under oxygen-free and water-free conditions.

[0021] Preferably according to the present invention, the reaction of pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine is carried out in a thick-walled pressure tube or an ampoule.

[0022] Preferably, the washing is performed by washing with DMF, ethanol and THF 2-3 times respectively, and then Soxhlet extraction is performed with THF and acetone for 15-48 hours respectively.

[0023] Preferably according to the present invention, the drying temperature is 80-120°C.

[0024] The method for preparing the sulfonated triphenylamino imidazole POPs comprises the steps of dispersing the prepared triphenylamino imidazole POPs in an organic solvent B, adding 1,3-propane sultone to react, and then filtering, washing and drying to obtain the sulfonated triphenylamino imidazole POPs.

[0025] Preferably according to the present invention, the organic solvent B is dichloromethane, N-methylpyrrolidone, mesitylene or tetrahydrofuran; and the mass ratio of the triphenylamino imidazole POPs to the organic solvent B is 0.4 g / L-5 g / L.

[0026] Preferably according to the present invention, the mass ratio of the triphenylamino imidazole POPs to 1,3-propane sultone is 1-10:1; preferably, the mass ratio of the triphenylamino imidazole POPs to 1,3-propane sultone is 2-6:1; further preferably, the mass ratio of the triphenylamino imidazole POPs to 1,3-propane sultone is 5.8:1 or 2.3:1.

[0027] According to the present invention, preferably, the reaction temperature is 10-120°C, the reaction time is 10-40 days, and the reaction is carried out under stirring conditions; preferably, the reaction temperature is 20-80°C, and the reaction time is 20-30 days; further preferably, the reaction temperature is 25°C or 80°C.

[0028] Preferably according to the present invention, the washing is done with water; and the drying temperature is 60-120°C.

[0029] The preparation method of the above-mentioned sulfonated triphenylamine imidazole POPs loaded with proton carrier comprises the steps of:

[0030] A proton carrier aqueous solution with a mass fraction of 80-90% is added dropwise to the above-mentioned sulfonated triphenylamino imidazole POPs, ground, and then washed and dried to obtain the sulfonated triphenylamino imidazole POPs loaded with proton carriers. The proton carrier is fixed in the POPs pores by triphenylamine groups, imidazole and sulfonic acid groups through ionic bonds or hydrogen bonds. Since the sulfonated triphenylamino imidazole POPs contain abundant proton carrier loading sites, POPs with high proton carrier loading can be obtained conveniently and effectively by adding a high-concentration proton carrier aqueous solution and directly grinding.

[0031] According to the preferred embodiment of the present invention, the proton carrier is phosphoric acid or imidazole. 3 PO 4 ) has high proton concentration, low volatility (>158℃), and high proton mobility.

[0032] Preferably, according to the present invention, the mass ratio of the sulfonated triphenylamino imidazole POPs to the volume ratio of the proton carrier aqueous solution is 10-15 mg / μL; the grinding temperature is room temperature, and the grinding time is 15-25 minutes.

[0033] The triphenylamine imidazole porous organic polymer is applied to proton exchange membranes in fuel cells and / or photocatalytic broad-spectrum antibacterial.

[0034] According to the preferred embodiment of the present invention, in the photocatalytic broad-spectrum antibacterial method, the irradiation light wavelength is 660nm laser, and the power is 80-120mW cm -2 .

[0035] The technical features and beneficial effects of the present invention are as follows:

[0036] 1. The present invention uses pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine as raw materials to synthesize a novel triphenylamine-based imidazole POPs containing high-density triphenylamine, imidazole and pyrene groups in one step through the Debus-Radziszewski reaction; the ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine, the organic solvent A used and the reaction temperature must be appropriate. If the ratio and the type of organic solvent A are not appropriate, the triphenylamine-based imidazole POPs with the structure and performance of the present invention cannot be obtained. At the same time, the reaction temperature also needs to be appropriate, and the preferred freeze-pump-thaw cycle is combined to obtain the triphenylamine-based imidazole POPs with the structure and performance of the present invention. The preparation method of the present invention as a whole makes the yield of the target product of the present invention higher, which can reach 90%.

