Molecularly sieving self-assembled light-responsive membrane, and preparation method and application thereof

Abstract

The present application relates to the technical field of molecular sieve, in particular to a kind of molecular sieve self-assembly light response membrane and its preparation method and application.Utilize the supramolecular assembly based on dithiophene ethylene derivative and calabash urea as basic functional unit, after being coated on substrate, it is introduced into oil phase solution, and composite polyamide membrane is formed on substrate surface using interfacial polymerization reaction.Based on the host-guest recognition ability of dithiophene ethylene derivative and calabash urea, a dynamic adjustable recognition system is formed.Under light condition, the recognition ability of the whole system to molecule is influenced by changing the configuration of molecule.The self-assembly light response membrane has good dye interception effect and small cut-off molecular weight, and can realize accurate screening of similar molecular weight dye molecules, and is expected to be widely applied in wastewater treatment field.

Description

Technical Field

[0001] This invention relates to the field of molecular sieving technology, and in particular to a self-assembled photoresponsive membrane based on molecular sieving, its preparation method, and its application. Background Technology

[0002] Membrane separation technology, as a highly efficient and energy-saving separation method, has been widely used in water treatment, biomedicine, chemical industry, and gas separation, among other fields. Its core advantage lies in the specific physical or chemical structure of the membrane material, which allows selective permeation of some components (such as solvents and small molecules) while blocking the passage of other components. The separation accuracy of traditional membranes mainly depends on the inherent static pore size and diffusion path within the membrane. Once prepared, its separation performance (including molecular weight cutoff, permeate flux, and selectivity) remains fixed. This static characteristic makes traditional membranes unsuitable for handling complex mixture systems, requiring dynamic adjustment of separation accuracy, or performing specific time-series separation tasks.

[0003] To endow separation membranes with dynamically adjustable intelligent properties, responsive smart membranes have been gradually developed. These membranes can transform external environmental stimuli (such as temperature, pH, light, electric fields, magnetic fields, or specific chemical substances) into changes in their own physical or chemical properties, thereby achieving precise control over separation performance. Among them, photoresponsive membranes, with their unique advantages of non-contact operation, instantaneous response, remote control, and precise spatiotemporal controllability, have become the forefront of current smart membrane research.

[0004] While existing photoresponsive membranes have made some progress in flux switching control and coarse sieving, many challenges remain in achieving high-precision, high-selectivity molecular sieving. Especially in dye wastewater treatment scenarios, the application of photoresponsive membranes faces numerous specific technical difficulties, mainly in the following aspects:

[0005] I. Insufficient pore size control and sieving precision: Dye molecules have diverse sizes, and the pore size control precision of existing photoresponsive membranes is limited, making it difficult to achieve precise sieving of dye molecules of different sizes. In addition, some membranes have too low water flux due to their dense structure, making it impossible to balance dye retention rate and treatment efficiency, and making it difficult to meet the separation requirements of complex dye wastewater systems.

[0006] Second, the disordered pore structure is prone to fouling: the lack of regularity and uniformity in the mass transfer channels within the membrane not only affects the selective separation of dye molecules, but also easily leads to the adsorption and accumulation of dye molecules within the pores, causing membrane fouling; moreover, simple water washing is difficult to completely remove pollutants, requiring chemical reaction cleaning, which increases the complexity of the treatment process.

[0007] 3. The coupling mechanism between photoresponse and dye separation is imperfect: the synergy between the isomerization reaction of photoresponse groups and the dye sieving process is poor. The changes in pore size and hydrophilicity / hydrophobicity under light control are difficult to accurately match the dye separation requirements, resulting in limited light control efficiency and the inability to achieve flexible and precise control of dye separation performance.

[0008] IV. Poor stability and reversibility, and limited service life: When used for long-term dye wastewater treatment, the membrane is prone to performance degradation during light cycle and dye adsorption-desorption process. After several retention cycles, the retention rate and water flux of some membranes will drop significantly. At the same time, the reversible isomerization ability of photoresponsive groups is easily affected by wastewater components, further shortening the actual service life of the membrane.

[0009] Therefore, there is an urgent need to develop a new type of photoresponsive separation membrane. Summary of the Invention

[0010] This invention aims to at least solve one of the technical problems existing in related technologies. Therefore, the first objective of this invention is to provide a method for preparing a molecular sieve self-assembled photoresponsive membrane; the second objective is to provide a molecular sieve self-assembled photoresponsive membrane; and the third objective is to provide an application of the molecular sieve self-assembled photoresponsive membrane.

