A molecularly imprinted photocatalytic composite glass fiber and its preparation method and application

Abstract

The present invention provides a molecularly imprinted photocatalytic composite glass fiber and its preparation method and application. The present invention first prepares a photosensitive coumarin-modified styrene monomer and a dopamine-modified acrylic monomer, which are then polymerized with a hydrophilic acrylic monomer to prepare a photosensitive amphiphilic random polymer; the resulting polymer and a template molecule are used as assembly units to collaboratively assemble with the template molecule to form molecularly imprinted composite nanoparticles (MIP NPs); the MIP NPs and titanium dioxide nanoparticles (TiO2 NPs) are used as building blocks to modify the glass fiber, and the template molecules are removed from the glass fiber by catalytic degradation of TiO2 under ultraviolet light to obtain the molecularly imprinted photocatalytic composite glass fiber. The molecularly imprinted photocatalytic composite glass fiber prepared by the present invention has the characteristics of specific enrichment of pollutants, high photocatalytic degradation efficiency, and strong sustainable degradation ability, and has good application prospects in the field of actual complex water environments.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials and organic pollutant degradation, and particularly relates to a molecularly imprinted photocatalytic composite glass fiber and a preparation method and application thereof. Background Art

[0002] With the impact of human activities and the development of industrial production, water pollution has become increasingly prominent, and pollutants have led to a deterioration in water quality. Although the organic pollutants in water pollution are not present in high concentrations, they are difficult to biodegrade and can spread along the food chain. How to effectively treat organic pollutants in water is a common challenge facing the world.

[0003] Photocatalytic oxidation technology is considered the most effective, clean, and low-cost advanced oxidation technology for treating water pollution. Among the many photocatalytic materials used in water treatment, nano-titanium dioxide (TiO2) exhibits unique advantages. Nano-TiO2 is simple to prepare, inexpensive, highly catalytically active, and chemically stable. Its photocatalytic reaction conditions are mild and non-polluting. TiO2 photocatalysts degrade organic pollutants in water primarily through the generation of oxygen-containing free radicals under ultraviolet light, which catalyze the oxidation of organic pollutants in water into environmentally friendly small molecules.

[0004] However, photocatalysts also have a disadvantage, namely poor selectivity. They preferentially degrade harmful substances with high concentrations and low toxicity, while substances with low concentrations and high toxicity cannot be effectively degraded and continue to exist in the environment, eventually transferring along the food chain and causing serious harm.

[0005] Due to the lack of enrichment of the target and suitable carrier materials, TiO2 has low efficiency in degrading low-concentration pollutants in large-capacity water environment systems, making it difficult to actually apply TiO2 in water environment systems.

[0006] Molecular imprinting utilizes molecularly imprinted polymers (MIPs) to mimic enzyme-substrate or antibody-antigen interactions, enabling specific recognition of template molecules. Currently, combining MIP with TiO2 photocatalysis has been successfully applied to the degradation and removal of organic pollutants in water. However, most applications utilize solid particle-based MIP photocatalysts, which are difficult to recycle and hinder industrial application. Summary of the Invention

[0007] The purpose of the present invention is to provide a molecularly imprinted photocatalytic composite glass fiber and a preparation method thereof, which utilizes molecularly imprinted composite nanoparticles to enrich organic pollutants on the surface of the composite glass fiber and utilizes photocatalysts to catalyze the degradation of organic pollutants into small molecules that are harmless to the environment.

[0008] Another object of the present invention is to provide an application of molecularly imprinted photocatalytic composite glass fiber for treating wastewater containing organic pollutants.

[0009] The specific technical solutions of the present invention are as follows:

[0010] A method for preparing a molecularly imprinted photocatalytic composite glass fiber comprises the following steps:

[0011] 1) dissolving a hydrophilic acrylic monomer, a photosensitive coumarin-modified styrene monomer, and a dopamine-modified acrylic monomer in an organic solvent, adding an initiator, and initiating a polymerization reaction. After the reaction is completed, the filtrate is precipitated in petroleum ether, and a solid is separated and purified, and dried to prepare a photosensitive amphiphilic random polymer (PAVD);

[0012] 2) dissolving a photosensitive amphiphilic random polymer and a template molecule in an organic solvent, and adding ultrapure water dropwise under stirring to induce self-assembly to form nanoparticles; after UV crosslinking, the organic solvent is removed by dialysis in distilled water to obtain molecularly imprinted composite nanoparticles (MIP NPs);

[0013] 3) Molecularly imprinted composite nanoparticles and titanium dioxide nanoparticles are modified on the surface of hydroxylated glass fibers, the template molecules are removed, and the fibers are washed with water and dried to obtain molecularly imprinted photocatalytic composite glass fibers (TiO2 / MIP NPs / GF).

[0014] In step 1), the molar ratio of the hydrophilic acrylic monomer to the photosensitive coumarin-modified styrene monomer and the dopamine-modified acrylic monomer is (1-5):(1-5):(1-5); the hydrophilic acrylic monomer is selected from hydrophilic acrylic acid, methyl methacrylate or methacrylic acid; the amount of the initiator added is 1.0% of the total molar number of the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer and the dopamine-modified acrylic monomer; the amount ratio of the hydrophilic acrylic monomer to the organic solvent is 0.1-0.2 mmol / mL; the organic solvent is 1,4-dioxane, N,N-dimethylformamide (DMF), tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO); the initiator is azobisisobutyronitrile (AIBN); the polymerization reaction conditions are stirring at 55-70°C for 18-28h under inert gas protection; the purification specifically comprises: dissolving the solid in tetrahydrofuran and then precipitating it in petroleum ether, filtering and separating the solid, and repeating 3 times; the drying refers to vacuum drying at 40°C to constant weight; in step 1), the photosensitive amphiphilic random polymer (PAVD) is obtained by free radical polymerization of a hydrophilic acrylic monomer, a hydrophobic photosensitive coumarin-modified styrene monomer, and a hydrophilic dopamine-modified acrylic monomer.