[0037] The obtained triphenylamino imidazole POPs can be partially sulfonated or completely sulfonated by introducing 1,3-propane sultone and then sulfonating. The sulfonation modification method has relatively mild sulfonation reaction conditions, and the prepared sulfonated triphenylamino imidazole POPs have clear sulfonation sites, and the sulfonation degree of the triphenylamino imidazole POPs can be controlled by adjusting the mass ratio of the reactants. The triphenylamino imidazole POPs and sulfonated triphenylamino imidazole POPs have functional groups such as triphenylamine, imidazole, and sulfonic acid groups on their skeletons. The presence of such groups makes these functionalized POPs have proton conductivity. In addition, the completely sulfonated triphenylamino imidazole POPs contain more abundant proton carrier loading sites, among which the presence of triphenylamine, imidazole and sulfonic acid groups can enhance the adsorption performance of POPs materials for proton carriers, and POPs with high proton carrier loading can be obtained directly by grinding in a short time, conveniently and effectively, thereby further enhancing the proton conductivity of the material.

[0038] 2. The triphenylamine imidazole POPs prepared by the present invention has a porous structure and a large specific surface area (the specific surface area can reach 887m 2 / g), regular pores, and high crystallinity.

[0039] 3. The high-density triphenylamine, imidazole and sulfonic acid groups in the fully sulfonated and modified triphenylamino imidazole POPs prepared by the present invention are excellent proton acceptors, and have free protons and proton carrier coordination sites, which can continue to load proton carriers to further improve the proton conductivity of POPs. Therefore, the triphenylamino imidazole porous organic polymer of the present invention has great potential as a proton conductive material. As a whole, the various groups of the present invention have complex interactions with each other, and compared with other existing porous organic polymers with other structures, it has better proton conductivity and stability in use.

[0040] The triphenylamine imidazole porous organic polymer prepared by the present invention exhibits good proton conductivity under a wide range of temperature conditions: under high humidity, the proton conductivity can reach 0.79×10 -1 S / cm, and its performance is comparable to that of the currently commercialized Nafion material (~1×10 -1 S / cm). This type of material has a rigid skeleton of triphenylamine and imidazole, so it has higher structural stability and use stability than similar materials; it is a new type of material that can be potentially used in proton exchange membrane fuel cells.

[0041] 4. The triphenylamine group introduced into the triphenylamine imidazole porous organic polymer prepared by the present invention is a typical photosensitive group, which can efficiently produce active oxygen species under light to kill bacteria, so it can be applied to the field of photocatalytic antibacterial. Since the photocatalytic process is accompanied by proton transfer, the higher proton conductivity of the triphenylamine imidazole porous organic polymer, especially the sulfonated triphenylamine imidazole POPs, also enhances its photocatalytic antibacterial ability. Therefore, the triphenylamine imidazole porous organic polymer prepared by the present invention also exhibits excellent photocatalytic broad-spectrum antibacterial effect and excellent antibacterial effect under various water conditions: in artificial water bodies and natural water bodies, the fully sulfonated triphenylamine imidazole POPs can achieve a bacterial disinfecting rate of >99% under visible light irradiation in only 15 minutes. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 The powder X-ray diffraction spectrum of the PyNTB-COF synthesized in Example 1 and the powder X-ray diffraction spectrum of the simulated AA stacking and AB stacking;

[0043] Figure 2 is the Fourier infrared spectrum of the PyNTB-COF and raw materials synthesized in Example 1;

[0044] Figure 3 The PyNTB-COF and PyNTB-COF-SO synthesized in Examples 1, 2 and 3 3 , PyNTB-COF-2SO 3 Fourier transform infrared spectrum;

[0045] Figure 4 The PyNTB-COF and PyNTB-COF-SO synthesized in Examples 1, 2 and 3 3 , PyNTB-COF-2SO 3 Nitrogen adsorption-desorption isotherms;

[0046] Figure 5 The Nyquist plots of PyNTB-COF synthesized in Example 1 at different temperatures (a) and the PyNTB-COF-SO synthesized in Example 2 are shown in FIG. 3 Nyquist plots at different temperatures (b), PyNTB-COF-2SO synthesized in Example 3 3 Nyquist plots at different temperatures (c), H synthesized in Example 4 3 PO 4 @PyNTB-COF-2SO 3 Nyquist plots at different temperatures (d);

[0047] Figure 6The agar plate photo of the PyNTB-COF synthesized in Example 1 and the raw materials on Escherichia coli (E. coli) after the photocatalytic experiment and the confocal laser scanning microscope (CLSM) image of E. coli after live / dead staining (scale bar: 20 μm);

[0048] Figure 7 is the bacterial disinfecting rate of PyNTB-COF synthesized in Example 1 and the raw materials against E. coli;

[0049] Figure 8 This is a scanning electron microscope image of the PyNTB-COF synthesized in Example 1 on E. coli before and after irradiation;