[0011] To achieve the first objective, the technical solution adopted by this invention is as follows:

[0012] A method for preparing a self-assembled photoresponsive membrane using molecular sieves includes the following steps:

[0013] S100, prepare an aqueous solution containing supramolecular assemblies and an oil solution containing 1,3,5-benzenetricarboxyl chloride respectively;

[0014] The structural formula of the supramolecular assembly is shown below:

[0015] ;

[0016] Among them, in the structural formula The chemical structural formula of cucurbituril is shown below:

[0017] ;

[0018] S200: After coating the aqueous solution onto the substrate surface, the oil solution is introduced, and a composite polyamide film is formed on the substrate surface by interfacial polymerization reaction.

[0019] The structural formula of the monomer forming the composite polyamide film structure under visible light conditions is shown below:

[0020] ;

[0021] The structural formula of the monomer that forms the composite polyamide film structure under ultraviolet light is shown below:

[0022] ;

[0023] S300. The composite polyamide film is thermally crosslinked and cured to obtain a molecular sieve self-assembled photoresponsive film.

[0024] Dithiophene ethylene derivatives, as a class of high-performance photochromic compounds, are based on a reversible electrocyclization reaction of two thiophene rings within the molecule under specific wavelengths of light. This reaction causes them to switch between open-ring and closed-ring states, accompanied by significant changes in physicochemical properties. As photochromic materials, DTE derivatives exhibit high fatigue resistance and thermal stability, while their rapid response speed and high quantum yield ensure switching efficiency. Meanwhile, cucurbituril (CB) molecules possess a highly symmetrical, rigid cage-like structure. Their hydrophobic cavities and hydrophilic ports composed of carbonyl oxygen atoms form a unique microenvironment that is externally hydrophilic and internally hydrophobic. This structural characteristic allows them to selectively and with high affinity bind organic cations, metal ions, and neutral molecules through various non-covalent interactions such as ion-dipole and hydrophobic interactions. Their excellent stability, water solubility, and controllable host-guest chemistry lay a solid foundation for the construction of supramolecular functional materials.

[0025] Further, in step S100, the preparation of the aqueous solution containing the supramolecular assembly includes the following process: dissolving the dithiophene ethylene-based derivative in a mixed solvent of trifluoroethanol and N,N-dimethylacetamide, then adding the aqueous solution of the cucurbituril, mixing evenly, to obtain the aqueous solution containing the supramolecular assembly;

[0026] The structural formula of the dithiophene ethylene-based derivative is shown below:

[0027] .

[0028] Furthermore, the volume ratio of trifluoroethanol to N,N-dimethylacetamide in the mixed solvent is 14:1 to 15:1.

[0029] Further, in step S100, the solvent of the oil phase solution containing 1,3,5-benzenetricarboxyl chloride is selected from n-hexane.

[0030] Furthermore, in step S200, after introducing the oil phase solution, a settling process is included, with a settling time of 5 to 10 minutes.

[0031] Further, in step S200, the substrate is selected from polyacrylonitrile (PAN) substrate.

[0032] Furthermore, in step S200, the wavelength of the visible light is greater than 550nm, and the wavelength of the ultraviolet light is 310nm to 360nm.

[0033] To achieve the second objective, the technical solution adopted by this invention is as follows:

[0034] A molecular sieve self-assembled photoresponsive membrane is prepared using any one of the above-described methods for preparing a molecular sieve self-assembled photoresponsive membrane.

[0035] To achieve the third objective, the technical solution adopted by this invention is as follows:

[0036] An application of a molecular sieve self-assembled photoresponsive membrane is disclosed, which is used to treat wastewater containing dye molecules.

[0037] The recognition of dye molecules by supramolecular assemblies formed from dithiophene ethylene derivatives and cucurbituril is based on host-guest interactions, which involve the synergistic effects of various non-covalent forces. The main types of interactions include:

[0038] I. Hydrophobic interactions are one of the most important driving forces: The internal cavity of cucurbituril is hydrophobic, enabling it to form strong hydrophobic interactions with the aromatic ring structure of dye molecules. Especially for dye molecules containing multiple aromatic rings, hydrophobic interactions provide a powerful binding driving force. Studies have shown that the high affinity of cucurbituril for aromatic compounds mainly stems from the hydrophobic effect.

