Preparation method of conjugated microporous polymer and application of conjugated microporous polymer in degradation of bisphenol A

Abstract

The invention discloses a preparation method of a conjugated microporous polymer and application of the conjugated microporous polymer in degradation of bisphenol A, and relates to the field of conjugated microporous polymers. The invention aims to solve the problems of high catalyst cost, poor stability, low utilization rate of active substances and limitation on large-scale industrial application in the catalytic degradation of bisphenol A by using a catalyst in the prior art. The structural formula of the conjugated microporous polymer is shown in the specification. The method comprises the following steps: 1, adding 1, 3, 6, 8-tetrabromo pyrene, 1, 3, 5-triacetylene benzene, tetrakis (triphenylphosphine) palladium and cuprous iodide into a mixed solvent of N, N-dimethylformamide and triethylamine to obtain a mixed solution; 2, hydrothermal reaction; and 3, cleaning and drying. According to the application of the conjugated microporous polymer to adsorption and / or degradation of bisphenol A in water, the method is simple and easy to operate, the degradation efficiency is high, the mineralization rate is high, the conjugated microporous polymer is repeatable, the use cost is low, and the conjugated microporous polymer is suitable for large-scale popularization and application.

Description

Technical Field

[0001] This invention relates to the field of conjugated microporous polymers, and more specifically to a method for preparing a conjugated microporous polymer and its application in the degradation of bisphenol A. Background Technology

[0002] Bisphenol A (BPA) is a widely used endocrine disruptor, found in a wide variety of products. It is a chemical substance frequently encountered by humans, affecting physical development and leading to endocrine disorders, childhood obesity, breast cancer, and other reproductive and developmental problems. Therefore, many countries have enacted laws and regulations to restrict its use. BPA concentrations in industrial and domestic wastewater range from 16 to 1465 ng / L, while those in surface water range from 170 to 3113 ng / L. The health effects of BPA may be cumulative and irreversible, endangering human life and health; therefore, the treatment of BPA wastewater is urgently needed.

[0003] Currently, the main methods for treating water bodies affected by BPA pollution include adsorption, biological methods, persulfate oxidation, ozone oxidation, and photocatalytic oxidation. However, all of these methods have drawbacks such as high cost, incomplete degradation, and limited applicability.

[0004] Adsorption is one of the important methods for the advanced treatment of BPA wastewater. This method enriches BPA using adsorption materials, and then recovers the BPA using other methods. However, because the pollutant is not completely degraded, the adsorbed materials pose a risk of secondary pollution.

[0005] Biological methods utilize microorganisms to biotransform / absorb foreign pollutants, achieving pollutant removal through efficient and environmentally friendly processes. However, they have drawbacks such as long operation cycles, poor treatment efficiency for high-concentration samples, and increased estrogen activity after biodegradation.

[0006] Persulfate oxidation typically involves photothermal stimulation or transition metal activation of persulfate to generate highly oxidizing sulfate radicals (SO4·4·4). - This technology uses mineralization to degrade organic molecules. However, in practical applications, it has drawbacks such as a narrow working pH range, easy dissolution of metal ions causing secondary pollution, and the need for post-processing of powdered catalysts, making them difficult to recycle and reuse.

[0007] Ozone oxidation utilizes the active sites on the surface of catalytic materials to accelerate the decomposition of ozone into O· and OH·, converting organic matter in water into non-toxic small molecules. However, ozone oxidation also suffers from problems such as poor mass transfer efficiency, low ozone utilization, complex catalyst preparation, and high cost.

[0008] Photocatalytic oxidation utilizes renewable solar energy or artificial light sources to activate photocatalysts, generating highly oxidizing free radicals (such as ·OH) that mineralize organic matter into CO2 and H2O. However, some photogenerated electron-hole pairs recombine during migration, causing energy to dissipate as heat and reducing photocatalytic efficiency.

[0009] Ultraviolet light has high energy and can degrade almost all organic matter to some extent, working on pollutants with different structures and properties. However, most photocatalysts can only absorb light energy in the ultraviolet region, while ultraviolet light accounts for only 4% of sunlight, resulting in low utilization efficiency of visible light. Summary of the Invention

[0010] The purpose of this invention is to address the problems of high catalyst cost, poor stability, and low utilization rate of active substances in the existing technology for catalytic degradation of bisphenol A, which limit its large-scale industrial application. The invention provides a method for preparing a conjugated microporous polymer and its application in the degradation of bisphenol A.

[0011] This invention provides a conjugated microporous polymer (CMP) with a specific structure, which forms a synergistic photocatalytic system with sodium persulfate. Under visible light (LED lamp), the persulfate is activated to generate sulfate radicals SO4·2- with high activity, high oxidizing power, and high stability. - This invention provides a novel, mild, and efficient method for the photocatalytic degradation of bisphenol A.