[0050] Fig. 9 The agar plate photo of the PyNTB-COF synthesized in Example 1 and the raw materials after the photocatalytic experiment on methicillin-resistant Staphylococcus aureus (MRSA) and the CLSM image of MRSA after live / dead staining (scale bar: 20 μm);

[0051] Fig.10 is the bacterial disinfecting rate of MRSA by the PyNTB-COF synthesized in Example 1 and the raw materials;

[0052] Fig.11 is a scanning electron microscope image of the PyNTB-COF synthesized in Example 1 to MRSA before and after irradiation;

[0053] Fig.12 The PyNTB-COF synthesized in Example 1 and the PyNTB-COF-2SO synthesized in Example 3 3 Photos of agar plates after treatment of artificial water samples with different light exposure times;

[0054] Fig.13 The PyNTB-COF synthesized in Example 1 and the PyNTB-COF-2SO synthesized in Example 3 3 Photographs of agar plates after treatment of natural water samples with different light exposure times. DETAILED DESCRIPTION

[0055] The present invention is further described below by specific examples in conjunction with the accompanying drawings, but the protection scope of the present invention is not limited thereto. The raw materials used in the examples can be obtained from commercial sources unless otherwise specified; the methods used are conventional methods unless otherwise specified, and the equipment used are conventional equipment unless otherwise specified.

[0056] Example 1

[0057] A preparation method of a triphenylamine-based imidazole porous organic polymer, namely PyNTB-COF, is as follows: pyrene-4,5,9,10-tetraone (0.048 mmol), ammonium acetate (0.093 mmol) and tri(4-formylphenyl)amine (0.032 mmol) are mixed and placed in an ampoule, and then solvents of mesitylene (0.8 mL), toluene (0.2 mL) and glacial acetic acid (0.1 mL) are added and mixed evenly. The reaction material was frozen into a solid under liquid nitrogen at -78°C, evacuated to a vacuum, and then thawed until the reaction material was a liquid. This process was repeated three times. After the three freeze-evacuate-thaw cycles, the ampoule was kept in a vacuum state, the tube was sealed, and then placed in an oven at 150°C for reaction for 5 days (the reactants were gradually heated from the low temperature after thawing to 150°C for reaction). The solid was filtered and washed twice with DMF, ethanol, and THF respectively, and then transferred to a Soxhlet extractor and extracted and washed with THF and acetone for 24 hours, and dried at 120°C to obtain a brown PyNTB-COF product with a molar yield of 90%.

[0058] The PyNTB-COF synthesized in this example and the raw materials pyrene-4,5,9,10-tetraketone (PyTO), ammonium acetate (NH 4 OAc) and tri(4-formylphenyl)amine (NTB-CHO) are shown in the Fourier transform infrared spectra. Figure 2 As shown in the figure, it can be seen that the target product is successfully prepared by the present invention.

[0059] Study on the crystallinity of PyNTB-COF:

[0060] The crystallinity of PyNTB-COF was examined by powder diffractometer. The powder X-ray diffraction spectrum was similar to the simulated AA stacking and AB stacking powder X-ray diffraction spectrum. Figure 1 XRD shows good peak shape and high peak intensity, indicating that PyNTB-COF has good crystallinity.

[0061] Study on the Porosity of PyNTB-COF:

[0062] Weigh about 80 mg of sample, activate it at 120℃ for 12 hours, and then test the nitrogen 77K isotherm adsorption curve of the sample by gas adsorption instrument. The nitrogen adsorption and desorption isotherm is as follows: Figure 4 The results show that the synthesized PyNTB-COF has a high specific surface area (884m 2 / g), and the pore size is 2.79nm.

[0063] Example 2

[0064] A triphenylamino imidazole porous organic polymer, namely a partially sulfonated triphenylamino imidazole POPs (PyNTB-COF-SO3 ) is prepared as follows:

[0065] 60 mg of the PyNTB-COF powder prepared by the method of Example 1 was dispersed in 30 mL of dichloromethane solution, and 10.4 mg of 1,3-propane sultone was added, followed by stirring at room temperature for 24 hours, filtering, and then thoroughly washing the solid with water. The obtained sample was then vacuum dried at 100 ° C for 24 hours to obtain dry PyNTB-COF-SO 3 .

[0066] The PyNTB-COF-SO synthesized in this example 3 The Fourier infrared spectrum of Figure 3 As shown, compared with PyNTB-COF, this example successfully prepared partially sulfonated triphenylamino imidazole POPs.