[0039] II. π-π stacking interactions play a crucial role in dye molecule recognition: Many dye molecules contain conjugated aromatic systems that can form π-π stacks with the methylene bridges or other aromatic groups on the inner surface of cucurbita cavities. This interaction not only enhances the stability of host-guest binding but also influences the electronic structure and spectral properties of dye molecules.

[0040] Third, electrostatic interactions are particularly important for the recognition of charged dye molecules: the carbonyl group at the port of cucurbituril has a certain degree of negative charge, which can form an electrostatic attraction with cationic dye molecules. Simultaneously, by introducing appropriate charged groups onto the dithiophene ethylene molecule, the electrostatic interaction between the entire supramolecular system and the dye molecules can be modulated, achieving selective recognition of dye molecules with different charge properties.

[0041] IV. Although hydrogen bonding interactions are not as important as hydrophobic interactions in the cucurbituril host-guest system, they still play a role under certain conditions. The carbonyl oxygen atom at the cucurbituril port can act as a hydrogen bond acceptor, forming hydrogen bond interactions with hydrogen bond donors (such as amino and hydroxyl groups) on the dye molecule.

[0042] A dynamically tunable recognition system is formed by combining the host-guest recognition ability of dithiopheneethylene derivatives with cucurbituril. Under light conditions, changes in the molecular configuration of dithiopheneethylene can modulate its interaction with cucurbituril, thereby affecting the overall system's recognition ability of dye molecules.

[0043] Furthermore, the dye molecules include one or more of methylene blue trihydrate, crystal violet, amaranth, Congo red, reactive black, and Alsin blue.

[0044] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0045] This invention provides a method for preparing a molecularly sieved self-assembled photoresponsive membrane. It utilizes a supramolecular assembly formed from a dithiophene ethylene derivative and cucurbituril as the basic functional unit. This assembly is coated onto a substrate and then introduced into an oil-phase solution. Interfacial polymerization is then used to form a composite polyamide film on the substrate surface. The photochromic properties of dithiophene ethylene are combined with the host-guest recognition ability of cucurbituril to form a dynamically tunable recognition system. Under illumination, changes in the molecular configuration of dithiophene ethylene can modulate its interaction with cucurbituril, thereby affecting the overall system's recognition ability of dye molecules.

[0046] The present invention provides a molecular sieving self-assembled photoresponsive membrane with good dye retention effect and small cutoff molecular weight, which can realize the precise sieving of dye molecules with similar molecular weight, and is expected to be widely used in the field of wastewater treatment.

[0047] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0048] Figure 1 This is a transmission electron microscope (TEM) image of the dithiophene ethylene derivative solution provided in Example 1 of the present invention.

[0049] Figure 2 This is a TEM image of the CB[7] aqueous solution provided in Example 1 of the present invention.

[0050] Figure 3 This is a TEM image of an aqueous solution containing supramolecular assemblies provided in Example 1 of the present invention.

[0051] Figure 4 This is a scanning electron microscope (SEM) image of the DTE@CB[7] film provided in Embodiment 1 of the present invention.

[0052] Figure 5 This is the Fourier transform infrared spectrum (FTIR) of the DTE@CB[7] film provided in Embodiment 1 of the present invention.

[0053] Figure 6 The graph shows the water flux detection results of the DTE@CB[7] membrane and the DTE membrane provided in Example 1 of this invention.

[0054] Figure 7 This is a graph showing the results of the detection of the retention of DTE@CB[7] membrane and DTE membrane provided in Example 2 of the present invention.

[0055] Figure 8 This is a graph showing the relationship between molecular weight and rejection rate provided in Example 2 of this invention.

[0056] Figure 9 This is a graph showing the detection results of the ultraviolet-visible spectrophotometer provided in Example 3 of the present invention. Detailed Implementation

[0057] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention, but cannot be used to limit the scope of this invention.

[0058] In the following embodiments, unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available, unless otherwise specified, and are carried out in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions.

[0059] Example 1

[0060] The process for preparing a self-assembled photoresponsive membrane using molecular sieves is as follows:

[0061] I. A dithiophene ethylene-based derivative (denoted as DTE) was prepared according to the preparation method disclosed in Example 1 of patent CN120795397A. .

[0062] 2. Preparation of aqueous solution.

