A triphenylamine-based imidazole porous organic polymer, a preparation method thereof and application thereof in proton conduction and photocatalytic antibiosis

Abstract

The application provides a triphenylamine-based imidazole porous organic polymer, a preparation method thereof and application thereof in proton conduction and photocatalytic antibiosis. The application uses pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine as raw materials to synthesize a triphenylamine-based imidazole POPS with high crystallinity, high specific surface area, porosity and high structural stability; the POPS containing high-density triphenylamine, imidazole and pyrene groups is subjected to sulfonation modification in different degrees and is loaded with a proton carrier after the sulfonation modification to obtain a series of functionalized triphenylamine-based imidazole porous organic polymers. The triphenylamine-based imidazole porous organic polymer material of the application exhibits good proton conduction capacity under a wide range of temperature conditions and has high use stability. Meanwhile, the triphenylamine-based imidazole porous organic polymer material of the application exhibits excellent photocatalytic broad-spectrum antibiosis effect and excellent antibiosis effect under various water conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to a triphenylamine-based imidazole porous organic polymer, a preparation method thereof and applications thereof in proton conduction and photocatalytic antibiosis, and belongs to the field of new energy materials and antibacterial materials in organic functional materials. BACKGROUND

[0002] Energy crisis and environmental pollution are important problems that human society currently faces and urgently needs to solve. In the future low-carbon society, because proton exchange membrane fuel cells have high conversion efficiency and are environmentally friendly, they are expected to become a powerful alternative to existing traditional fossil fuel-based power technologies. As one of the core technologies of fuel cells, the proton conduction performance of the proton exchange membrane directly affects the final performance of the entire fuel cell. The currently commercialized material in the field of proton exchange membrane technology is a perfluorosulfonic acid-based electrolyte polymer called Nafion; however, its complex synthesis steps, narrow temperature range for use and high cost seriously restrict the application and promotion of the material.

[0003] On the other hand, bacterial contamination in water bodies has become a hidden danger that seriously threatens public health. Antibiotics, as the current general method, often result in a sharp decline in bactericidal effect due to bacterial resistance. Recently, photocatalytic oxidation disinfection technology, as a promising alternative technology for sterilization, can effectively avoid the problem of antibiotic resistance. However, current in-depth research on photocatalysts mainly focuses on inorganic semiconductors (such as TiO2, CdSe and ZnO) and noble metal complexes (such as ruthenium, rhodium and palladium). The metal / dye toxicity and non-recyclability of such traditional photocatalysts seriously 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 due to their special structure and excellent physical and chemical properties. Their inherent organic characteristics endow them with chemical and functional tunability, and they have been widely and deeply studied in many fields such as gas adsorption and separation, sensing, catalysis, energy storage and conversion, etc. 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 application in proton-conducting materials. The invention uses pyrene-4,5,9,10-tetraone, ammonium acetate and tetraaldehyde phenyl porphyrin as raw materials to synthesize a porphyrin-based imidazole POPs with high crystallinity, high specific surface area, porosity, large pore size and high structural stability. The POPs containing high-density porphyrin groups, porphyrin imidazole and pyrene groups are respectively modified by sulfonation, loaded with phosphoric acid and modified by sulfonation and then loaded with phosphoric acid to obtain a series of functionalized porphyrin-based imidazole POPs materials. The POPs material of the invention exhibits good proton conduction ability under a wide range of temperature and humidity conditions, as well as under anhydrous conditions, and has very high stability. However, its sulfonation modification uses chlorosulfonic acid as raw material, the sulfonation conditions are relatively harsh, and the modification site has certain uncertainty; and it does not have antibacterial effect. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a triphenylamine-based imidazole porous organic polymer, its preparation method and application in proton conduction and photocatalytic antibacterial. The invention uses pyrene-4,5,9,10-tetraone, ammonium acetate and tri(4-formylphenyl)amine as raw materials to synthesize a triphenylamine-based 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 modified by sulfonation to different degrees and then loaded with a proton carrier to obtain a series of functionalized triphenylamine-based imidazole porous organic polymers. The triphenylamine-based imidazole porous organic polymer material of the invention exhibits good proton conduction ability under a wide range of temperature conditions, and has very high stability. At the same time, the triphenylamine-based imidazole porous organic polymer material of the invention exhibits excellent photocatalytic broad-spectrum antibacterial effect and excellent antibacterial effect under various water conditions.