[0067] Nitrogen adsorption-desorption isotherms Figure 4 As shown in the figure, its specific surface area is 422m 2 / g, and the pore size is 2.46nm.

[0068] Example 3

[0069] A triphenylamino imidazole porous organic polymer, namely a completely sulfonated triphenylamino imidazole POPs (PyNTB-COF-2SO 3 ) is prepared as follows:

[0070] 60 mg of the PyNTB-COF powder prepared by the method of Example 1 was dispersed in 30 mL of dichloromethane solution, and 26 mg of 1,3-propane sultone was added, followed by stirring and reacting at 80 ° C for 24 hours, filtering, and then thoroughly washing the solid with water. The obtained sample was then vacuum dried at 100 ° C for 24 hours to obtain dry PyNTB-COF-2SO 3 .

[0071] The PyNTB-COF-2SO synthesized in this example 3 The Fourier infrared spectrum of Figure 3 As shown, compared with PyNTB-COF, this example successfully prepared completely sulfonated triphenylamino imidazole POPs.

[0072] Nitrogen adsorption-desorption isotherms Figure 4 As shown in the figure, its specific surface area is 162m 2 / g, and the pore size is 2.28nm.

[0073] Example 4

[0074] A triphenylamino imidazole porous organic polymer, namely a proton carrier-completely sulfonated triphenylamino imidazole POPs (abbreviated as H 3 PO 4 @PyNTB-COF-2SO 3 ) is prepared as follows:

[0075] Take 60 mg of PyNTB-COF-2SO prepared by the method of Example 3 3 Place it in a mortar, then add 5 μL of 85% phosphoric acid aqueous solution dropwise, and continue grinding at room temperature for 20 minutes. Then, the solid is thoroughly washed with distilled water until the eluent reaches pH = 7. Then, the obtained sample is dried at 120°C for 24 hours to obtain a dried loaded proton carrier-completely sulfonated modified triphenylamino imidazole POPs.

[0076] Example 5

[0077] A triphenylamine imidazole porous organic polymer, as described in Example 1, except that the reaction temperature is 120°C; the other steps and conditions are the same as in Example 1. The molar yield is 75%. The specific surface area is 328 m 2 / g.

[0078] It can be seen from this embodiment that if the reaction temperature is not suitable, the yield and specific surface area of ​​the target product will be greatly reduced.

[0079] Example 6

[0080] A triphenylamine imidazole porous organic polymer, as described in Example 1, except that: the three freeze-pump-thaw cycles are replaced by one vacuuming by a pumping method; the other steps and conditions are the same as in Example 1. The molar yield is 78%. The specific surface area measured by the method in Example 1 is 653 m 2 / g.

[0081] It can be seen from this embodiment that the simple vacuuming method is used to evacuate once, which cannot effectively maintain the oxygen-free and water-free conditions of the reaction environment, resulting in a significant reduction in the yield and specific surface area of ​​the target product.

[0082] Comparative Example 1

[0083] A triphenylamine imidazole porous organic polymer, as described in Example 1, except that the solvent is n-butanol (0.6 mL), dioxane (0.2 mL) and o-dichlorobenzene (0.3 mL); the other steps and conditions are the same as in Example 1. The molar yield is 39%. The specific surface area measured by the method of Example 1 is 126 m 2 / g.

[0084] It can be seen from this comparative example that the choice of solvent type has an important influence on the yield and specific surface area of ​​the target product.

[0085] Comparative Example 2

[0086] A triphenylamine imidazole porous organic polymer, as described in Example 1, except that the solvent is N-methylpyrrolidone (1.6 mL) and mesitylene (1 mL); the other steps and conditions are the same as in Example 1. The molar yield is 65%. The specific surface area measured by the method of Example 1 is 417 m 2 / g.

[0087] It can be seen from this comparative example that the choice of solvent type has an important influence on the yield and specific surface area of ​​the target product.

[0088] Comparative Example 3

[0089] A triphenylamine imidazole porous organic polymer, as described in Example 1, except that the amount of pyrene-4,5,9,10-tetraketone is 0.03 mmol; the other steps and conditions are the same as in Example 1. The molar yield is 63%. The specific surface area measured by the method in Example 1 is 477 m 2 / g.

[0090] It can be seen from this comparative example that the ratio of raw materials has an important influence on the yield and specific surface area of ​​the target product.