[0063] The previously prepared DTE (3 mg) was added to a mixed solvent containing trifluoroethanol (2.8 mL) and N,N-dimethylacetamide (DMAC) (0.2 mL), and the solution was sonicated until completely dissolved to obtain a DTE solution. Its TEM image is shown below. Figure 1 As shown;

[0064] Separately, 9 mg of cucurbituril[7] (CB[7]) was dissolved in 1 mL of deionized water to obtain an aqueous solution of CB[7]. The TEM image of the solution is shown below. Figure 2 As shown;

[0065] The DTE solution was mixed with the CB[7] aqueous solution and stirred thoroughly to assemble the two into a supramolecular assembly, resulting in an aqueous solution containing the supramolecular assembly. Its TEM image is shown below. Figure 3 As shown;

[0066] The supramolecular assembly is denoted as DTE / CB[7], and its structural formula is shown below.

[0067] ;

[0068] Among them, in the structural formula The chemical structure of CB[7] is shown below:

[0069] .

[0070] III. Preparation of oil phase solution.

[0071] 1,3,5-Trimethylbenzene chloride (TMC) was dissolved in n-hexane to prepare a 0.1% (w / v) TMC n-hexane solution, which was used as the oil phase reaction solution.

[0072] To prepare an oil phase reaction solution (5 mL), add TMC (5 mg) to the container, then add n-hexane and bring the volume up to 5 mL to obtain the oil phase reaction solution.

[0073] IV. Forming composite polyamide films using interfacial polymerization reactions.

[0074] The prepared aqueous solution of DTE / CB[7] was poured evenly onto the surface of the PAN substrate to ensure that the aqueous solution completely covered the surface. After pouring, it was left to stand for 5 to 10 minutes. Then, the excess aqueous solution on the surface was removed, and a roller was used to remove the residual droplets on the membrane surface. Then, the treated substrate was placed back into the film forming mold, and the oil phase reaction solution (5 mL) was added to the mold to carry out the interfacial polymerization reaction. After the reaction time was 5 minutes, the composite polyamide membrane was obtained. The excess oil phase reaction solution on the membrane surface was poured off, and then the membrane surface was rinsed with n-hexane. After rinsing, the membrane was transferred to an oven preheated to 60°C for thermal crosslinking treatment. After the treatment time was 10 minutes, the membrane was taken out of the oven and naturally cooled to room temperature (about 25°C) to obtain the molecular sieve self-assembled photoresponsive membrane, which was named DTE@CB[7] membrane. The responsive membrane was stored in deionized water for further use.

[0075] The above preparation process was carried out at room temperature (approximately 25°C) and relative humidity of 45%–60%.

[0076] When the DTE@CB[7] film is irradiated with ultraviolet light (310-360nm) for 30-60s, it transforms into a closed-loop structure (DTE@CB[7]-C). When irradiated with visible light (wavelength>550nm) for 90-120s, it reverts to an open-loop structure (DTE@CB[7]-O), as shown below:

[0077] .

[0078] SEM images of the DTE@CB[7] membrane, as shown Figure 4 As shown;

[0079] Figure A shows the surface morphology of the DTE@CB[7] membrane. From this figure, it can be seen that the membrane is composed of uniformly stacked submicron particles with a rough surface and rich nanoscale pores. This structure not only significantly increases the specific surface area of ​​the membrane, providing sufficient active sites for catalytic reactions or adsorption processes, but also forms precise molecular / ion sieving channels, indicating good separation accuracy and selectivity.

[0080] Figure B shows the cross-sectional morphology of the DTE@CB[7] membrane. This figure further confirms the layered structure of the membrane. The interface between the upper functional layer and the lower support layer is clear and tightly bonded. The functional layer has a uniform thickness and internal through-holes, which not only ensures the efficient permeation of fluid and gives the membrane the potential high flux performance, but also improves the mechanical stability and deformation resistance of the membrane through the interlayer support, making it less likely to collapse or delaminate under actual working conditions.

[0081] Overall, this granular and layered microstructure endows membrane materials with comprehensive advantages in separation efficiency, mass transfer kinetics and mechanical reliability, providing a solid structural foundation for their application in separation, catalysis or energy storage.

