Responsive porous material, preparation method and application thereof, intelligent membrane and preparation method and application thereof

Abstract

The invention belongs to the technical field of intelligent materials, and particularly relates to a response type porous material, a preparation method and application thereof, an intelligent film and a preparation method and application thereof. The response type porous material is a long-range ordered crystalline porous material and is stable in structure, ordered response groups / fragments are arranged in an ion channel, an ordered molecular array is formed, ion transmission between an external stimulation signal and a response site is more efficient, and the response type porous material can be applied to the fields of acid-base, temperature, solvent, ion recognition and the like. And the charge density in the structure and the size of the nano-fluid channel are stimulated to change, so that excellent selectivity and permeability are achieved, ion flow in the ion channel can be intelligently adjusted, a fine ion transmission function equivalent to that of an organism is realized, ions are selectively transmitted, specific ions are rapidly conducted, and ion flow is responsively controlled.

Description

Technical Field

[0001] The present invention belongs to the technical field of smart materials, and specifically relates to a responsive porous material and a preparation method and application thereof, a smart membrane and a preparation method and application thereof. Background Art

[0002] Smart materials, also known as stimulus-responsive materials, are a type of material that can produce reversible, visible and tangible responses to external stimuli, such as mechanical stress, heat, light, gas, electricity, and pH. They are currently receiving widespread attention in many cutting-edge fields such as sensors, actuators, optoelectronic devices, information storage, and medical treatment. The key to the preparation of smart materials is to introduce responsive groups or parts into their structures, which can respond to external stimuli to perform chemical / physical changes.

[0003] At present, the design and construction of smart materials mainly focus on materials such as polymers, carbon materials and hydrogels. However, these materials have no ordered structure or only have a low-order structure (that is, the response group / part is disordered in the structure), which inevitably leads to defects such as relatively low response speed. Summary of the invention

[0004] The purpose of the present invention is to provide a responsive porous material and a preparation method and application thereof, a smart membrane and a preparation method and application thereof. The responsive porous material provided by the present invention has more efficient ion transmission and faster response speed.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a responsive porous material, the unit cell structure of which is shown in Formula I or Formula II; the responsive porous material contains a responsive group, and the responsive group includes at least one of a carboxyl group, a hydroxyl group and a nitrogen-containing heterocycle;

[0007]

[0008] In Formula I and Formula II, A is one of the structures shown in Formula A-1 to Formula A-10, and B is one of the structures shown in Formula B-1 to Formula B-14;

[0009]

[0010]

[0011] The present invention also provides a method for preparing the responsive porous material described in the above scheme, comprising the following steps:

[0012] Mixing the first monomer, the second monomer, the catalyst and the organic solvent for polycondensation to obtain the responsive porous material;

[0013] Alternatively, the first monomer, the second monomer and the catalyst are mixed with two-phase organic solvents to form a two-phase reaction solution to perform an interfacial polymerization reaction to obtain the responsive porous material;

[0014] The first monomer is one of the compounds represented by formula C-1 to formula C-10; the second monomer is one of the compounds represented by formula D-1 to formula D-14;

[0015]

[0016]

[0017] The present invention also provides the use of the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme in a stimulus-responsive device.

[0018] The present invention also provides a smart membrane, the components of which include the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme.

[0019] Preferably, the raw material of the smart membrane further includes a modified component; the modified component is a special engineering plastic; the special engineering plastic is modified polyethersulfone, and the structure of the modified polyethersulfone is shown in Formula III:

[0020]

[0021] In Formula III, m is 200 to 400, n is 200 to 400, and E is one of the structures of Formula E-1 and Formula E-2;

[0022]

[0023] Preferably, the preparation method of the modified polyethersulfone comprises the following steps: mixing a third monomer, a fourth monomer, a fifth monomer, a water-carrying agent, a catalyst and an organic solvent for polycondensation to obtain the modified polyethersulfone; the structure of the third monomer is shown in Formula F:

[0024]

[0025] The structure of the fourth monomer is shown in Formula G:

[0026]

[0027] The fifth monomer includes at least one of the monomers of formula H-1 and formula H-2:

[0028]

[0029] Preferably, the smart membrane further comprises a modified component membrane; the modified component membrane is prepared from a modified component; both sides of the modified component membrane are infiltrated with the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme.