[0015] In step 1), the preparation method of the photosensitive coumarin-modified styrene monomer is:

[0016] Hydroxycoumarin, potassium carbonate and 4-chloromethylstyrene are added to an organic solvent, heated for reaction, and then filtered. The filtrate is precipitated in water, and a solid is separated and purified and dried to obtain a photosensitive coumarin-modified styrene monomer.

[0017] In the preparation method of the photosensitive coumarin-modified styrene monomer, the molar ratio of the hydroxycoumarin, potassium carbonate, and 4-chloromethylstyrene is 1:(0.5-4):(0.2-4); the amount ratio of the hydroxycoumarin to the organic solvent is 0.0005-0.0015 mol / mL; the hydroxycoumarin is preferably 7-hydroxy-4-methylcoumarin; the organic solvent is a good solvent, preferably, the organic solvent is N,N-dimethylformamide (DMF), 1,4-dioxane, and dimethyl sulfoxide (DMSO); the heating reaction conditions are: stirring the reaction at 55-70°C under inert gas protection for 18-28 hours, the purification is specifically: dissolving the solid in tetrahydrofuran and then precipitating it in a mixture of ethanol and water with a volume ratio of 1:1, filtering and separating to obtain a solid, and repeating three times, and the drying refers to vacuum drying at 40°C to constant weight.

[0018] In step 1), the preparation method of the dopamine-modified acrylic acid monomer is:

[0019] Dopamine hydrochloride is added to a saturated solution formed by dissolving borax and bicarbonate or phosphate in water, and an acrylic acylating agent is dissolved in an organic solvent and then added dropwise to the saturated salt solution while maintaining the pH of the solution above 8 for reaction. After the reaction, the product is washed, the pH is adjusted to less than 2, and then extracted, dried, purified, and oven-dried to obtain a dopamine-modified acrylic monomer.

[0020] In the preparation method of the dopamine-modified acrylic monomer, the mass ratio of borax to bicarbonate or phosphate is (1-5):1; the dosage ratio of dopamine hydrochloride to borax is 5-6 mmol / g; the dosage ratio of dopamine hydrochloride to water is 0.5-0.6 mmol / mL; the borax is sodium borate; the bicarbonate is selected from sodium bicarbonate; the organic solvent is tetrahydrofuran (THF), N,N-dimethylformamide (DMF), or dimethyl sulfoxide (DMSO); the acrylic acylating agent is methacrylic anhydride or methacryloyl chloride; the dosage ratio of the acrylic acylating agent dissolved in the organic solvent is 2-3 mmol / mL; and the dopamine hydrochloride is added to the water. The molar ratio of the amount of the acrylic acylating agent to the amount of the acrylic acylating agent is (0.1-5):1; the reaction is carried out under inert gas protection at room temperature with stirring for 10-18 hours, and the pH is adjusted to above 8 with a sodium hydroxide solution; and the pH is adjusted to below 2 with a hydrochloric acid solution; the washing specifically comprises: washing the solution with ethyl acetate twice, filtering out the solid; the extraction specifically comprises: extracting with ethyl acetate three times, and combining the dark brown upper layers obtained from the three extractions; the drying specifically comprises: adding anhydrous sodium sulfate to absorb moisture and drying for more than 4 hours; the purification specifically comprises: precipitating the ethyl acetate layer obtained from the extraction in n-hexane, separating the solid by suction filtration, and repeating three times; and the drying refers to vacuum drying at 40°C to constant weight.

[0021] In step 2), the mass ratio of the photosensitive amphiphilic random polymer to the template molecule is (5-100):1; the template molecule is nitrophenol or hydroquinone, preferably p-nitrophenol PNP, o-nitrophenol ONP, m-nitrophenol MNP or hydroquinone HQ; the amount ratio of the photosensitive amphiphilic random polymer to the organic solvent is 10-60 mg·mL -1 , preferably 20 mg·mL -1 The organic solvent is 1,4-dioxane, N,N-dimethylformamide (DMF), tetrahydrofuran (THF), and dimethyl sulfoxide (DMSO); the photosensitive amphiphilic random polymer and the template molecule are dissolved in the organic solvent and stirred overnight before use; the volume ratio of the organic solvent to ultrapure water is 6:1-1:6; the UV crosslinking refers to irradiating under UV conditions for more than 2 hours, and the UV power is 600mW / cm 2 In this step, the addition of ultrapure water is to utilize the assembly units (photosensitive amphiphilic random polymers, template molecules) to self-assemble in a mixed solvent, and to utilize hydrophobic effects and weak interactions between the assembly units to induce the polymer and template molecules to synergistically assemble to form MIP NPs. The obtained MIP NPs have a particle size of 20-400 nm.

[0022] In step 2), the dialysis is performed in distilled water using a dialysis bag (MW: 8000-14000) for 1 day to remove the organic solvent. The purpose of dialysis is to remove the organic solvent and excess template molecules and retain the molecularly imprinted composite nanoparticles.

[0023] The addition of ultrapure water in step 2) allows the assembly units to self-assemble to form macromolecular composite nanoparticles. The principle behind this self-assembly is that one of the effects of the nanoparticles' formation is hydrophilicity and hydrophobicity. The long chains of amphiphilic molecules formed by the polymerization of hydrophilic and hydrophobic monomers are then added. Adding water to these chains causes the hydrophobic groups to aggregate together to avoid water. This is because the hydrophobic groups of the hydrophobic monomers repel water. Hydrophobic groups are generally non-polar groups, and this repulsive effect draws the hydrophobic groups closer together, concentrating and structuring the water to a greater extent, leading to self-assembly into macromolecular composite nanoparticles.

[0024] The hydroxylated glass fiber described in step 3) is prepared by ultrasonically treating the glass fiber in acetone and (2-12) mol / L hydrochloric acid, followed by rinsing with ultrapure water and drying to obtain the hydroxylated glass fiber. The purpose of hydroxylating the glass fiber is that the main component of the glass fiber is SiO2, which exists in the form of Si-O-Si bonds and is difficult to wet with water. Hydroxylation can hydrolyze the Si-O bonds to produce Si-OH, a highly active hydrophilic group that easily supports particles on its surface in an aqueous system.