[0012] A method for preparing a conjugated microporous polymer, wherein the structural formula of the conjugated microporous polymer is as follows: Formula I; Formula I is composed of alternating connections of the structures shown in Formula II and Formula III; the molar ratio of the structures shown in Formula II to those shown in Formula III is 3:4;

[0013] Formula IⅠ; Formula III;

[0014] The preparation method is completed according to the following steps:

[0015] 1. Add 1,3,6,8-tetrabromopyrene, 1,3,5-triethynylbenzene, tetra(triphenylphosphine)palladium and cuprous iodide to a mixed solvent of N,N-dimethylformamide and triethylamine, and stir until homogeneous to obtain a mixed solution;

[0016] 2. Transfer the mixed solution to the polytetrafluoroethylene liner of the reactor; evacuate the reaction system and then purge with nitrogen; repeat the above evacuation and nitrogen purging operations several times to remove dissolved oxygen, then install the polytetrafluoroethylene liner into the stainless steel reactor outer shell and tighten the seal; transfer the reactor to an oven at a temperature of 80℃~120℃ for reaction; after the reaction is completed, cool to room temperature to obtain a solid product;

[0017] Third, the solid product is cleaned, then vacuum dried and ground to obtain a brownish-red solid powder, which is the conjugated microporous polymer.

[0018] Application of the conjugated microporous polymer in the adsorption and / or degradation of bisphenol A in water.

[0019] The principle of this invention:

[0020] CMP materials, under light irradiation, generate photoelectrons that can activate H2O2 or persulfate to efficiently produce ·O2. - ·OH or SO4· - Active free radicals are used to degrade pollutants, improving degradation efficiency. The degradation mechanism is described in [link to documentation]. Figure 22 As shown:

[0021] Under illumination, electrons in CMPs that are in the HOMO orbital (valence band) transfer to the LUMO orbital (conduction band), simultaneously generating photogenerated electrons (electrons). - ) and holes (h + Yes; the generated photogenerated carriers rapidly migrate to the material surface and react with adsorbed oxygen (O2) and other substances to generate superoxide radicals (·O2). - When persulfate is present, photogenerated electrons will activate S2O8. 2- One molecule of the highly reactive species SO4 is generated. ·– and one molecule of SO4 2- Meanwhile, SO4· - It is possible to be with - OH generates another highly reactive species, ·OH. Subsequently, the highly reactive species generated in situ in the system synergistically degrades BPA molecules enriched in the micropores of CMPs, ultimately breaking them down into harmless carbon dioxide and water through a series of redox reactions. The entire process is driven by light energy, while the high specific surface area and tunable electronic structure of CMPs ensure extremely high catalytic efficiency.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] I. The present invention is a conjugated microporous polymer with a specific D-π-A structure, which is responsive to visible light. It can be combined with sodium persulfate to form a CMP / PDS synergistic photocatalytic system for the visible light photocatalytic degradation of bisphenol A. It has the characteristics of high degradation efficiency, high mineralization rate, can be activated by common visible light, high efficiency, high stability and reusability. It is suitable for complex actual water environments and is suitable for large-scale promotion and application.

[0024] II. The conjugated microporous polymer of the present invention can be used to adsorb and / or degrade bisphenol A. The method is simple and easy to operate, with high degradation efficiency and high mineralization rate. The conjugated microporous polymer is reproducible and has low cost of use, making it suitable for large-scale promotion and application.

[0025] Third, the conjugated microporous polymer prepared using this invention can achieve a degradation efficiency of 99% for bisphenol A. Attached Figure Description

[0026] Figure 1 The synthetic route diagram for CMP2-170 prepared in Example 1 of this invention;

[0027] Figure 2 This is a SEM image of CMP2-170 prepared in Example 1 of the present invention at a resolution of 200 nm;

[0028] Figure 3 The N2-BET spectrum of CMP2-170 prepared in Example 1 of this invention;

[0029] Figure 4 The micropore size distribution diagram of CMP2-170 prepared in Example 1 of this invention;

[0030] Figure 5 The infrared spectra of CMP2-170 and its raw materials prepared in Example 1 of this invention are shown below.

[0031] Figure 6 The XPS full spectrum of CMP2-170 prepared in Example 1 of this invention;

[0032] Figure 7 The XPS fine spectrum of CMP2-170 prepared in Example 1 of this invention is shown below. a represents C1S; b represents O1s; c represents N1s; and d represents Br3d3 / 2.

[0033] Figure 8 The UV-Vis spectrum of CMP2-170 prepared in Example 1 of this invention;

[0034] Figure 9 The VB-XPS spectrum of CMP2-170 prepared in Example 1 of this invention;

[0035] Figure 10The conduction band potential diagram of CMP2-170 prepared in Example 1 of this invention;

[0036] Figure 11 The transient photocurrent response diagram of CMP2-170 prepared in Example 1 of this invention;

[0037] Figure 12 Thermogravimetric analysis (TGA) curve of CMP2-170 prepared in Example 1 of this invention;

[0038] Figure 13 This is a comparison chart showing the adsorption and photocatalytic degradation effects of CMPs materials with different structures on bisphenol A in Example 1.

[0039] Figure 14 This is a comparison chart of the photocatalytic degradation effects of bisphenol A in each experimental group in Example 2.

[0040] Figure 15 This is a comparison of the photocatalytic degradation effects of commonly used photocatalysts TiO2, g-C3N4, and CMP2-170 in combination with PDS in Example 3 on bisphenol A.

[0041] Figure 16 The graph shows the degradation effect of CMP2-170 prepared in Example 1 of Application Example 4 on bisphenol A when used in combination with PDS at different dosages.

[0042] Figure 17 The graph shows the degradation effect of PDS combined with CMP2-170 prepared in Example 1 on bisphenol A under different dosages in Example 5.