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

[0007] A triphenylamine-based imidazole porous organic polymer, the organic polymer is a triphenylamine-based imidazole POPs, a sulfonated modified triphenylamine-based imidazole POPs or a sulfonated modified triphenylamine-based imidazole POPs loaded with a proton carrier;

[0008] The triphenylamine-based imidazole POPs and the sulfonated modified triphenylamine-based imidazole POPs are two-dimensional porous polymers having structural units shown in the following formula (I) and (II) respectively.

[0009]

[0010]

[0011] In formula (II), R1 is a propane sulfonic acid anion group, and R2 is H or a propane sulfonic acid group.

[0012] According to the application, preferably, the proton carrier is phosphoric acid or imidazole.

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

[0014] The preparation method of the triphenylamine-based imidazole POPs comprises the following steps: 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 obtain the triphenylamine-based imidazole POPs.

[0015] According to the application, the pyrene-4,5,9,10-tetraone and tri(4-formylphenyl)amine have the following structures:

[0016]

[0017] According to the application, preferably, 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; and the molar amount of pyrene-4,5,9,10-tetraone and the volume of the organic solvent A are in a ratio of 0.01-0.1 mol / L.

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

[0019] According to the application, the reaction temperature of pyrene-4, 5, 9, 10-tetraone, ammonium acetate and tris (4-formylphenyl) amine is 80-150 DEG C, and the reaction time is 2-8 days; most preferably, the reaction temperature is 150 DEG C, and the reaction time is 5 days.

[0020] According to the application, the reaction of pyrene-4, 5, 9, 10-tetraone, ammonium acetate and tris (4-formylphenyl) amine needs one to three freeze-pumping-thaw cycles before reaction to keep the reaction system in vacuum state, so as to ensure the reaction under the conditions of no oxygen and no water.

[0021] According to the application, the reaction of pyrene-4, 5, 9, 10-tetraone, ammonium acetate and tris (4-formylphenyl) amine is carried out in a thick-walled pressure-resistant tube or an ampoule.

[0022] According to the application, the washing is carried out with DMF, ethanol and THF for 2-3 times respectively, and then THF and acetone are used for Soxhlet extraction for 15-48 hours.

[0023] According to the application, the drying temperature is 80-120 DEG C.

[0024] The preparation method of the sulfonated modified triphenylamine-based imidazole POPs comprises the steps of dispersing the prepared triphenylamine-based imidazole POPs in an organic solvent B, adding 1, 3-propane sulfone lactone for reaction, and then filtering, washing and drying to obtain the sulfonated modified triphenylamine-based imidazole POPs.

[0025] According to the application, the organic solvent B is dichloromethane, N-methyl pyrrolidone, mesitylene or tetrahydrofuran; and the mass ratio of the triphenylamine-based imidazole POPs to the organic solvent B is 0.4 g / L-5 g / L.

[0026] According to the application, the mass ratio of the triphenylamine-based imidazole POPs to 1, 3-propane sulfone lactone is 1-10:1; preferably, the mass ratio of the triphenylamine-based imidazole POPs to 1, 3-propane sulfone lactone is 2-6:1; and further preferably, the mass ratio of the triphenylamine-based imidazole POPs to 1, 3-propane sulfone lactone is 5.8:1 or 2.3:1.

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

[0028] According to the application, the washing is carried out with water; and the drying temperature is 60-120 DEG C.

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

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

[0031] According to the application, the proton carrier is preferably phosphoric acid or imidazole. The phosphoric acid (H3PO4) has a high proton concentration, low volatility (>158℃) and high proton mobility.

[0032] According to the application, the mass of the sulfonated modified triphenylamine-based imidazole POPs and the volume of the proton carrier aqueous solution are preferably 10-15 mg / μL, the grinding temperature is room temperature, and the grinding time is 15-25 minutes.

[0033] The above-mentioned triphenylamine-based imidazole porous organic polymers are applied to proton exchange membranes in fuel cells or / and photocatalytic broad-spectrum antibacterial.

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

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

[0036] 1. The application uses pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine as raw materials to synthesize a new triphenylamine-based imidazole POPs containing high-density triphenylamine, imidazole and pyrene groups through a Debus-Radziszewski reaction in one step; the ratio of pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine, the organic solvent A used and the reaction temperature need to be appropriate, otherwise the triphenylamine-based imidazole POPs with the structure and properties of the application cannot be obtained. At the same time, the reaction temperature also needs to be appropriate, and the method of combining freezing-pumping-thawing cycles is used to obtain the triphenylamine-based imidazole POPs with the structure and properties of the application. The preparation method of the application as a whole makes the yield of the target product of the application higher, which can reach 90%.