[0025] The molecularly imprinted composite nanoparticles and titanium dioxide nanoparticles described in step 3) are assembled and modified onto the surface of the hydroxylated glass fiber layer by layer by sequential immersion. The hydroxylated glass fiber is immersed in two solutions, first in the molecularly imprinted composite nanoparticle solution and then in the titanium dioxide nanoparticle solution. The concentration of the molecularly imprinted composite nanoparticle solution used is (0.1-50) mg·mL -1 The concentration of titanium dioxide nanoparticle solution is (0.1-50) mg·mL -1 The mass ratio of the molecularly imprinted composite nanoparticles to the hydroxylated glass fiber in the solution is 1:(1-20), and the mass ratio of the titanium dioxide nanoparticles to the hydroxylated glass fiber in the solution is 1:(1-15). The immersion time in the molecularly imprinted composite nanoparticle solution is greater than 3 hours, and the immersion time in the titanium dioxide nanoparticle solution is greater than 0.5 hours. The layer-by-layer assembly comprises two layers, one containing the molecularly imprinted composite nanoparticles and the other containing the titanium dioxide nanoparticles. Therefore, the glass fiber is immersed in the molecularly imprinted composite nanoparticle solution and the titanium dioxide nanoparticle solution once respectively.

[0026] In step 3), the template molecules are removed by ultraviolet light irradiation, and the ultraviolet light irradiation time is greater than 1 hour; the ultraviolet light irradiation to remove the template molecules is to use ultraviolet light greater than the band gap width of the TiO2 photocatalyst to make the photocatalyst generate oxygen-containing free radicals, and the oxygen-containing free radicals oxidatively degrade the template molecules into small molecules such as H2O, CO2, N2 that are harmless to the environment, thereby obtaining imprinted holes with complementary shapes, sizes, and active groups, and obtaining a structurally stable molecularly imprinted photocatalytic composite glass fiber, which can be used to enrich and degrade a specific pollutant.

[0027] In step 3), the drying refers to drying at 40° C. to constant weight.

[0028] In the above preparation method, the inert gas is nitrogen or argon.

[0029] In the present invention, the dopamine-modified acrylic monomer in the photosensitive amphiphilic random polymer is obtained by a substitution reaction between an acrylic acylating agent and dopamine hydrochloride containing a catechol structure. The carbon-carbon double bond of the acrylic acylating agent provides a conditional basis for the polymerization of the monomer. The dopamine hydrochloride containing a catechol structure is easy to self-crosslink and has a strong interaction force with inorganic materials (TiO2, glass fiber), thereby achieving adhesion of the composite nanoparticles to the glass fiber and anchoring effect on nano-TiO2, preventing the MIP NPs from bonding with TiO2. NPs fall off from the glass fiber; the photosensitive coumarin-modified styrene monomer in the photosensitive amphiphilic random polymer is obtained by substitution reaction between 4-chloromethylstyrene and hydroxycoumarin. The carbon-carbon double bond of 4-chloromethylstyrene provides the basis for the polymerization of the monomer. The coumarin group not only has a certain weak interaction with the template molecule, but also can trigger moderate cross-linking of the self-assembly through light to fix the molecular imprinting site, improve the selectivity of the imprinting hole to the template molecule, and enhance the stability of the polymer structure; the hydrophilic acrylic monomer in the photosensitive amphiphilic random polymer can form multiple interaction sites (hydrogen The invention discloses a photosensitive amphiphilic random polymer synthesized from a hydrophilic acrylic monomer, a photosensitive coumarin-modified styrene monomer (hydrophobic), and a dopamine-modified acrylic monomer (hydrophilic) to form micro-nano aggregates with dispersed distribution of hydrophilic and hydrophobic microdomains in aqueous solution. The hydrophobic microdomains are frozen, forming dispersed physical cross-linking points, which stabilize the morphology of the aggregates. The hydrophilic microdomains are in a highly elastic state, allowing the polymer chain segments to move freely, maintaining the flexibility of the aggregates. This microstructure with moderate hardness and softness is suitable for further multi-level assembly on the surface of a carrier material.

[0030] Glass fiber, an inorganic non-metallic material with low cost, large specific surface area, and excellent light transmittance, can be used as a carrier for photocatalysts and fabricated into photocatalytic reactors of various shapes and sizes, with potential industrial applications. To address issues such as poor photocatalytic degradation selectivity and the difficulty in recycling particulate photocatalysts, molecular imprinting technology, photocatalytic degradation, and macromolecular self-assembly techniques have been effectively combined to construct a multifunctional composite glass fiber for water pollution treatment that combines specific molecule enrichment with efficient photodegradation, enabling industrial application.

[0031] The molecularly imprinted photocatalytic composite glass fiber provided by the present invention is prepared by adopting the above method.

[0032] The present invention provides a molecularly imprinted photocatalytic composite glass fiber for use in wastewater treatment, particularly for removing organic pollutants from water, particularly nitrophenol and diphenol, wherein the concentration of the organic pollutants in the water is 1 mg / L to 50 mg / L.

[0033] In the present invention, dialysis is carried out in distilled water, and other water used is ultrapure water.

[0034] Compared with the prior art, the molecularly imprinted photocatalytic composite glass fiber provided by the present invention has the following advantages: the photosensitive amphiphilic random polymer and the template molecule are directly used as the assembly unit, and the template molecule is wrapped inside or on the surface of the nanoparticle to form MIP. NPs do not require pre-polymerization reaction, and do not need to add cross-linking agents or pore-forming agents, thus eliminating complex steps; photosensitive groups are introduced into the polymer molecular structure to cooperate with photocatalytic responsive components to achieve the removal of template molecules while enhancing the imprinting recognition sites by UV cross-linking, thus avoiding the complex template molecule elution steps in traditional molecular imprinting materials; glass fibers with low cost and large specific surface area are used as carrier materials to induce molecular imprinting composite nanoparticles and inorganic nanocatalysts to achieve multi-component co-assembly on the glass fiber surface, which can give full play to the nano-micro structural effect of the composite glass fibers; the controllable self-assembly of macromolecules, the molecular recognition characteristics of molecular imprinting materials and the photocatalytic properties of inorganic nanomaterials are combined to realize the design and controllable preparation of molecular imprinting photocatalytic composite glass fibers that integrate molecular recognition, enrichment and photocatalytic degradation functions, providing new ideas for the development of high-efficiency water pollution treatment materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Photosensitive amphiphilic random polymer (PAVD) 1 H NMR spectrum;