[0043] Figure 18 The graph shows the adsorption and degradation effect of CMP2-170 prepared in Example 1 of Application Example 6 in combination with PDS on bisphenol A in water containing bisphenol A at different pH values.

[0044] Figure 19 The graph shows the adsorption and degradation effects of CMP2-170 combined with PDS on bisphenol A in water containing different competing ions.

[0045] Figure 20 The graph shows the degradation effect of CMP2-170 prepared in Example 1 on bisphenol A after repeated use.

[0046] Figure 21 The graph shows the photocatalytic degradation kinetics of CMP2-170 prepared in Example 1 of Application Example 9; where Adsorption represents adsorption, Desorption represents desorption, and Relative Pressure (p / p) represents desorption. oThe symbol () represents relative pressure, that is, the ratio of the pressure here to the standard atmospheric pressure. Quantity Adsorbed represents the amount of adsorption, measured in cm³. 3 / g; PoreWidth represents the micropore diameter in nm; dV / dlogD represents the pore area in cm². 3 g -1 nm -1 Stretching vibration refers to stretching vibration, bending vibration refers to bending vibration, and wavelength refers to wavelength. Binding energy refers to binding energy. Energy refers to energy. Raw refers to raw data, fitting curve refers to the fitted curve, and background refers to the background. Potential refers to electric potential in V, and vs. NHE refers to the potential relative to the standard hydrogen electrode (NHE). Current refers to transient photocurrent, Time refers to time, and second refers to seconds. Weight refers to weight, and Temperature refers to temperature in °C. Light On / Light refers to illumination, Light Off refers to no illumination, and Dark refers to a light-protected environment. c (mg / L) refers to the concentration of bisphenol A in the solution, Time of visible light exposure refers to the exposure time of visible light, h refers to hours, and min refers to minutes. c / c0 (%) and c t / c0 (%) represents the concentration of bisphenol A in the solution at different times, c, c t The percentage relative to the initial concentration c0 of bisphenol A in the solution;

[0047] Figure 22 Mechanism of CMP materials for degrading pollutants. Detailed Implementation

[0048] Specific Implementation Method 1: The structural formula of the conjugated microporous polymer described in this implementation method is as follows: The preparation method is completed according to the following steps:

[0049] 1. Add 1,3,6,8-tetrabromopyrene, 1,3,5-triethynylbenzene, tetra(triphenylphosphine)palladium and cuprous iodide to a mixed solvent of N,N-dimethylformamide and triethylamine, and stir until homogeneous to obtain a mixed solution;

[0050] 2. Transfer the mixed solution to the polytetrafluoroethylene liner of the reactor; evacuate the reaction system and then purge with nitrogen; repeat the above evacuation and nitrogen purging operations several times to remove dissolved oxygen, then install the polytetrafluoroethylene liner into the stainless steel reactor outer shell and tighten the seal; transfer the reactor to an oven at a temperature of 80℃~120℃ for reaction; after the reaction is completed, cool to room temperature to obtain a solid product;

[0051] Third, the solid product is cleaned, then vacuum dried and ground to obtain a brownish-red solid powder, which is the conjugated microporous polymer.

[0052] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the molar ratio of 1,3,6,8-tetrabromopyrene, 1,3,5-triethynylbenzene, tetra(triphenylphosphine)palladium, and cuprous iodide in step one is 60:80:1:9. The other steps are the same as in Specific Implementation Method One.

[0053] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 1 or 2 in that the volume ratio of N,N-dimethylformamide to triethylamine in the mixed solvent of N,N-dimethylformamide and triethylamine in step 1 is (2~3):1. The other steps are the same as in Specific Implementation Method 1 or 2.

[0054] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the volume ratio of the amount of 1,3,6,8-tetrabromopyrene mentioned in step one to the volume ratio of the mixed solvent of N,N-dimethylformamide and triethylamine is 0.06 mmol: (3 mL to 10 mL). The other steps are the same as in Specific Implementation Methods One to Three.

[0055] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: in step two, the mixed solution is transferred to the polytetrafluoroethylene liner of the reactor; the reaction system is evacuated for 2 to 3 minutes, and then nitrogen is introduced; in step two, the reactor is transferred to an oven at a temperature of 80°C to 120°C and reacted for 12 to 24 hours. Other steps are the same as in Specific Implementation Methods One to Four.

[0056] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that: the method for cleaning the solid product in step three is as follows: first, add the solid product to deionized water, stir magnetically for 3-5 minutes, and then filter; repeat the above operation 2-3 times; then add the solid product to methanol, stir magnetically for 3-5 minutes, and then filter; repeat the above operation until the filtrate is colorless, and collect the solid product; the vacuum drying temperature in step three is 80℃-100℃, and the vacuum drying time is 6-8 hours. Other steps are the same as in Specific Implementation Methods One to Five.

[0057] Specific Implementation Method Seven: This implementation method is the application of the conjugated microporous polymer in the adsorption and / or degradation of bisphenol A in water.

[0058] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that the conjugated microporous polymer is used in combination with sodium persulfate for photocatalytic degradation of bisphenol A. The other steps are the same as in Specific Implementation Methods One to Seven.