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

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

[0039] 3、The completely sulfonated triphenylamine-based imidazole POPs prepared in the application have high-density triphenylamine groups, imidazole groups and sulfonic acid groups, which are excellent proton acceptors and have free protons and proton carrier coordination sites, so that the proton carrier can be further loaded to further improve the proton conductivity of the POPs. Therefore, the triphenylamine-based imidazole porous organic polymer has great potential as a proton conducting material. The various groups in the application interact with each other as a whole, and compared with other porous organic polymers of the prior art, the triphenylamine-based imidazole porous organic polymer has more excellent proton conductivity and use stability.

[0040] The triphenylamine-based imidazole porous organic polymer prepared in the application exhibits good proton conductivity under a wide range of temperature conditions: under high humidity, the proton conductivity can reach 0.79 x 10 -1 S / cm, which is comparable to the performance of the current commercial Nafion material (-1 x 10 -1 S / cm). The material has a triphenylamine and imidazole rigid skeleton, and therefore has higher structural stability and use stability compared with similar materials, and is a potential new material that can be applied to proton exchange membrane fuel cells.

[0041] 4、The triphenylamine-based imidazole porous organic polymer prepared by the method has triphenylamine groups introduced as a typical photosensitive group, which can generate active oxygen species under light to kill bacteria, and therefore can be applied to the field of photocatalytic antibacterial. Due to the proton transfer in the photocatalytic process, the higher proton conductivity of the triphenylamine-based imidazole porous organic polymer, especially the sulfonated modified triphenylamine-based imidazole POP, also enhances the photocatalytic antibacterial ability. Therefore, the triphenylamine-based imidazole porous organic polymer prepared by the method also has excellent photocatalytic broad-spectrum antibacterial effect and excellent antibacterial effect under various water conditions: in artificial water and natural water, the completely sulfonated modified triphenylamine-based imidazole POP can achieve > 99% of the bacterial killing rate under visible light irradiation for only 15 minutes. BRIEF DESCRIPTION OF DRAWINGS

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

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

[0044] Figure 3 is the Fourier infrared spectrum of the PyNTB-COF, PyNTB-COF-SO3 and PyNTB-COF-2SO3 synthesized in Examples 1, 2 and 3;

[0045] Figure 4 is the nitrogen adsorption-desorption isotherm of the PyNTB-COF, PyNTB-COF-SO3 and PyNTB-COF-2SO3 synthesized in Examples 1, 2 and 3;

[0046] Figure 5 is the Nyquist plot of the PyNTB-COF synthesized in Example 1 at different temperatures (a), the Nyquist plot of the PyNTB-COF-SO3 synthesized in Example 2 at different temperatures (b), the Nyquist plot of the PyNTB-COF-2SO3 synthesized in Example 3 at different temperatures (c), and the Nyquist plot of the H3PO4@PyNTB-COF-2SO3 synthesized in Example 4 at different temperatures (d);

[0047] Figure 6 is the agar plate photo of E. coli after photocatalysis of the PyNTB-COF synthesized in Example 1 and the raw material, and the CLSM image of E. coli after vital / dead staining (scale: 20 μm);

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

[0049] Figure 8 is the scanning electron microscope images of the PyNTB-COF synthesized in Example 1 against E. coli before and after light irradiation;

[0050] Figure 9 is the agar plate photos of the PyNTB-COF synthesized in Example 1 and the raw material against methicillin-resistant Staphylococcus aureus (MRSA) after photocatalysis experiment and the CLSM images of MRSA after vital / dead staining (scale bar: 20 μm);

[0051] Figure 10 is the bactericidal rate of the PyNTB-COF synthesized in Example 1 and the raw material against MRSA;

[0052] Figure 11 is the scanning electron microscope images of the PyNTB-COF synthesized in Example 1 against MRSA before and after light irradiation;

[0053] Figure 12 is the agar plate photos of the PyNTB-COF synthesized in Example 1 and the PyNTB-COF-2SO3 synthesized in Example 3 after treating artificial water samples and after different light irradiation time;

[0054] Figure 13 is the agar plate photos of the PyNTB-COF synthesized in Example 1 and the PyNTB-COF-2SO3 synthesized in Example 3 after treating natural water samples and after different light irradiation time. DETAILED DESCRIPTION