[0036] Figure 2 Scanning electron microscopy images of MIP NPs;

[0037] Figure 3 Particle size distribution and potential maps of MIP NPs assembled with different concentrations of PAVD;

[0038] Figure 4 Scanning electron microscopy images of different functionalized composite glass fibers;

[0039] Figure 5 Removal rate diagram of wastewater degradation by different functionalized composite glass fibers;

[0040] Figure 6 Removal rate diagram of wastewater degradation by TiO2 / MIP NPs / GF made of different polymer ratios;

[0041] Figure 7 Removal efficiency of TiO2 / MIP NPs / GF made of different polymer concentrations for wastewater degradation;

[0042] Figure 8 Removal efficiency of TiO2 / MIP NPs / GF for wastewater with different initial concentrations;

[0043] Figure 9 Removal rate of TiO2 / MIP NPs / GF made of different template molecules for degradation of different wastewaters. DETAILED DESCRIPTION

[0044] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments and test examples of the present invention will be clearly and completely described below in combination with the embodiments and test examples of the present invention. Obviously, the described embodiments and test examples are exemplary and are part of the embodiments and test examples of the present invention, rather than all the embodiments and test examples. Based on the embodiments and test examples in the present invention, any technician familiar with the art can make many possible changes and modifications to the technical solutions of the present invention by using the methods and technical contents disclosed above, without departing from the spirit and technical solutions of the present invention, or modify them into equivalent embodiments of equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments and test examples based on the technical essence of the present invention without departing from the content of the technical solutions of the present invention are still within the scope of protection of the technical solutions of the present invention.

[0045] The terms “include,” “including,” “have,” “contain,” “preferably,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0046] Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.

[0047] If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0048] Example 1

[0049] A method for preparing a molecularly imprinted photocatalytic composite glass fiber comprises the following steps:

[0050] 1) Preparation of photosensitive coumarin-modified styrene monomer:

[0051] 0.03 mol of 7-hydroxy-4-methylcoumarin was dissolved in 30 mL of DMF and stirred to dissolve, followed by the addition of 0.03 mol of anhydrous potassium carbonate. After uniform stirring, 0.03 mol of 4-chloromethylstyrene was added to the solution, and the mixture was reacted in an oil bath at 65°C under argon for 24 hours. After the reaction, suspended solids were removed by filtration, and the filtrate was precipitated in water to obtain a slightly yellow solid powder. This solid was then dissolved in THF and precipitated in a mixture of ethanol and water (1:1 by volume). This process was repeated three times, and the mixture was dried under vacuum at 40°C to obtain the photosensitive coumarin-modified styrene monomer (VMc).

[0052] 2) Preparation of dopamine-modified acrylic acid monomer:

[0053] 10g of sodium borate and 4g of sodium bicarbonate (protected catechol) were weighed and dissolved in a flask containing 100mL of ultrapure water to form a saturated salt solution. Under inert gas, 52.8mmol of dopamine hydrochloride (DA·HCl) was added to fully dissolve the complex. 58.1mmol of methacrylic anhydride was added dropwise to 25mL of THF, mixed thoroughly, and then added dropwise to the dopamine aqueous solution using a constant pressure dropping funnel. The pH of the solution was maintained above 8, adjusted with sodium hydroxide as needed. The mixed solution was reacted at room temperature under nitrogen for 14 hours. After the reaction, the solution was washed twice with ethyl acetate, and the solids were removed by vacuum filtration. The resulting aqueous solution was adjusted to a pH of less than 2 with HCl and extracted three times with ethyl acetate. The dark brown ethyl acetate layers (upper layers) obtained from the three extractions were combined and dried over anhydrous sodium sulfate for at least 4 hours. The solids were removed by vacuum filtration, and the ethyl acetate layers were precipitated three times in n-hexane. The precipitate was vacuum dried at 40°C to obtain dopamine-modified acrylic monomer (DOMA).

[0054] 3) Preparation of photosensitive amphiphilic random polymers:

[0055] 5mmol of hydrophilic acrylic monomer (AA), 5mmol of photosensitive coumarin-modified styrene monomer (VMc), and 10mmol of dopamine-modified acrylic monomer (DOMA) were weighed (the molar ratio of hydrophilic acrylic monomer, photosensitive coumarin-modified styrene monomer, and dopamine-modified acrylic acid was 1:1:2), dissolved in 40mL of 1,4-dioxane, and azobisisobutyronitrile (AIBN, 1.0% of the total molar number of monomers) was used as an initiator. The reaction was carried out at 65°C under inert gas protection for 24h. After the reaction was terminated, the reaction solution was first precipitated with petroleum ether, then dissolved with THF and precipitated again. The precipitation was dissolved three times, and the resulting solid was vacuum dried at 40°C to obtain a photosensitive amphiphilic random polymer (PAVD). Figure 1 The chemical shift δ in the figure shows that δ2.50 is the solvent peak; the H c The characteristic peak appears at chemical shift δ12; the H s and H r Characteristic peaks appear at chemical shifts of δ8.84-8.64; H l The characteristic peak appears at the chemical shift of δ6.1, indicating that the photosensitive amphiphilic random polymer (PAVD) was successfully synthesized through the free radical polymerization of three functional monomers.