[0091] Test Example 1

[0092] Test of proton conductivity:

[0093] The AC impedance of the thin sheets pressed from the materials prepared in Examples 1-4 was tested at a certain humidity and temperature using an electrochemical workstation, and the conductivity value was calculated using the formula σ=L / RA, where σ is the proton conductivity, L is the thickness of the thin sheet membrane, A is the area of ​​the membrane, and R is the resistance.

[0094] Test of proton conductivity changing with temperature under high humidity:

[0095] Keep the humidity (98% RH) constant, change the temperature by 30℃, 40℃, ..., 80℃, etc., and measure the AC impedance graphs respectively, as shown in Figure 5 As shown; the corresponding resistance values ​​are read out through software fitting, and the proton conductivity is calculated. Figure 5 The results showed that the higher the temperature, the higher the proton conductivity.

[0096] Depend on Figure 5 It can be seen that under the conditions of 80℃ and 98%RH, the synthesized H 3 PO 4 @PyNTB-COF-2SO 3It has a high proton conductivity, which can reach 0.79×10 -1 S / cm, which is comparable to the proton conductivity of commercial Nafion (~1×10 -1 S / cm). Under the conditions of 80℃ and 98%RH, PyNTB-COF, PyNTB-COF-SO 3 and PyNTB-COF-2SO 3 The proton conductivity is 8.64×10 -4 S / cm,4.73×10 -3 S / cm and 5.29×10 -2 S / cm.

[0097] Test Example 2

[0098] Antibacterial test:

[0099] Antimicrobial testing for Escherichia coli (E.coli) and methicillin-resistant Staphylococcus aureus (MRSA):

[0100] Dilute the bacterial suspension to 10 6 CFU mL -1 Then, 150 μL of the diluted bacterial solution was added to the 96-well plate and mixed with 50 μL of a 10 mg / L sample solution (dissolved in pure liquid culture medium). The irradiation light wavelength was 660 nm laser with a power of 100 mW cm -2 , for 30 minutes. The 96-well plates after different treatments were cultured at 37°C for 24 hours. The control group used only bacterial solution and culture medium. The pyrene-4,5,9,10-tetraone, tris(4-formylphenyl)amine, and PyNTB-COF (prepared by the method of Example 1) groups were plated with bacteria treated with designated samples and light irradiation. Subsequently, the bacterial suspension was diluted 1000 times with PBS solution, spread on a solid agar plate, cultured at 37°C for 12 hours, and then the colony forming units (CFU) were counted and photographed.

[0101] Figure 6-8 This is the antibacterial test data for Escherichia coli. Figure 9-11 This is the antibacterial test data for methicillin-resistant Staphylococcus aureus (MRSA). Figure 6-11It can be seen that compared with the control group, pyrene-4,5,9,10-tetraketone and tri(4-formylphenyl)amine, PyNTB-COF has a more significant antibacterial effect under visible light irradiation. Electron microscopy photos show that the cell walls of the two bacteria treated with PyNTB-COF were severely damaged after light irradiation, and the contents leaked out. This also proves the excellent photocatalytic antibacterial effect of PyNTB-COF. The above antibacterial experiments fully demonstrate that the synthesized PyNTB-COF has excellent photocatalytic broad-spectrum antibacterial effects.

[0102] Test Example 3

[0103] Water antibacterial test:

[0104] A certain amount of water samples were randomly selected from artificial or natural waters, and the bacterial suspension in the water samples was diluted to 10 6 CFU mL -1 Then, 150 μL of the diluted bacterial solution was added to the 96-well plate and mixed with 50 μL of a 10 mg / L sample solution (materials prepared by the methods of Examples 1 and 3, dissolved in pure liquid culture medium). The irradiation light wavelength was 660 nm laser with a power of 100 mW cm -2 The sample solutions with different treatment times were transferred to a 96-well plate and cultured at 37°C for 24 hours. Subsequently, the bacterial suspension was diluted 1000 times with PBS solution, plated on a solid agar plate, cultured at 37°C for 12 hours, and then the colony forming units (CFU) were counted and photographed.

[0105] Depend on Fig.12 It can be seen that PyNTB-COF-2SO 3 It only takes 15 minutes to achieve >99% bacterial disinfecting rate under visible light irradiation. Under the same conditions, PyNTB-COF takes about 6 hours to achieve the same bacterial disinfecting effect. This shows that the synthesized PyNTB-COF-2SO 3 It shows a more excellent photocatalytic water antibacterial effect.