[0059] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that: under visible light, the conjugated microporous polymer and sodium persulfate are used in combination for photocatalytic degradation of bisphenol A; this includes: mixing the conjugated microporous polymer with water containing bisphenol A, adding sodium persulfate, and irradiating the solution with 420nm-780nm visible light to degrade bisphenol A; or mixing the conjugated microporous polymer with water containing bisphenol A, adsorbing it in the dark, then adding sodium persulfate and irradiating the solution with 420nm-780nm visible light to degrade bisphenol A. Other steps are the same as in Specific Implementation Methods One to Eight.

[0060] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that: the mass ratio of the conjugated microporous polymer to bisphenol A in the water containing bisphenol A is (1~4):0.3; the mass ratio of sodium persulfate to bisphenol A in the water containing bisphenol A is (0.95~19):0.3; the concentration of bisphenol A in the water containing bisphenol A is 1~15 mg / L; and the visible light irradiation time of the solution is greater than or equal to 30 min. Other steps are the same as in Specific Implementation Methods One to Nine.

[0061] The beneficial effects of the present invention are verified using the following embodiments:

[0062] Example 1: A method for preparing a conjugated microporous polymer (CMP2-170), wherein the structural formula of the conjugated microporous polymer is as follows: Formula I; Formula I is composed of alternating connections of the structures shown in Formula II and Formula III; the molar ratio of the structures shown in Formula II to those shown in Formula III is 3:4;

[0063] Formula IⅠ; Formula III;

[0064] The preparation method is completed according to the following steps:

[0065] 1. Add 0.06 mmol of 1,3,6,8-tetrabromopyrene, 0.08 mmol of 1,3,5-triethynylbenzene, 0.001 mmol of tetra(triphenylphosphine)palladium and 0.009 mmol of cuprous iodide to a mixed solvent consisting of 2 mL of N,N-dimethylformamide and 1 mL of triethylamine, and stir until homogeneous to obtain a mixed solution;

[0066] 2. Transfer the mixed solution to the polytetrafluoroethylene liner of a 25 mL reactor; evacuate the reaction system for 2 min, then purge with nitrogen for protection; repeat the above evacuation and nitrogen purging operations twice to remove dissolved oxygen, then insert the polytetrafluoroethylene liner into the stainless steel reactor outer shell and tighten the seal; transfer the reactor to an oven at 120°C and react for 24 h; after the reaction is completed, cool to room temperature to obtain the solid product;

[0067] 3. The solid product was washed, then vacuum dried at 80℃ for 6 hours, and ground to obtain a brownish-yellow solid powder, which is the conjugated microporous polymer (denoted as CMP2-170), with a yield of 33 mg and a recovery rate of 80%.

[0068] The method for cleaning the solid product in step three is as follows: First, add the solid product to 20 mL of deionized water, stir magnetically for 3 min, and then filter; repeat the above operation twice; then add the solid product to 20 mL of methanol, stir magnetically for 3 min, and then filter; repeat the above operation until the filtrate is colorless, and collect the solid product.

[0069] Example 1 describes the preparation of conjugated microporous polymers (CMPs) via a solvothermal synthesis method based on the Sonogashira reaction. The synthetic route is shown in [reference needed]. Figure 1 .

[0070] Characterization of CMP2-170 prepared in Example 1:

[0071] The phase composition of CMP2-170 prepared in Example 1 was characterized using SEM, XPS, and N2-BET techniques. Meanwhile, the photoelectric properties of CMP2-170 prepared in Example 1 were tested using UV-Vis diffuse reflectance, VB-XPS, and transient photocurrent response techniques.

[0072] SEM images of CMP2-170 prepared in Example 1 at 200 nm resolution are shown below. Figure 2 The N2-BET spectrum can be found here. Figure 3 The micropore size distribution of CMP2-170 prepared in Example 1 is shown in the figure. Figure 4 The infrared spectra of CMP2-170 and raw materials prepared in Example 1 are shown below. Figure 5 The XPS spectrum of CMP2-170 prepared in Example 1 is shown in [reference needed]. Figure 6-7 ;

[0073] Figure 2 The CMP2-170 exhibits a porous structure with varying pore sizes. Around the larger pores and on the surface of the material, there are also many smaller pores.

[0074] Figure 3 and Figure 4The specific surface area of ​​CMP2-170 is 471.7 m². 2 / g, with an average pore size of 1.8nm.

[0075] Figure 5 The infrared spectra of CMP2-170 and two monomers are shown. The 3278 cm⁻¹ region in CMP2-170 is... -1 810cm -1 and 606cm -1 The strong absorption peak at 3278 cm⁻¹ is attributed to the stretching / bending vibration of the terminal alkyne group in the starting monomer and the characteristic vibration of the C-Br group. -1 and 606cm -1 The disappearance of the characteristic peak at 810 cm⁻¹ clearly proves the complete reaction of the alkynyl functional group; while 810 cm⁻¹ -1 The decrease in peak intensity indicates that only a small number of C-Br bonds remain on the surface of the CMP material.