[0056] 4) Preparation of molecularly imprinted composite nanoparticles:

[0057] Prepare 20 mg mL -1 The photosensitive amphiphilic random polymer was dissolved in DMF. After it was completely dissolved, the template molecule p-nitrophenol (PNP) was added to the above solution. The concentration of p-nitrophenol was 1 mg mL -1 The mass ratio of the photosensitive amphiphilic random polymer and the template molecule was 20:1. After stirring overnight to allow for interaction, 5 times the volume of ultrapure water was added dropwise under stirring to induce the assembly units to self-assemble into nanoparticles. The UV power was 600 mW / cm 2 UV crosslinking for 3 h, followed by dialysis in distilled water (MW: 8000-14000) for one day, yielding a concentration of 2 mg mL -1 The scanning electron micrograph of MIP NPs is shown in Figure 2 According to the same method, the concentration of the photosensitive amphiphilic random polymer was changed to 10 mg·mL -1 , 30mg·mL -1 , 40mg·mL -1 , 50mg·mL -1 , 60mg·mL -1The particle size distribution and potential of MIP NPs assembled with different concentrations of PAVD are shown in Figure 2. Figure 3 As shown in the particle size distribution and potential diagram, it can be seen that with the increase of PAVD concentration, the average particle size of MIP NPs increases slightly, and the potential increases. This is because the increase in PAVD concentration increases the number of molecular chains in the solution, the number of particle aggregations, and the average charge per unit volume. -1 The particle size of MIP NPs assembled by PAVD is about 50 nm. Figure 2 corresponding to the scanning electron microscope.

[0058] 5) Preparation of molecularly imprinted photocatalytic composite glass fibers:

[0059] 250 mg of hydroxylated glass fiber was placed in a 2 mg mL -1 The MIP NPs were immersed in water for 5 h, taken out and dried, and then the MIP NPs were immersed in water to form a 6 mg mL -1 The samples were immersed in TiO2 NPs for 2 h, with the mass ratio of molecularly imprinted composite nanoparticles to hydroxylated glass fibers in the solution being 1:10, and the mass ratio of titanium dioxide nanoparticles to hydroxylated glass fibers in the solution being 1:8. Titanium dioxide was irradiated with ultraviolet light for 1 h to degrade residual p-nitrophenol (PNP). After washing with water, the samples were dried at 40 °C to obtain molecularly imprinted photocatalytic composite glass fibers (TiO2 / MIP NPs / GF).

[0060] The hydroxylated glass fiber is prepared by ultrasonically treating the glass fiber in acetone and (2-12) mol / L hydrochloric acid, followed by rinsing with ultrapure water and drying to obtain the hydroxylated glass fiber. The purpose of hydroxylating the glass fiber is that the main component of glass fiber is SiO2, which exists in the form of Si-O-Si bonds and is difficult to wet with water. Hydroxylation hydrolyzes the Si-O bonds to produce Si-OH, a highly active hydrophilic group that easily supports particles on its surface in aqueous systems.

[0061] Example 2-Example 7

[0062] The preparation was carried out according to the method of Example 1, except that, in the preparation of Examples 2 to 7, the molar ratios of the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer were 4:1:1, 2:1:1, 1:1:1, 1:2:1, 1:4:1, and 1:1:4, respectively. The other preparation steps were the same as those in Example 1, and the molar ratio of Example 1 was 1:1:2.

[0063] For easy identification, use FGF Xrepresents molecularly imprinted photocatalytic composite glass fibers made of polymers synthesized with different monomer feed ratios, and the subscript x represents the molar percentage of the hydrophilic monomer acrylic acid (AA) in the polymer, such as FGF 33 The theoretical molar percentage of the hydrophilic monomer acrylic acid in the polymer used to make the molecularly imprinted photocatalytic composite glass fiber is 33 mol%. 67 , FGF 50 , FGF 33 The ratios of the polymer hydrophilic acrylic monomer, photosensitive coumarin modified styrene monomer and dopamine modified acrylic monomer used to make molecularly imprinted photocatalytic composite glass fibers are 4:1:1, 2:1:1 and 1:1:1 respectively; while FGF 25-1 , FGF 25-2 , FGF 17-1 , FGF 17-2 The ratios of the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer used to make the molecularly imprinted photocatalytic composite glass fiber are 1:2:1, 1:1:2, 1:4:1, and 1:1:4, respectively.

[0064] Example 8

[0065] When preparing the sensitive amphiphilic random polymer, the hydrophilic acrylic acid monomer was replaced with methacrylic acid, and the other preparation steps were the same as in Example 1.

[0066] Example 9

[0067] When preparing the sensitive amphiphilic random polymer, the hydrophilic acrylic acid monomer was replaced with methyl methacrylate, and the other preparation steps were the same as in Example 1.

[0068] Example 10

[0069] When preparing sensitive amphiphilic random polymers, the photosensitive coumarin-modified styrene monomer VMc is replaced by Methylpropional Glycidyl acrylate , the other preparation steps are the same as those in Example 1.

[0070] The prepared TiO2 / MIP NPs / GF was used to photocatalytically degrade p-nitrophenol (PNP) in water to investigate its ability to degrade wastewater.

[0071] Test Example 1

[0072] An application of a molecularly imprinted photocatalytic composite glass fiber comprises the following steps:

[0073] The TiO2 / MIP NPs / GF prepared in Example 1 was added to 10 mL of a 10 mg·L -1The solution of p-nitrophenol PNP was placed in a shaking table, enriched for 2 hours, and irradiated with ultraviolet light for 4 hours. The absorbance at the highest point of the ultraviolet characteristic peak of PNP in the wastewater was measured by ultraviolet spectrophotometer to calculate the concentration of PNP remaining in the water after degradation. The concentration change of PNP in the water before and after degradation (C) was obtained by subtracting the concentration of PNP remaining in the water after degradation (C) from the initial concentration of PNP in the water (C0). O -C), using the concentration change (C O -C) divided by the initial concentration of PNP in water (C0) to obtain the removal efficiency of PNP in water by TiO2 / MIP NPs / GF. The removal efficiency is shown in the following formula:

[0074]

[0075] Where: C0 is the initial concentration of PNP in water;

[0076] C is the concentration of PNP remaining in the water after degradation.

[0077] In order to verify the ability of different functionalized composite glass fibers (FGF) to degrade PNP in water, the following comparative experiments were designed.

[0078] Comparative experiment 1: hydroxylated glass fiber (GF).

[0079] Comparative Experiment 2: After GF was soaked in MIP NPs, the hydroxylated glass fiber was soaked in TiO2 NPs. The other preparation steps were the same as those in Example 1 to obtain molecularly imprinted composite glass fibers (MIP NPs / GF).

[0080] Comparative Experiment 3: When preparing MIP NPs, the template molecule PNP was not added, and the other preparation steps were the same as those in Example 1 to obtain non-molecularly imprinted photocatalytic composite glass fibers (TiO2 / PAVD NPs / GF).