[0082] FT-IR image of DTE@CB[7] membrane, as shown Figure 5 As shown in the figure, it can be seen that in the Fourier transform infrared spectrum, ~1530cm -1 Amide II band (NH bending / CN stretching) and ~1640cm -1 The significant changes in the amide I band (C=O stretching) jointly confirm the formation of amide bonds during interfacial polymerization. Meanwhile, ~1730 cm⁻¹ -1 The characteristic absorption of carbonyl groups in the vicinity of CB[7] is significantly enhanced, further indicating that DTE@CB[7] has been successfully introduced and formed a polyamide functional layer. These spectral features together confirm the successful preparation of the DTE@CB[7] functionalized polyamide composite film.

[0083] Comparative Example

[0084] I. Preparation of DTE and formulation of its solution are the same as in Example 1.

[0085] II. Preparation of the oil phase solution is the same as in Example 1.

[0086] III. Forming composite polyamide films using interfacial polymerization reactions.

[0087] Except for replacing the added DTE / CB[7] aqueous solution with DTE solution, the rest of the process is the same as in Example 1. The resulting composite polyamide membrane is denoted as DTE membrane.

[0088] Detection Example 1

[0089] The water flux of the DTE@CB[7] membrane and the DTE membrane was detected using a cross-flow device. The process is as follows: The DTE@CB[7] membrane and the DTE membrane prepared above were installed in the cross-flow filtration system. The test solution was deionized water. After turning on the device, the system pressure was increased to 4 bar. After maintaining the pressure for 30 minutes, the test was started. The water flux detection results are as follows: Figure 6 As shown in the figure, the water flux of the DTE membrane is approximately 12 L·m. -2 ·h -1 ·bar -1 The water flux of the DTE@CB[7] membrane was increased to approximately 18 L·m -2 ·h -1 ·bar -1The increase in water flux of the DTE@CB[7] membrane is about 50% higher than that of the DTE membrane. The improvement in water flux of the DTE@CB[7] membrane can be attributed to the regulation of the membrane microstructure by the host-guest inclusion interaction: the introduction of CB[7] makes the membrane surface more abundant with nanoscale pores and rough morphology, increasing the effective contact area and permeation channels of water; at the same time, the through-pores in the layered structure reduce the resistance to water molecule transport, thereby significantly improving the water permeability without sacrificing structural stability. This result shows that regulating the micromorphology and pore structure of the membrane through the host-guest chemical strategy is an effective way to optimize the flux of high-performance separation membranes, providing structural and performance basis for subsequent applications in the fields of photoresponse separation and water treatment.

[0090] Detection Example 2

[0091] The retention of different dye molecules by DTE@CB[7]-O membrane, DTE@CB[7]-C membrane, DTE-O membrane and DTE-C membrane was detected by cross-flow device. The process is as follows: The DTE@CB[7] membrane and DTE membrane prepared above were installed in the cross-flow filtration system. The test solution was an aqueous solution of the aforementioned dye molecules (concentration of 20ppm). After the device was turned on, the system pressure was increased to 4 bar. After maintaining the pressure for 30 minutes, the test was started. The retention results were as follows: Figure 7 As shown;

[0092] Figure A shows the retention rates of different dye molecules in two different states of the DTE@CB membrane, and Figure B shows the retention rates of different dye molecules in two different states of the DTE membrane.

[0093] From these two figures, it can be seen that both membrane materials (DTE@CB[7] membrane and DTE membrane) exhibit the rule that the retention rate of the closed ring state (-C) is greater than that of the open ring state (-O), especially for small molecule dyes (methylene blue trihydrate, crystal violet); the introduction of CB[7] improves the retention capacity of the open ring state for small molecule dyes, while reducing the performance difference between the two light-controlled states.

[0094] The molecular weights of the different dyes are as follows: Methylene Blue Trihydrate is 374 Da, Crystal Violet is 408 Da, Amaranth Red is 604 Da, Congo Red is 697 Da, Reactive Black is 995 Da, and Alsin Blue is 1299 Da. The relationship between the molecular weight of different dyes and their retention rates is shown in the following graph: Figure 8 As shown in the figure, it can be seen that the smaller the molecular weight, the better the retention effect of the closed-ring DTE@CB[7]-C membrane compared to the open-ring DTE@CB[7]-O membrane. This result indicates that the closed-ring state (-C) can effectively enhance the retention capacity of small molecule dyes and realize the function of light-controlled sieving. Therefore, the DTE@CB[7] membrane can be used for selective separation, that is, small molecules can pass through in the open-ring state, and small molecules are retained in the closed-ring state, while large molecules are always retained.