[0076] X-ray photoelectron spectroscopy (XPS) was used to analyze the elemental composition and chemical state of the CMP material surface. Figure 6 The X-ray photoelectron spectroscopy full spectrum analysis of material CMP2-170 shows that its surface mainly contains four elements: C, Br, O, and N. Figure 7 A detailed analysis of the four elements mentioned above is provided: The high-resolution spectrum of C1s shows three peaks at 284.18 eV, 284.78 eV, and 288.36 eV, corresponding to the C=C double bond in the aromatic ring (284.18 eV, 72%), the C≡C triple bond in the alkynyl unit (284.78 eV, 21%), and the CO / C=O bond (288.36 eV, 7%), which may originate from the residual solvent DMF or carbon oxidation products on the material surface. Figure 7 a). The high-resolution spectrum of O1s shows the presence of two oxygen-containing functional groups: C–O and C=O (a). Figure 7 b), while the weak single peak appearing in the N1s spectrum is attributed to the nitrogen element in the residual solvent triethylamine or DMF (b). Figure 7 c). The Br3d spectrum can be unconvolved to reveal two characteristic peaks at 69.62 eV (Br3d5 / 2) and 70.64 eV (Br3d3 / 2), confirming the presence of unreacted C–Br bonds at the polymer ends. This is consistent with the C–Br bond signal in the FTIR spectrum of CMP2-170. Figure 7 d).

[0077] The photoelectric properties of CMP2-170 were tested: the band gap energy (or band gap) of CMP2-170 was calculated to be 1.90 eV using the UV-Vis diffuse reflectance spectrum and the Kubelka–Munk function equation (see [link to relevant documentation]). Figure 8The valence band potential of CMP2-170 was determined to be 0.96V by valence band X-ray photoelectron spectroscopy (VB-XPS) (see...). Figure 9 Furthermore, the valence band potential of material CMP2-170 relative to the standard hydrogen electrode (NHE) was calculated to be 0.72V (see...). Figure 10 The transient photocurrent response of the material indicates that CMP2-170 exhibits good photocurrent response performance, with a photocurrent density of 1.5 μA / cm². 2 This indicates that its photoinduced electron-hole pair separation efficiency is relatively high (see...). Figure 11 The above data demonstrates that the CMP2-170 has a good visible light response.

[0078] Figure 12 The display material CMP2-170 exhibits excellent thermal stability, remaining thermally stable below 309℃ with a mass loss of only 5%; when heated to 600℃, the mass decreases by approximately 50%. This demonstrates that CMP2-170 possesses good chemical stability.

[0079] Comparative Example 1: The difference between this example and Example 1 is that in step one, 0.1 mmol of 1,3,6,8-tetrabromopyrene, 0.2 mmol of 1,4-diethynylbenzene, 0.0015 mmol of tetra(triphenylphosphine)palladium and 0.005 mmol of cuprous iodide were added to a mixed solvent consisting of 2 mL of N,N-dimethylformamide and 1 mL of triethylamine, and stirred until homogeneous to obtain a mixed solution; the conjugated microporous polymer obtained in step three is designated as CMP2-169.

[0080] Comparative Example 2: The difference between this example and Example 1 is that in step one, 0.06 mmol of 1,3,6,8-tetrabromopyrene, 0.08 mmol of 1,3,5-tris(4-ethynylphenyl)benzene, 0.001 mmol of tetra(triphenylphosphine)palladium and 0.005 mmol of cuprous iodide were added to a mixed solvent consisting of 2 mL of N,N-dimethylformamide and 1 mL of triethylamine, and stirred until homogeneous to obtain a mixed solution; the conjugated microporous polymer obtained in step three is designated as CMP2-171.

[0081] Comparative Example 3: The difference between this example and Example 1 is that in step one, 0.04 mmol of 1,3,6,8-tetrabromopyrene, 0.08 mmol of 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine, 0.003 mmol of tetra(triphenylphosphine)palladium and 0.0012 mmol of cuprous iodide were added to a mixed solvent consisting of 2 mL of N,N-dimethylformamide and 1 mL of triethylamine, and stirred until homogeneous to obtain a mixed solution; the conjugated microporous polymer obtained in step three is designated as CMP2-172.

[0082] Photocatalysis experiment:

[0083] Application Example 1:

[0084] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 50 mg / L bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 rpm) for 1 h in the dark. Sodium persulfate was then added to bring the final concentration to 2 mmol / L. The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as 2-170.

[0085] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 2 mg of CMP2-169 prepared in Comparative Example 1. All other steps and operations were the same, and it was referred to as 2-169.

[0086] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 2 mg of CMP2-171 prepared in Comparative Example 2. All other steps and operations were the same, and it was referred to as 2-171.

[0087] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 2 mg of CMP2-172 prepared in Comparative Example 3. All other steps and operations were the same, and it was referred to as 2-172.

[0088] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 13 As shown;

[0089] from Figure 13 It can be seen that, in terms of the total elimination rate, CMP2-170 prepared in Example 1 has the best effect, reaching 69%, which is better than the total elimination rate of CMP2-169 prepared in Comparative Example 1 (23%), the total elimination rate of CMP2-171 prepared in Comparative Example 2 (67%), and the total elimination rate of CMP2-172 prepared in Comparative Example 3 (66%).

[0090] Application Example 2:

[0091] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h in the dark. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L. The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as CMP 2 mg + PDS 2 mM.