[0030] The present invention also provides a method for preparing the smart membrane described in the above scheme, comprising the following steps:

[0031] The responsive porous material and the organic solvent are mixed, and then filtered and the solvent is removed in sequence to obtain the smart membrane;

[0032] Alternatively, the first monomer, the second monomer and the catalyst are mixed with two phases of organic solvents to form a two-phase reaction solution to perform an interfacial polymerization reaction to obtain the smart membrane;

[0033] Alternatively, the responsive porous material and the organic solvent are mixed, and then cast and the solvent is removed in sequence to obtain the smart membrane.

[0034] Preferably, when the smart membrane includes a modified component, the preparation method of the smart membrane is: (1) mixing the modified component with an organic solvent and then standing, filtering and drying in sequence to obtain a modified polyethersulfone membrane; (2) on both sides of the modified polyethersulfone membrane, independently mixing a first monomer, a second monomer, a catalyst and an organic solvent for a condensation reaction.

[0035] The present invention also provides the use of the smart membrane described in the above scheme or the smart membrane obtained by the preparation method described in the above scheme in an osmotic energy conversion and collection device.

[0036] The present invention provides a responsive porous material. The responsive porous material provided by the present invention is a long-range ordered crystalline porous material, which has a stable structure, an ordered response group / fragment inside the ion channel, and forms an ordered molecular array, so that the ion transmission between the external stimulus signal and the response site is more efficient, and the charge density inside the stimulus structure and the size of the nanofluid channel change in the acid-base, temperature, solvent and ion recognition scenes, and has excellent selectivity and permeability, and can intelligently regulate the ion flow in the ion channel, and realize the fine ion transmission function comparable to that of an organism, selectively transmit ions, quickly conduct specific ions, and responsively control the flow of ions; in addition, the clear structure helps to use various technologies and high-tech equipment, such as in-situ spectroscopy and single crystal / powder X-ray diffraction and other basic structural characterization methods, to in-situ characterize its structural transformation at the molecular level, so as to facilitate the study and understanding of the mechanism behind the stimulus response behavior and structure-property relationship, and finally realize the practical application of multi-scenario smart membranes in energy conversion or biochemical sensing and other fields.

[0037] The present invention also provides a method for preparing the responsive porous material described in the above scheme. The preparation method provided by the present invention has simple steps, and a more suitable preparation method can be selected according to specific circumstances, and has strong adaptability and low cost.

[0038] The present invention also provides the use of the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme in a stimulus-responsive device. The responsive porous material provided by the present invention has more efficient ion transmission, faster response speed, and stable structure, and is suitable for use in stimulus-responsive devices.

[0039] The present invention also provides a smart membrane. The smart membrane provided by the present invention has excellent selectivity and permeability, intelligently regulates ion flow in ion channels, realizes a fine ion transmission function comparable to that of organisms, selectively transmits ions, rapidly conducts specific ions, responsively controls ion flow, and has broad application prospects.

[0040] The present invention also provides a method for preparing the smart membrane of the above scheme. The preparation method provided by the present invention is easy to operate, safe, efficient and has good stability.

[0041] The present invention also provides the application of the smart membrane described in the above scheme or the smart membrane obtained by the preparation method described in the above scheme in an osmotic energy conversion and collection device. The present invention utilizes the designability of responsive porous materials to introduce responsive groups, such as acid-base responsive groups, temperature responsive groups, solvent responsive groups or ion recognition responsive groups, into the framework structure of responsive porous materials to obtain smart membranes for multiple scenarios. The smart membrane provided by the present invention can be effectively designed according to the needs of the scenario, changing the charge density of the ion transmission space and the size of the nanochannel to achieve excellent ion selectivity and permeability. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 The X-ray diffraction spectrum of the powder of the smart film prepared in Example 1;

[0044] Figure 2 This is the infrared spectrum of the smart film prepared in Example 1;