[0081] Comparative experiment 4: Without preparing MIP NPs, GF was directly soaked in TiO2 NPs. The other preparation steps were the same as those in Example 1 to obtain a photocatalytic composite glass fiber (TiO2 / GF).

[0082] Comparative experiment 5: GF was first soaked in TiO2 NPs and then soaked in MIP NPs. The other preparation steps were the same as those in Example 1 to obtain photocatalytic molecularly imprinted composite glass fiber (MIP NPs / TiO2 / GF).

[0083] Comparative Experiment 6: The molecularly imprinted photocatalytic composite glass fiber (TiO2 / MIP NPs / GF) obtained in Example 1 was subjected to Test Example 1, taken out and dried to obtain a recovered molecularly imprinted photocatalytic composite glass fiber (RE TiO2 / MIP NPs / GF).

[0084] The scanning electron microscopy images of GF obtained in comparative experiment 1, MIP NPs / GF obtained in comparative experiment 2, TiO2 / MIPNPs / GF obtained in Example 1, and RE TiO2 / MIP NPs / GF obtained in comparative experiment 6 are shown in FIG. Figure 4 As shown, corresponding to Figure 4 a, b, c, d in. Figure 4 In a, we can see that there are no particles on the GF surface at the same magnification; Figure 4 In b, we can see that the surface of MIP NPs / GF is loaded with MIP NPs of about 50 nm. Figure 4 In Figure c, it can be seen that there are not only MIP NPs of about 50nm but also TiO2 NPs of 3-5nm on the surface of TiO2 / MIP NPs / GF, indicating that the experiment successfully modified the molecularly imprinted nanoparticles and titanium dioxide photocatalysts onto the glass fiber, proving that the idea is feasible. Figure 4 In middle d, it can be seen that the MIP NPs and TiO2 NPs on the surface of RE TiO2 / MIP NPs / GF have slightly fallen off.

[0085] The removal rates of PNP in water degraded by different FGFs obtained in Example 1 and comparative experiments 1-5 were obtained by the steps of Test Example 1. Figure 5 As shown in the figure. Under the condition of 4h photodegradation, the removal rate of molecularly imprinted photocatalytic composite glass fiber (TiO2 / MIPNPs / GF) was the highest, followed by the photocatalytic molecularly imprinted composite glass fiber (MIP NPs / TiO2 / GF). The removal rate of photocatalytic composite glass fiber (TiO2 / GF) was about 20% lower than that of molecularly imprinted photocatalytic composite glass fiber (TiO2 / MIP NPs / GF), and the removal rate of molecularly imprinted composite glass fiber (MIP NPs / GF) was about 42%.

[0086] Since MIP NPs / TiO2 / GF first loads TiO2 NPs on the surface of glass fiber and then loads MIP NPs on the surface of glass fiber, and the interaction force between TiO2 NPs and glass fiber is weak, some TiO2 NPs fall off the surface of glass fiber; secondly, in the process of photodegradation of wastewater, since MIP NPs are on the outside, they will block ultraviolet light, reduce the light receiving area of ​​TiO2 photocatalyst, and reduce the degradation rate. The TiO2 / MIP NPs / GF composite first loads MIP NPs onto the surface of glass fibers. The catechol polymer structure creates strong interactions with the inorganic materials (TiO2 and glass fibers), ensuring adhesion between the MIP NPs and the glass fibers and anchoring the nano-TiO2, preventing the MIP NPs and TiO2 NPs from falling off the glass fibers. MIP NPs then utilize their specific recognition to concentrate organic pollutants in the water onto the composite glass fiber surface. Under UV light, the TiO2 photocatalyst generates oxygen-containing free radicals, which oxidize the organic pollutants into environmentally friendly small molecules. The imprinted pores of the MIP NPs are then exposed, allowing them to re-enrich the organic pollutants in the water, allowing the TiO2 photocatalyst to continue degrading them, repeating the cycle. While the TiO2 photocatalyst is highly effective at degrading high-concentration organic pollutants, the TiO2 photocatalyst lacks a concentration function and is therefore less effective at degrading low-concentration organic pollutants. Due to the presence of enrichment capacity in MIP NPs / GF, once the enrichment capacity reaches saturation, the absence of TiO2 photocatalysts to re-expose the pores in the MIP NPs leads to low degradation efficiency. Therefore, molecularly imprinted photocatalytic composite glass fibers (TiO2 / MIP NPs / GF) will be studied in the future.

[0087] Test Example 2

[0088] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 2 in a ratio of 4:1:1. 67 ) FGF was obtained by test example 1 67 Removal rate of PNP in degradation water.

[0089] Test Example 3

[0090] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 3 in a ratio of 2:1:1. 50 ) FGF was obtained by test example 1 50Removal rate of PNP in degradation water.

[0091] Test Example 4

[0092] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 4 in a ratio of 1:1:1. 33 ) FGF was obtained by test example 1 33 Removal rate of PNP in degradation water.

[0093] Test Example 5

[0094] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 5 in a ratio of 1:2:1. 25-1 ) FGF was obtained by test example 1 25-1 Removal rate of PNP in degradation water.

[0095] Test Example 6

[0096] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 1 in a ratio of 1:1:2. 25-2 ) FGF was obtained by test example 1 25-2 Removal rate of PNP in degradation water.

[0097] Test Example 7

[0098] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 6 in a ratio of 1:4:1. 17-1 ) FGF was obtained by test example 1 17-1 Removal rate of PNP in degradation water.

[0099] Test Example 8

[0100] The molecularly imprinted photocatalytic composite glass fiber (FGF) was prepared by mixing the hydrophilic acrylic monomer, the photosensitive coumarin-modified styrene monomer, and the dopamine-modified acrylic monomer of the photosensitive amphiphilic random polymer of Example 7 in a ratio of 1:1:4. 17-2 ) FGF was obtained by test example 1 17-2 Removal rate of PNP in degradation water.