[0055] The application is further described below by specific examples and in conjunction with the drawings, but the scope of protection of the application is not limited thereto. In the examples, the raw materials used are commercially available unless otherwise specified; the methods used are conventional methods unless otherwise specified; and the equipment used is 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, then solvent mesitylene (0.8 mL), toluene (0.2 mL) and glacial acetic acid (0.1 mL) are added and uniformly mixed. The reaction material is frozen into a solid under liquid nitrogen at -78℃, is pumped to vacuum, and then is thawed to be a liquid, and the above-mentioned three freezing-pumping-thawing cycles are repeated three times, after the three freezing-pumping-thawing cycles, the ampoule is kept in a vacuum state, is sealed, and then is placed in an oven at 150℃ for 5 days (the reaction is carried out as the reaction material gradually warms up from low temperature after thawing to 150℃), is filtered to obtain a solid, is sequentially washed with DMF, ethanol and THF each for two times, and then is sequentially subjected to Soxhlet extraction with THF and acetone each for 24 hours in a Soxhlet extractor, and is dried at 120℃ to obtain a brown PyNTB-COF product with a molar yield of 90%.

[0058] The Fourier infrared spectra of the synthesized PyNTB-COF and raw materials pyrene-4,5,9,10-tetraone (PyTO), ammonium acetate (NH4OAc) and tri(4-formylphenyl)amine (NTB-CHO) are as shown in Figure 2 The figure shows that the target product is successfully prepared.

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

[0060] The crystallinity of PyNTB-COF is tested by a powder diffractometer, and powder X-ray diffraction spectra of the simulated AA stacking and AB stacking are as shown in Figure 1 The XRD shows good peak type and very high peak intensity, indicating that PyNTB-COF has good crystallinity.

[0061] Research on the porosity of PyNTB-COF:

[0062] About 80 mg of the sample is weighed, activated at 120℃ for 12 hours, and then the nitrogen 77K adsorption isotherm of the sample is tested by a gas adsorption instrument, and the nitrogen adsorption / desorption isotherm is as shown in Figure 4 The results show that the synthesized PyNTB-COF has a relatively high specific surface area (884 m 2 / g) and a pore size of 2.79 nm.

[0063] Example 2

[0064] A preparation method of a triphenylamine-based imidazole porous organic polymer, namely partially sulfonated modified triphenylamine-based imidazole POPs (abbreviated as PyNTB-COF-SO3), is as follows:

[0065] Take 60 mg of PyNTB-COF powder prepared by the method of Example 1, disperse it in 30 mL of dichloromethane solution, add 10.4 mg of 1,3-propane sultone, then stir the reaction at room temperature for 24 hours, filter, then wash the solid thoroughly with water, then vacuum dry the resulting sample at 100°C for 24 hours to obtain dried PyNTB-COF-SO3.

[0066] The Fourier infrared spectrum of PyNTB-COF-SO3 synthesized in this example is shown in Figure 3 As can be seen from the comparison with PyNTB-COF, the partially sulfonated modified triphenylamine-based imidazole POPs are successfully prepared in this example.

[0067] The nitrogen adsorption-desorption isotherm is shown in Figure 4 As can be seen from the figure, the specific surface area is 422 m 2 / g, and the pore size is 2.46 nm.

[0068] Example 3

[0069] A preparation method of a triphenylamine-based imidazole porous organic polymer, i.e. completely sulfonated modified triphenylamine-based imidazole POPs (abbreviated as PyNTB-COF-2SO3), is as follows:

[0070] Take 60 mg of PyNTB-COF powder prepared by the method of Example 1, disperse it in 30 mL of dichloromethane solution, add 26 mg of 1,3-propane sultone, then stir the reaction at 80°C for 24 hours, filter, then wash the solid thoroughly with water, then vacuum dry the resulting sample at 100°C for 24 hours to obtain dried PyNTB-COF-2SO3.

[0071] The Fourier infrared spectrum of PyNTB-COF-2SO3 synthesized in this example is shown in Figure 3 As can be seen from the comparison with PyNTB-COF, the completely sulfonated modified triphenylamine-based imidazole POPs are successfully prepared in this example.

[0072] The nitrogen adsorption-desorption isotherm is shown in Figure 4 As can be seen from the figure, the specific surface area is 162 m 2 / g, and the pore size is 2.28 nm.