[0092] As a control, the use of sodium persulfate in Application Example 2 was omitted, and all other steps and operations were the same, denoted as CMP 2mg;

[0093] As a control, the CMP2-170 prepared in Example 1 of Application Example 2 was omitted, and all other steps and operations were the same, denoted as PDS 2mM;

[0094] Blank control, omitting the use of sodium persulfate in Application Example 2 and CMP2-170 prepared in Example 1, with all other steps and operations being the same, is denoted as -;

[0095] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 14 As shown;

[0096] from Figure 14 It can be seen that after 2 hours of illumination, the total elimination rate of bisphenol A in the blank control group without CMP2-170 and PDS was only 3%; the total elimination rate of bisphenol A in the control group with only CMP2-170 was 60%, indicating that the photocatalyst CMP2-170 has good photocatalytic degradation performance; the total elimination rate of bisphenol A in the control group containing only PDS was 10%; and the total elimination rate of bisphenol A in the experimental group containing both CMP2-170 and PDS was as high as 99%, indicating that the photocatalytic system of CMP2-170 combined with PDS can significantly improve the degradation efficiency of bisphenol A.

[0097] Application Example 3:

[0098] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L of bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h in the dark. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L. The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as CMP2-170 2 mg + PDS 2 mM.

[0099] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 2 mg of TiO2, and all other steps and operations were the same, denoted as TiO2 2 mg + PDS 2 mM;

[0100] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 2 mg of g-C3N4, and all other steps and operations were the same, denoted as g-C3N4 2 mg + PDS 2 mM;

[0101] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 15 As shown;

[0102] Figure 15 This is a comparison of the photocatalytic degradation effects of commonly used photocatalysts TiO2, g-C3N4, and CMP2-170 in Example 3, respectively, on bisphenol A when combined with PDS. In the figure, CMP2-170 2mg + PDS 2mM represents adsorption and photocatalytic degradation using CMP2-170 prepared in Example 1 and sodium persulfate; TiO2 2mg + PDS 2mM represents photocatalytic degradation using TiO2 and sodium persulfate; and g-C3N4 2mg + PDS 2mM represents photocatalytic degradation using g-C3N4 and sodium persulfate.

[0103] from Figure 15It can be seen that after 2 hours of illumination, the final degradation rate of the photocatalysts TiO2 and g-C3N4 combined with PDS reached only 17%, while the final degradation rate of CMP2-170 prepared in Example 1 combined with PDS reached 99%. This indicates that the photocatalyst CMP2-170 of this invention has superior performance in the combined degradation of bisphenol A with PDS. The total organic carbon in the solution of the CMP2-170+PDS system after 2 hours of illumination was measured by a TOC analyzer, and the mineralization efficiency of this method was 54% (the concentration of bisphenol A in the original solution was 15 mg / L, the theoretical total organic carbon content was 11.85 mg / L, the measured total organic carbon content in the original solution was 10.42 mg / L, and the total organic carbon content in the solution after the reaction was 4.76 mg / L), which is quite excellent. Increasing the illumination time can further improve the mineralization efficiency of the reaction.

[0104] Application Example 4:

[0105] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L of bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h in the dark. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L (2 mM). The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as CMP 2 mg + PDS 2 mM.

[0106] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 1 mg of CMP2-170 prepared in Example 1, and all other steps and operations were the same, which was recorded as CMP 1 mg + PDS 2 mM;

[0107] As a control, 2 mg of CMP2-170 prepared in Example 1 was replaced with 4 mg of CMP2-170 prepared in Example 1, and all other steps and operations were the same, which was recorded as CMP 4 mg + PDS 2 mM;

[0108] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 16 As shown;

[0109] from Figure 16It can be seen that the total elimination rate of bisphenol A is significantly increased from 70% to over 99%. The results show that for every 0.3 mg of bisphenol A, the amount of CMP2-170 used is preferably at least 1.0 mg, more preferably 1.0 mg-4.0 mg, and most preferably 2.0 mg-4.0 mg.

[0110] Application Example 5:

[0111] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L of bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) under light-protected conditions for 1 h. Sodium persulfate (PDS) was then added to bring the final concentration to 0.2 mmol / L (0.2 mM). The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as CMP 2 mg + PDS 0.2 mM.

[0112] As a control, sodium persulfate (PDS) was added to make the final concentration of sodium persulfate 2 mmol / L (2 mM). All other steps and operations were the same, and it was recorded as CMP 2 mg + PDS 2 mM.

[0113] As a control, sodium persulfate (PDS) was added to make the final concentration of sodium persulfate 4 mmol / L (4 mM). All other steps and operations were the same, and it was recorded as CMP 2 mg + PDS 4 mM.

[0114] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 17 As shown;

[0115] from Figure 17 It was found that when the PDS concentration was in the range of 0-4 mM, the total elimination rate of bisphenol A increased from 60% to 99% with increasing PDS dosage. When the PDS dosage was 2 mM, the total elimination rate of bisphenol A increased to 99%. However, when the PDS dosage increased to a certain level, the increase in the total elimination rate of bisphenol A was not significant. Further increasing the concentration to 4 mM did not improve the degradation efficiency further. This phenomenon may be due to the self-quenching reaction of PDS, leading to its own capture of sulfate free radicals. The results showed that for every 0.3 mg of bisphenol A, the preferred dosage of PDS was at least 0.952 mg, further preferably 4.76 mg-9.52 mg, and most preferably 9.52 mg-19.04 mg.

[0116] In real-world environments, wastewater pH varies, and changes in pH in water can not only alter the form of antibiotics but also affect the generation rate of reactive free radicals. Therefore, this experiment investigated the effects of different pH conditions on the CMP / PDS synergistic photocatalytic system, see Application Example 6.