Claims

1. A triphenylamine imidazole porous organic polymer, characterized in that: The organic polymer is triphenylamino imidazole POPs, sulfonated triphenylamino imidazole POPs or sulfonated triphenylamino imidazole POPs loaded with a proton carrier; The triphenylamino imidazole POPs and the sulfonated triphenylamino imidazole POPs are two-dimensional porous polymers having structural units represented by the following formulas (I) and (II), respectively; Wherein, in formula (II), R1 is a propane sulfonic acid anion group, and R2 is H or a propane sulfonic acid group.

2. The triphenylamine imidazole porous organic polymer according to claim 1, characterized in that: Includes one or more of the following conditions: i. The proton carrier is phosphoric acid or imidazole; ii. The specific surface area of ​​the organic polymer is 150-900m 2 / g, and a pore size of 1-15nm; the organic polymer has good crystallinity.

3. The method for preparing triphenylamino imidazole POPs as claimed in claim 1, comprising the steps of: reacting pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine in an organic solvent A, and then filtering, washing and drying to prepare triphenylamino imidazole POPs.

4. The method for preparing triphenylamino imidazole POPs according to claim 3, characterized in that: Includes one or more of the following conditions: i. The organic solvent A is a mixed solvent of mesitylene, toluene and glacial acetic acid; the volume ratio of mesitylene, toluene and glacial acetic acid is 1-10:1-10:1, preferably 4-8:2-4:1, and more preferably 8:2:1; the volume ratio of the amount of pyrene-4,5,9,10-tetraketone to the organic solvent A is 0.01-0.1 mol / L; ii. The molar ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine is (1.2-2):(1-5):1; preferably, the molar ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine is (1.2-1.8):(2.5-3.5):1; further preferably, the molar ratio of pyrene-4,5,9,10-tetraketone, ammonium acetate and tri(4-formylphenyl)amine is 1.5:2.9:1; iii. The reaction temperature of pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine is 80-150° C., and the reaction time is 2-8 days; most preferably, the reaction temperature is 150° C., and the reaction time is 5 days; iv. One to three freeze-pump-thaw cycles are required before the reaction of pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine.

5. The method for preparing sulfonated triphenylamino imidazole POPs as claimed in claim 1, comprising the steps of dispersing triphenylamino imidazole POPs in an organic solvent B, adding 1,3-propane sultone to react, and then filtering, washing, and drying to obtain sulfonated triphenylamino imidazole POPs.

6. The method for preparing sulfonated triphenylamino imidazole POPs according to claim 5, characterized in that: Includes one or more of the following conditions: i. The organic solvent B is dichloromethane, N-methylpyrrolidone, mesitylene or tetrahydrofuran; the mass ratio of the triphenylamino imidazole POPs to the organic solvent B is 0.4 g / L-5 g / L; ii. The mass ratio of the triphenylamino imidazole POPs to 1,3-propane sultone is 1-10:1; preferably, the mass ratio of the triphenylamino imidazole POPs to 1,3-propane sultone is 2-6:1; further preferably, the mass ratio of the triphenylamino imidazole POPs to 1,3-propane sultone is 5.8:1 or 2.3:1; iii. The reaction temperature is 10-120°C, the reaction time is 10-40 days, and the reaction is carried out under stirring; preferably, the reaction temperature is 20-80°C, and the reaction time is 20-30 days; further preferably, the reaction temperature is 25°C or 80°C.

7. The method for preparing the sulfonated triphenylamino imidazole POPs loaded with a proton carrier as claimed in claim 1, comprising the steps of: A proton carrier aqueous solution with a mass fraction of 80-90% is added dropwise to the sulfonated triphenylamino imidazole POPs, and the mixture is ground, washed and dried to obtain the sulfonated triphenylamino imidazole POPs loaded with proton carriers.

8. The method for preparing the sulfonated triphenylamino imidazole POPs loaded with proton carrier according to claim 7, characterized in that: Includes one or more of the following conditions: i. The proton carrier is phosphoric acid or imidazole; ii. The mass ratio of the sulfonated triphenylamino imidazole POPs to the proton carrier aqueous solution is 10-15 mg / μL; the grinding temperature is room temperature, and the grinding time is 15-25 minutes.

9. The use of the triphenylamine imidazole porous organic polymer as claimed in claim 1, characterized in that: Proton exchange membranes and / or photocatalytic broad-spectrum antibacterial properties used in fuel cells.

10. The use according to claim 9, characterized in that: In the photocatalytic broad-spectrum antibacterial method, the irradiation light wavelength is 660nm laser and the power is 80-120mW cm -2 .

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