[0101] Test Example 2-8 obtained FGF made of different ratios of polymers67 , FGF 50 , FGF 33 , FGF 25-1 , FGF 25-2 , FGF 17-1 , FGF 17-2 The removal rate of PNP in the degradation water is shown in Figure 6 As shown by FGF 67 , FGF 50 , FGF 33 , FGF 25 The changes in the removal rate of PNP in the degradation water show that the removal rate of PNP in the FGF degradation water increases with the reduction of hydrophilic acrylic monomers, indicating that the increase of photosensitive coumarin-modified styrene monomers and dopamine-modified acrylic monomers is beneficial to improving the removal rate of PNP in the FGF degradation water. The cross-linking of the self-assembly initiated by the photosensitive coumarin-modified styrene monomer fixes the molecular imprinting site, improves the selectivity of the imprinting hole to the template molecule, and enhances the stability of the polymer structure. The adhesion of the dopamine-modified acrylic monomer makes it have a strong interaction force with TiO2 NPs and glass fibers, preventing MIP NPs and TiO2NPs from falling off the glass fibers. 17-1 The sudden decrease in the removal rate of PNP in the degradation water may be due to the low content of dopamine-modified acrylic monomer, which caused the MIP NPs and TiO2 NPs to fall off from the glass fiber, and the excessive content of photosensitive coumarin-modified styrene monomer caused excessive cross-linking of the self-assembly, which caused the FGF 17-1 The recognition performance of FGF 17-2 The sudden decrease in the removal rate of PNP in the degradation water may be due to the high content of dopamine-modified acrylic acid monomer, which causes TiO2 NPs to be embedded in MIP NPs, greatly reducing its light-receiving area, and the low content of photosensitive coumarin-modified styrene monomer makes the cross-linking degree of the self-assembly unable to meet the use requirements of the material; while FGF 25-1 , FGF 25-2 The removal rate of PNP in the degradation water is the highest. The content of each monomer in the photosensitive amphiphilic random polymer is moderate. The synergistic effect of the three monomers makes the material performance reach the best state. 25-1 The removal rate of PNP in degraded water is lower than that of FGF 25-2 The removal rate of PNP in the degradation water is due to the fact that the adhesion of dopamine-modified acrylic monomer plays a vital role in the removal rate of PNP in the degradation water by molecularly imprinted photocatalytic composite glass fiber. Therefore, the molecularly imprinted photocatalytic composite glass fiber (abbreviated as FGF) prepared by using the hydrophilic acrylic monomer of photosensitive amphiphilic random polymer, photosensitive coumarin-modified styrene monomer and dopamine-modified acrylic monomer in a ratio of 1:1:2 was subsequently prepared. 25-2) as the research object.

[0102] Test Example 9

[0103] The concentration of the photosensitive amphiphilic random polymer in Example 1 was 20 mg·mL -1 Changed to 10 mg mL -1 ,20mg·mL -1 , 30mg·mL -1 , 40mg·mL -1 , 50mg·mL -1 , 60mg·mL -1 The prepared molecularly imprinted photocatalytic composite glass fiber (TiO2 / MIP NPs / GF) was subjected to Test Example 1 to obtain the effect of the concentration of the photosensitive amphiphilic random polymer on the removal rate of PNP in water degradation by the molecularly imprinted photocatalytic composite glass fiber, as shown in FIG. Figure 7 As shown. Figure 7 It can be seen that the concentration of polymer has little effect on the removal rate of PNP in water by molecularly imprinted photocatalytic composite glass fiber, but the concentration of polymer is 20 mg·mL -1 The removal rate is the highest, indicating that the concentration of polymer is 20 mg·mL -1 The number of molecular chains and the number of particle aggregations, as well as the degree of molecular chain cross-linking, are most appropriate and are most conducive to the removal rate of PNP in water; the concentration is 20 mg·mL -1 The number of molecular chains and particle aggregations below is relatively small, and the concentration is 20 mg·mL -1 The number of molecular chains and particle aggregation is too large, and the molecular chains are excessively cross-linked, which reduces the recognition and enrichment ability and the removal rate. Therefore, the concentration of the photosensitive amphiphilic random polymer is 20 mg·mL. -1 The prepared molecularly imprinted photocatalytic composite glass fiber was used as the research object.

[0104] Test Example 10

[0105] The concentration of 10mg·L of 10mL of p-nitrophenol PNP aqueous solution in Test Example 1 was 10mg·L -1 Changed to 1 mg·L -1 ,2mg·L -1 , 5mg·L -1 , 10mg·L -1 , 20mg·L -1 , 50mg·L -1 The molecularly imprinted photocatalytic composite glass fiber prepared in Example 1 was subjected to the above steps to obtain the effect of the initial concentration of PNP in water on the removal rate, as shown in FIG. Figure 8 shown. Figure 8 It can be seen that from 1-10 mg·L -1With the increase of PNP concentration, the removal rate of PNP increases continuously. This is because at very low concentrations, MIPNPs are difficult to be enriched on the surface of molecularly imprinted photocatalytic composite glass fibers. -1 As the PNP concentration increases, the removal rate of PNP decreases due to the degradation ability of the material. -1 The aqueous solution of organic pollutants was taken as the research object.

[0106] Test Example 11

[0107] The PNP aqueous solution in Test Example 1 was increased to four types, namely PNP aqueous solution, o-nitrophenol (ONP) aqueous solution, m-nitrophenol (MNP) aqueous solution, and hydroquinone (HQ) aqueous solution (the volume and concentration of the four aqueous solutions were the same as those in Test Example 1), and the removal rates of PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution were calculated by TiO2 / MIP NPs / GF (abbreviated as PNP / FGF) with PNP as the template molecule.

[0108] Test Example 12

[0109] The template molecule PNP in the preparation of Example 1 was replaced with o-nitrophenol (ONP), and the other preparation steps were the same as those of Example 1. The PNP aqueous solution in Test Example 1 was increased to four solutions: a PNP aqueous solution, an ONP aqueous solution, an MNP aqueous solution, and an HQ aqueous solution (the volumes and concentrations of the four aqueous solutions were the same as those in Test Example 1). The removal rates of the PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution were calculated by TiO2 / MIP NPs / GF (abbreviated as ONP / FGF) using ONP as the template molecule.