[0117] Application Example 6:

[0118] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L bisphenol A at pH 1 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h under light-protected conditions. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L (2 mM). The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as pH=1.

[0119] As a control, 20 mL of water containing 15 mg / L of bisphenol A with a pH of 1 was replaced with 20 mL of water containing 15 mg / L of bisphenol A with a pH of 3, denoted as pH=3.

[0120] As a control, 20 mL of water containing 15 mg / L of bisphenol A with a pH of 1 was replaced with 20 mL of water containing 15 mg / L of bisphenol A with a pH of 5. All other steps and operations were the same, and this was recorded as pH=5.

[0121] As a control, 20 mL of water containing 15 mg / L of bisphenol A with a pH of 1 was replaced with 20 mL of water containing 15 mg / L of bisphenol A with a pH of ≈7. All other steps and operations were the same, and this was recorded as -.

[0122] As a control, 20 mL of water containing 15 mg / L of bisphenol A with a pH of 1 was replaced with 20 mL of water containing 15 mg / L of bisphenol A with a pH of 9. All other steps and operations were the same, and this was recorded as pH=9.

[0123] As a control, 20 mL of water containing 15 mg / L of bisphenol A with a pH of 1 was replaced with 20 mL of water containing 15 mg / L of bisphenol A with a pH of 11. All other steps and operations were the same, and this was recorded as pH=11.

[0124] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 18 As shown;

[0125] Figure 18 The graph shows the adsorption and degradation effect of CMP2-170 prepared in Example 1 of Application Example 6 in combination with PDS on bisphenol A in water containing bisphenol A at different pH values.

[0126] from Figure 18 It can be seen that when the pH is close to that of the original solution (pH=6.3), the degradation efficiency of bisphenol A (BPA) does not decrease significantly. The efficiency decreases slightly under acidic conditions, which is due to the electrostatic repulsion between protonated BPA and CMP2-170. Under alkaline conditions, the efficiency decreases significantly, even dropping to 60% at pH=9.0. Therefore, the CMP / PDS synergistic photocatalytic system exhibits excellent degradation efficiency under weakly acidic conditions.

[0127] To simulate the actual conditions of water bodies, this experiment further investigated the effect of low-concentration salt solutions on the degradation of bisphenol A by the CMP / PDS synergistic photocatalytic system, see Application Example 7;

[0128] Application Example 7:

[0129] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h in the dark. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L (2 mM). The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography (HPLC) and recorded as -.

[0130] As a control, the water containing bisphenol A also contained 0.2 mmol / L NaCl. All other steps and operations were the same, and this was recorded as NaCl 0.2M.

[0131] As a control, the water containing bisphenol A also contained 0.2 mmol / L NaHCO3. All other steps and operations were the same, and it was recorded as NaHCO3 0.2M.

[0132] As a control, the water containing bisphenol A also contained 0.2 mmol / L NH4Cl. All other steps and operations were the same, and this was recorded as NH4Cl 0.2M.

[0133] As a control, the water containing bisphenol A also contained 0.2 mmol / L Na2SO4. All other steps and operations were the same, and it was recorded as Na2SO4 0.2M.

[0134] As a control, the water containing bisphenol A also contained 0.2 mmol / L NaNO2. All other steps and operations were the same, and it was recorded as NaNO2 0.2M.

[0135] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 19 As shown;

[0136] Figure 19 The results showed Cl - This has a significant impact on degradation efficiency, causing it to drop below 75%. Conversely, NH4 + HCO3 - NO2 - Other inorganic ions have a relatively weak impact on degradation efficiency, but the degradation efficiency still remains above 80%. Clearly, the CMP / PDS synergistic photocatalytic system is less affected by common inorganic anions, demonstrating its good applicability.

[0137] In addition to the technical requirement of excellent degradation performance, the cost of the degradation method must also be considered from an economic perspective. Therefore, this invention studies the reproducibility of the photocatalytic performance of the material, as shown in Application Example 8;

[0138] Application Example 8:

[0139] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h in the dark. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L (2 mM). The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography and recorded as CMP2-170.

[0140] As a control, CMP2-170 was collected by filtration after the experiment. The used CMP2-170 was washed with deionized water and methanol in sequence and then recovered. It was dried in a vacuum drying oven and used for the next cycle experiment. One cycle was recorded as 1st, two cycles as 2nd, and three cycles as 3rd.

[0141] The above adsorption and photocatalytic degradation effects of bisphenol A are shown in the figure. Figure 20 As shown;

[0142] from Figure 20 It can be seen that after three cycles of use, the total elimination rate only decreased from 97.7% to 73.9%, indicating that CMP2-170 has good reusability and has certain practical application prospects and economic benefits.

[0143] The degradation kinetics were studied under the optimal photocatalytic degradation conditions, using a zero-order kinetic model (c0-c). t = k0t), first-order dynamic model (ln(c0 / c) t ) = k1t) and second-order dynamic model (1 / c t – 1 / c0 = k2t) was used to fit the degradation kinetics data; see Application Example 9.

[0144] Application Example 9:

[0145] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 r / min) for 1 h in the dark. Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L (2 mM). The photocatalytic degradation experiment was then initiated for 2 h using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to each sample to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography (HPLC). (See attached image). Figure 21 As shown in the middle left figure.