[0073] Example 4

[0074] A preparation method of a triphenylamine-based imidazole porous organic polymer, i.e. proton carrier-loaded completely sulfonated modified triphenylamine-based imidazole POPs (abbreviated as H3PO4@PyNTB-COF-2SO3), is as follows:

[0075] Take 60 mg of PyNTB-COF-2SO3 prepared by the method of Example 3 and place it in a mortar, then add 5 μL of 85% mass fraction phosphoric acid aqueous solution drop by drop, and continue to grind at room temperature for 20 minutes, then wash the solid with distilled water until the eluent reaches pH = 7, then dry the obtained sample at 120°C for 24 hours to obtain a dried proton carrier-loaded fully sulfonated modified triphenylamine-based imidazole POP.

[0076] Example 5

[0077] A triphenylamine-based imidazole porous organic polymer was prepared as described in Example 1, except that the reaction temperature was 120°C; the other steps and conditions were the same as in Example 1. The molar yield was 75%. Its specific surface area was 328 m 2 / g, tested according to the method of Example 1.

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

[0079] Example 6

[0080] A triphenylamine-based imidazole porous organic polymer was prepared as described in Example 1, except that the three freeze-pumping-thaw cycles were replaced by a single vacuum pumping process using a pump; the other steps and conditions were the same as in Example 1. The molar yield was 78%. Its specific surface area was 653 m 2 / g, tested according to the method of Example 1.

[0081] It can be seen from this example that a single vacuum pumping process using a pump 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-based imidazole porous organic polymer was prepared as described in Example 1, except that the solvent was n-butanol (0.6 mL), dioxane (0.2 mL), and o-dichlorobenzene (0.3 mL); the other steps and conditions were the same as in Example 1. The molar yield was 39%. Its specific surface area was 126 m 2 / g, tested according to the method of Example 1.

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

[0085] Comparative Example 2

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

[0087] From this comparative example, it can be seen that the selection of the solvent has an important influence on the yield and specific surface area of the target product.

[0088] Comparative Example 3

[0089] A triphenylamine-based imidazole porous organic polymer was prepared as described in Example 1, except that the amount of pyrene-4,5,9,10-tetraone was 0.03 mmol; the other steps and conditions were the same as in Example 1. The molar yield was 63%. The specific surface area was tested according to the method of Example 1 and was 477 m 2 / g.

[0090] From this comparative example, it can be seen that the proportion of the 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 pressed sheet of the material prepared in Examples 1-4 was tested using an electrochemical workstation at a certain humidity and temperature, and the conductivity value was calculated using the formula σ = L / RA, where σ is the proton conductivity, L is the thickness of the sheet film, A is the area of the film, and R is the resistance.

[0094] Test of the change in proton conductivity with temperature at high humidity:

[0095] The humidity (98% RH) was kept constant, and the temperature was changed to 30°C, 40°C, …, 80°C, and so on, and the AC impedance diagrams were measured, as shown in Figure 5 The corresponding resistance values were read out by software fitting, and the proton conductivity was calculated. From the Figure 5 It was found that the higher the temperature, the higher the proton conductivity.

[0096] From the Figure 5 It can be seen that the synthesized H3PO4@PyNTB-COF-2SO3 has very high proton conductivity under the conditions of 80°C and 98% RH, and can reach a proton conductivity of 0.79 x 10 -1 S / cm, which is comparable to the proton conductivity of commercial Nafion (~1 x 10 -1S / cm) at 80 °C, 98% RH. The proton conductivities of PyNTB-COF, PyNTB-COF-SO3 and PyNTB-COF-2SO3 were 8.64 x 10 -4 S / cm, 4.73 x 10 -3 S / cm and 5.29 x 10 -2 S / cm, respectively.

[0097] Test Example 2

[0098] Test of the antibacterial experiment:

[0099] Antibacterial test of E. coli and MRSA:

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

[0101] Figures 6-8 is the antibacterial test data of E. coli, Figures 9-11 is the antibacterial test data of MRSA. It can be seen from Figures 6-11 that compared with the control group, pyrene-4,5,9,10-tetraone and tris(4-formylphenyl)amine, PyNTB-COF has a more significant antibacterial effect under visible light irradiation. The electron microscope photos show that the cell walls of the two types of bacteria treated with PyNTB-COF are severely damaged after light irradiation, and the inclusions are exuded. 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 effect.

[0102] Test Example 3

[0103] Water body antibacterial test:

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

[0105] Depend on Figure 12 It was found that PyNTB-COF-2SO3 achieved a bacterial elimination rate of >99% within just 15 minutes under visible light irradiation. Under the same conditions, PyNTB-COF required approximately 6 hours to achieve the same bacterial elimination effect. This indicates that the synthesized PyNTB-COF-2SO3 exhibits superior photocatalytic antibacterial effects in water.