[0110] Test Example 13

[0111] The template molecule PNP in the preparation of Example 1 was replaced with m-nitrophenol MNP, and the other preparation steps were the same as those of Example 1. The PNP aqueous solution in Test Example 1 was increased to four solutions: PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution (the volumes and concentrations of the four aqueous solutions were the same as those in Test Example 1). The removal rates of the PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution were calculated by TiO2 / MIP NPs / GF (abbreviated as MNP / FGF) using MNP as the template molecule.

[0112] Test Example 14

[0113] The template molecule PNP in the preparation of Example 1 was replaced with hydroquinone HQ, and the other preparation steps were the same as those of Example 1. The PNP aqueous solution in Test Example 1 was increased to four solutions: PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution (the volumes and concentrations of the four aqueous solutions were the same as those in Test Example 1). The removal rates of the PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution were calculated for the TiO2 / MIP NPs / GF (abbreviated as HQ / FGF) using HQ as the template molecule.

[0114] The removal rates of FGF made from different template molecules in Test Examples 11-14 for degradation of PNP aqueous solution, ONP aqueous solution, MNP aqueous solution, and HQ aqueous solution are shown in Table 1. Figure 9 As shown in the figure. It can be seen that the FGF prepared with the same template molecule treats different types of wastewater. When the type of wastewater is the same as the template molecule of FGF, its removal rate is the highest. The removal efficiency difference between the prepared PNP / FGF in degradation of PNP wastewater and HQ wastewater is about 35%. When the FGF prepared with different template molecules treats the same type of wastewater, its removal rate is the highest when the template molecule of FGF is the same as the type of wastewater. This shows that the MIP NPs in the molecularly imprinted photocatalytic composite glass fiber play a role in enriching specific pollutants on the material surface, the TiO2 photocatalyst plays a photodegradation role, and the overall synergistic effect of the molecularly imprinted photocatalytic composite glass fiber makes the removal rate the highest when the template molecule of FGF is the same as the type of wastewater.

[0115] FGFs prepared with different template molecules were used to treat corresponding types of wastewater. When the template molecule of FGF and the type of wastewater were both PNP, since PNP contained hydroxyl, nitro, and benzene ring groups, and the hydroxyl and nitro groups were in the para position, it was easier to form multiple interaction points (especially hydrogen bonds, electrostatic interactions, and hydrophobic interactions) with the molecular chains in MIP NPs. Therefore, the removal rate of PNP degradation by FGF was the highest, reaching 98.41%.

[0116] The detailed description of a molecularly imprinted photocatalytic composite glass fiber and its preparation method and application based on the above reference embodiments is illustrative rather than restrictive. Several embodiments can be listed according to the limited scope. Therefore, changes and modifications without departing from the overall concept of the present invention should fall within the scope of protection of the present invention.

Claims

1. A method for preparing a molecularly imprinted photocatalytic composite glass fiber, characterized in that: The preparation method comprises the following steps: 1) A hydrophilic acrylic monomer, a photosensitive coumarin-modified styrene monomer, and a dopamine-modified acrylic monomer are dissolved in an organic solvent, an initiator is added, and a polymerization reaction is initiated. After the reaction, the filtrate is precipitated in petroleum ether, and the solid is separated, purified, and dried to prepare a photosensitive amphiphilic random polymer (PAVD); 2) The photosensitive amphiphilic random polymer and template molecule are dissolved in an organic solvent, and ultrapure water is added dropwise under stirring to induce self-assembly to form nanoparticles. After UV cross-linking, the organic solvent is removed by dialysis in distilled water to obtain molecularly imprinted composite nanoparticles (MIP NPs). 3) Molecularly imprinted composite nanoparticles and titanium dioxide nanoparticles are modified on the surface of hydroxylated glass fiber, the template molecules are removed, and the fiber is washed with water and dried to obtain molecularly imprinted photocatalytic composite glass fiber (TiO2 / MIP NPs / GF).

2. The preparation method according to claim 1, characterized in that In step 1), the molar ratio of the hydrophilic acrylic monomer to the photosensitive coumarin-modified styrene monomer and the dopamine-modified acrylic monomer is (1-5):(1-5):(1-5).

3. The preparation method according to claim 1, characterized in that The polymerization reaction conditions are as follows: stirring at 55-70° C. for 18-28 h under inert gas protection.

4. The preparation method according to claim 1, characterized in that In step 1), the preparation method of the photosensitive coumarin-modified styrene monomer is: Hydroxycoumarin, potassium carbonate and 4-chloromethylstyrene are added to an organic solvent, heated for reaction, and then filtered. The filtrate is precipitated in water, and a solid is separated and purified and dried to obtain a photosensitive coumarin-modified styrene monomer.

5. The preparation method according to claim 1, characterized in that In step 1), the preparation method of the dopamine-modified acrylic monomer is as follows: dopamine hydrochloride is added to a saturated solution formed by dissolving borax and bicarbonate or phosphate in water, an acrylic acylating agent is dissolved in an organic solvent and then added dropwise to the above saturated salt solution while maintaining the pH of the solution above 8, and reacting, washing, adjusting the pH to less than 2, extracting, drying, purifying, and oven-drying to obtain the dopamine-modified acrylic monomer.

6. The preparation method according to claim 1, characterized in that In step 2), the mass ratio of the photosensitive amphiphilic random polymer to the template molecule is (5-100):1; the template molecule is nitrophenol or hydroquinone.

7. The preparation method according to claim 1, characterized in that In step 3), the hydroxylated glass fiber is first immersed in two solutions, first in the molecularly imprinted composite nanoparticle solution, and then in the titanium dioxide nanoparticle solution.

8. The preparation method according to claim 7, characterized in that In step 3), the concentration of the molecularly imprinted composite nanoparticle solution is (0.1-50) mg·mL -1 The concentration of titanium dioxide nanoparticle solution is (0.1-50) mg·mL -1 .

9. A molecularly imprinted photocatalytic composite glass fiber prepared by the preparation method according to any one of claims 1 to 8.

10. An application of the molecularly imprinted photocatalytic composite glass fiber according to claim 9, characterized in that: Used for wastewater treatment of organic pollutants.

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