[0146] Two mg of CMP2-170 prepared in Example 1 and 20 mL of water containing 15 mg / L bisphenol A at pH 7 were added to a test tube. The tube was then placed in a Newbit Phchem III photochemical reactor and stirred (700 rpm). Sodium persulfate (PDS) was then added to bring the final concentration to 2 mmol / L (2 mM). The photocatalytic degradation experiment was initiated for 2 hours using an LED lamp (36W, white visible light, wavelength: 420 nm-780 nm). Samples were taken periodically, and methanol was added to the samples to quench free radicals and terminate the photocatalytic degradation reaction. After filtration through a 13 mm × 0.45 μm aqueous filter membrane, the concentration of bisphenol A in the filtrate was measured using high-performance liquid chromatography (HPLC). Figure 21 As shown in the middle right figure.

[0147] Figure 21 The graph shows the photocatalytic degradation kinetics of CMP2-170 prepared in Example 1 of Application Example 9;

[0148] Figure 21 c t Let be the concentration of bisphenol A in the solution at time t, c0 be the initial concentration of bisphenol A, t be the illumination time, and k be the corresponding reaction rate. Figure 21 It can be seen that the degradation of bisphenol A in solution by CMP2-170 / PDS is a first-order reaction (R0 of the fitted straight line). 2 The concentration was 0.998, and the reaction rate was 1.40 h⁻¹. -1 .

Claims

1. A method of making a conjugated microporous polymer, characterized by: The conjugated microporous polymer has a structural formula of The preparation method is completed according to the following steps: I. 1,3,6,8-tetrabromopyrene, 1,3,5-triethynylbenzene, tetrakis(triphenylphosphine)palladium and cuprous iodide are added into a mixed solvent of N,N-dimethylformamide and triethylamine, and stirred uniformly to obtain a mixed solution; II. The mixed solution is transferred into a polytetrafluoroethylene liner of a reaction kettle; The reaction system is vacuumed and then filled with nitrogen, and the above-mentioned vacuuming and nitrogen filling operations are repeated for several times to remove dissolved oxygen, and then the polytetrafluoroethylene liner is installed into a stainless steel reaction kettle jacket and tightly sealed; the reaction kettle is transferred into an oven with a temperature of 80-120 DEG C for reaction; after the reaction is completed, the reaction kettle is cooled to room temperature to obtain a solid product; III. The solid product is washed, vacuum-dried and ground to obtain a brownish solid powder, which is the conjugated microporous polymer.

2. The method of claim 1, wherein: The molar ratio of 1,3,6,8-tetrabromopyrene, 1,3,5-triethynylbenzene, tetrakis(triphenylphosphine)palladium and cuprous iodide in step I is 60:80:1:

9.

3. The method of claim 1, wherein: The volume ratio of N,N-dimethylformamide to triethylamine in the mixed solvent of N,N-dimethylformamide and triethylamine in step I is (2-3):

1.

4. The method of claim 1, wherein: The volume ratio of the amount of substance of 1,3,6,8-tetrabromopyrene to the mixed solvent of N,N-dimethylformamide and triethylamine in step I is 0.06 mmol:(3-10 mL).

5. The method of claim 1, wherein: In step II, the mixed solution is transferred into a polytetrafluoroethylene liner of a reaction kettle; the reaction system is vacuumed for 2-3 min and then filled with nitrogen; in step II, the reaction kettle is transferred into an oven with a temperature of 80-120 DEG C for reaction for 12-24 h.

6. The method of claim 1, wherein: In step III, the solid product is washed by first adding the solid product into deionized water, magnetically stirring for 3-5 min and then filtering; the above-mentioned operation is repeated for 2-3 times; then the solid product is added into methanol, magnetically stirred for 3-5 min and then filtered; the above-mentioned operation is repeated until the filtrate is colorless, and the solid product is collected; the temperature of vacuum drying in step III is 80-100 DEG C, and the time of vacuum drying is 6-8 h.

7. Use of the conjugated microporous polymer prepared according to the process of any one of claims 1 to 6. The conjugated microporous polymer is used in adsorption and / or degradation of bisphenol A in water.

8. Use of the conjugated microporous polymer according to claim 7, characterized in that: The conjugated microporous polymer is used in combination with sodium peroxodisulfate for photocatalytic degradation of bisphenol A under visible light.

9. Use of the conjugated microporous polymer according to claim 8, characterized in that: The conjugated microporous polymer is used in combination with sodium peroxodisulfate for photocatalytic degradation of bisphenol A under visible light. The conjugated microporous polymer is mixed with water containing bisphenol A, and then sodium peroxodisulfate is added, and the solution is irradiated with 420-780 nm visible light to degrade bisphenol A; or the conjugated microporous polymer is mixed with water containing bisphenol A in the dark for adsorption, and then sodium peroxodisulfate is added, and the solution is irradiated with 420-780 nm visible light to degrade bisphenol A.

10. Use of the conjugated microporous polymer according to claim 9, characterized in that: The mass ratio of the conjugated microporous polymer to bisphenol A in water containing bisphenol A is (1-4):0.3; the mass ratio of sodium peroxodisulfate to bisphenol A in water containing bisphenol A is (0.95-19):0.3; the concentration of bisphenol A in water containing bisphenol A is 1-15 mg / L; the time of irradiating the solution with visible light is greater than or equal to 30 min.

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