Claims

1. A triphenylaminoimidazolium porous organic polymer, characterized in that, The organic polymer is triphenylaminoimidazolium POPs, sulfonated triphenylaminoimidazolium POPs, or sulfonated triphenylaminoimidazolium POPs loaded with a proton carrier. The triphenylaminoimidazolium POPs and the sulfonated triphenylaminoimidazolium POPs are two-dimensional porous polymers having the structural units shown in formulas (I) and (II), respectively. （I） (II) In formula (II), R1 is a propane sulfonic acid anionic group, and R2 is H or a propane sulfonic acid group.

2. The triphenylaminoimidazolium porous organic polymer according to claim 1, characterized in that, Includes one or more of the following conditions: i. The proton carrier is phosphate or imidazole; ii. The specific surface area of ​​the organic polymer is 150-900 m². 2 / g, with a pore size of 1-15 nm; the organic polymer has good crystallinity.

3. The method for preparing triphenylaminoimidazolium POPs as described in claim 1, comprising the steps of: reacting pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine in organic solvent A, and then preparing triphenylaminoimidazolium POPs by filtration, washing and drying.

4. The method for preparing triphenylaminoimidazolium 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; the molar amount of pyrene-4,5,9,10-tetraone and the volume ratio of organic solvent A are 0.01-0.1 mol / L. ii. The molar ratio of pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine is (1.2-2):(1-5):1; iii. The reaction temperature of pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine is 80-150 °C, and the reaction time is 2-8 days; iv. Before reacting with pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine, one to three freezing-evacuation-thawing cycles are required.

5. The method for preparing triphenylaminoimidazolium POPs according to claim 4, characterized in that, Includes one or more of the following conditions: i. The volume ratio of mesitylene, toluene and glacial acetic acid is 4-8:2-4:1; ii. The molar ratio of pyrene-4,5,9,10-tetraone, ammonium acetate and tris(4-formylphenyl)amine is (1.2-1.8):(2.5-3.5):

1.

6. The method for preparing sulfonated triphenylaminoimidazolium POPs as described in claim 1, comprising the steps of: dispersing triphenylaminoimidazolium POPs in organic solvent B, adding 1,3-propanesulfonyl lactone for reaction, and then filtering, washing, and drying to obtain sulfonated triphenylaminoimidazolium POPs.

7. The method for preparing sulfonated triphenylaminoimidazolium POPs according to claim 6, 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 triphenylaminoimidazolium POPs to the volume ratio of the organic solvent B is 0.4 g / L-5 g / L; ii. The mass ratio of the triphenylaminoimidazolium POPs to 1,3-propanesulfonyl lactone is 1-10:1; iii. The reaction temperature is 10-120 ℃, the reaction time is 10-40 days, and the reaction is carried out under stirring conditions.

8. The method for preparing sulfonated triphenylaminoimidazolium POPs according to claim 7, characterized in that, Includes one or more of the following conditions: i. The mass ratio of the triphenylaminoimidazolium POPs to 1,3-propanesulfonyl lactone is 2-6:1; ii. The reaction temperature is 20-80℃, and the reaction time is 20-30 days.

9. The method for preparing sulfonated triphenylaminoimidazolium POPs supported on a proton carrier as described in claim 1, comprising the steps of: Add an 80-90% (w / w) proton carrier aqueous solution to the above sulfonated triphenylaminoimidazolium POPs dropwise, grind, and then wash and dry to obtain sulfonated triphenylaminoimidazolium POPs loaded with proton carrier.

10. The method for preparing sulfonated triphenylaminoimidazolium POPs supported on a proton carrier according to claim 9, characterized in that, Includes one or more of the following conditions: i. The proton carrier is phosphate or imidazole; ii. The mass ratio of sulfonated triphenylaminoimidazolium POPs to the volume ratio of the proton carrier aqueous solution was 10-15 mg / μL; the grinding temperature was room temperature, and the grinding time was 15-25 minutes.

11. The application of the triphenylaminoimidazolium porous organic polymer as described in claim 1, characterized in that, Proton exchange membranes and / or photocatalytic broad-spectrum antibacterial agents used in fuel cells.

12. The application according to claim 11, characterized in that, In photocatalytic broad-spectrum antibacterial activity, the irradiation light wavelength is 660nm laser with a power of 80-120 mW / cm². -2 .

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