[0095] Detection Example 3

[0096] The retention of different dye molecules by DTE@CB[7]-O membrane and DTE@CB[7]-C membrane was detected using a cross-flow device. The process is as follows: The DTE@CB[7] membrane prepared above was installed in the cross-flow filtration system. The test solution was an aqueous solution of crystal violet (CV), an aqueous solution of methylene blue trihydrate (MB), and a mixed aqueous solution of binary dyes CV and MB (binary feed solution). After the device was turned on, the system pressure was increased to 4 bar and the pressure was maintained for 30 minutes before the test was started. The absorbance of the dye molecules at the characteristic wavelength was detected by a UV-Vis spectrophotometer. The results are as follows. Figure 9 As shown;

[0097] Figure A shows the UV spectrum of the CB and MB single-component aqueous solutions, and Figure B shows the UV spectrum of the feed solution of the CV and MB binary dyes through the DTE@CB[7]-O membrane and the DTE@CB[7]-C membrane.

[0098] The figure shows that after the binary feed liquid of CV and MB passes through the DTE@CB[7]-O membrane and the DTE@CB[7]-C membrane, CV in the solution is retained on the membrane, while MB remains in the solution. This result confirms that the DTE@CB[7] membrane can achieve precise sieving of dye molecules with similar molecular weights.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a self-assembled photoresponsive membrane using molecular sieves, characterized in that, Includes the following steps: S100, prepare an aqueous solution containing supramolecular assemblies and an oil solution containing 1,3,5-benzenetricarboxyl chloride respectively; The structural formula of the supramolecular assembly is shown below: ； Among them, in the structural formula The chemical structural formula of cucurbituril is shown below: ； S200: After coating the aqueous solution onto the substrate surface, the oil solution is introduced, and a composite polyamide film is formed on the substrate surface by interfacial polymerization reaction. The structural formula of the monomer forming the composite polyamide film structure under visible light conditions is shown below: ； The structural formula of the monomer that forms the composite polyamide film structure under ultraviolet light is shown below: ； S300. The composite polyamide film is thermally crosslinked and cured to obtain a molecular sieve self-assembled photoresponsive film.

2. The method for preparing a self-assembled photoresponsive membrane using molecular sieves as described in claim 1, characterized in that, In step S100, the preparation of the aqueous solution containing the supramolecular assembly includes the following process: dissolving the dithiophene ethylene-based derivative in a mixed solvent of trifluoroethanol and N,N-dimethylacetamide, then adding the aqueous solution of the cucurbituril, mixing evenly, to obtain the aqueous solution containing the supramolecular assembly; The structural formula of the dithiophene ethylene-based derivative is shown below: 。 3. The method for preparing a self-assembled photoresponsive membrane using molecular sieves as described in claim 2, characterized in that, The volume ratio of trifluoroethanol to N,N-dimethylacetamide in the mixed solvent is 14:1 to 15:

1.

4. The method for preparing a self-assembled photoresponsive membrane using molecular sieves as described in claim 1, characterized in that, In step S100, the solvent of the oil phase solution containing 1,3,5-benzenetricarboxyl chloride is selected from n-hexane.

5. The method for preparing a self-assembled photoresponsive membrane using molecular sieves as described in claim 1, characterized in that, In step S200, after the oil phase solution is introduced, a settling process is included, and the settling time is 5 to 10 minutes.

6. The method for preparing a self-assembled photoresponsive membrane using molecular sieves as described in claim 1, characterized in that, In step S200, the substrate is selected from polyacrylonitrile substrate.

7. The method for preparing a self-assembled photoresponsive membrane using molecular sieves as described in claim 1, characterized in that, In step S200, the wavelength of the visible light is greater than 550nm, and the wavelength of the ultraviolet light is 310nm to 360nm.

8. A self-assembled photoresponsive membrane based on molecular sieves, characterized in that, It is prepared using the method for preparing a molecular sieve self-assembled photoresponsive membrane as described in any one of claims 1 to 7.

9. An application of a molecular sieve self-assembled photoresponsive membrane, characterized in that, Wastewater containing dye molecules is treated using the molecular sieve self-assembled photoresponsive membrane as described in claim 8.

10. The application of the molecular sieve self-assembled photoresponsive membrane as described in claim 9, characterized in that, The dye molecules include one or more of the following: methylene blue trihydrate, crystal violet, amaranth, Congo red, reactive black, and Alsin blue.

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