[0045] Figure 3 This is a scanning electron microscope surface image of the smart film prepared in Example 1;

[0046] Figure 4Thermogravimetric analysis spectrum of the smart membrane prepared in Example 1;

[0047] Figure 5 The X-ray diffraction spectrum of the powder of the smart film prepared in Example 2;

[0048] Figure 6 This is the infrared spectrum of the smart film prepared in Example 2;

[0049] Figure 7 This is a scanning electron microscope surface image of the smart film prepared in Example 2;

[0050] Figure 8 This is the thermogravimetric analysis spectrum of the smart membrane prepared in Example 2;

[0051] Fig. 9 The IV curve of the ion transport performance test of the smart membrane prepared in Example 1 in the same electrolyte solution;

[0052] Fig.10 A curve diagram showing the osmotic energy collected by the smart membrane prepared in Example 1 in an electrolyte solution with a concentration gradient of 50 times;

[0053] Fig.11 The open circuit voltage and short circuit current diagram of the smart membrane prepared in Example 1 in a multi-gradient pH environment;

[0054] Fig.12 The IV curve of the ion transport performance test of the smart membrane prepared in Example 2 in the same electrolyte solution;

[0055] Fig.13 A curve diagram showing the osmotic energy collected by the smart membrane prepared in Example 2 in an electrolyte solution with a concentration gradient of 50 times;

[0056] Fig.14 This is a graph of the ionic conductivity of the smart membrane prepared in Example 2 in a multi-gradient concentration methanol organic solvent environment. DETAILED DESCRIPTION

[0057] The present invention provides a responsive porous material, the unit cell structure of which is shown in Formula I or Formula II; the responsive porous material contains a responsive group, and the responsive group includes at least one of a carboxyl group, a hydroxyl group and a nitrogen-containing heterocycle;

[0058]

[0059] In Formula I and Formula II, A is one of the structures shown in Formula A-1 to Formula A-10, and B is one of the structures shown in Formula B-1 to Formula B-14;

[0060]

[0061]

[0062] In the present invention, when A in the responsive porous material of Formula I is a structure shown in Formula A-1, and B is a structure shown in Formula B-1, the pore structure unit of the responsive porous material (6 repeating units form a hexagonal macrocycle, with a topological design form of "C2+C3", C2 refers to two reactive sites on the monomer participating in the reaction, and C3 refers to three reactive sites on the monomer participating in the reaction, forming a pore structure unit) is as shown in Formula I-1:

[0063]

[0064] In the present invention, when A in the responsive porous material of Formula I is a structure shown in Formula A-2, and B is a structure shown in Formula B-1, the pore structure unit of the responsive porous material is as shown in Formula I-2:

[0065]

[0066] In the present invention, when A in the responsive porous material of Formula I is a structure shown in Formula A-3, and B is a structure shown in Formula B-1, the pore structure unit of the responsive porous material is as shown in Formula I-3:

[0067]

[0068] In the present invention, when A in the responsive porous material of Formula I is a structure shown in Formula A-4, and B is a structure shown in Formula B-1, the pore structure unit of the responsive porous material is as shown in Formula I-4:

[0069]

[0070] In the present invention, when A in the responsive porous material of formula II is a structure shown in formula A-5, and B is a structure shown in formula B-13, the three-dimensional structural unit of the responsive porous material (the four repeating units are not in the same plane, which is a three-dimensional COF-tetrahedron, and the body topology design form is "C2+C4", C2 refers to the monomer participating in the reaction containing two reactive sites, and C4 refers to the monomer participating in the reaction containing four reactive sites, forming a three-dimensional structural unit) is as shown in formula II-1:

[0071]

[0072] In the present invention, when A in the responsive porous material of formula II is a structure shown in formula A-5, and B is a structure shown in formula B-14, the three-dimensional structural unit of the responsive porous material is as shown in formula II-2:

[0073]

[0074] In the present invention, when A in the responsive porous material of formula II is a structure shown in formula A-6, and B is a structure shown in formula B-13, the three-dimensional structural unit of the responsive porous material is as shown in formula II-3:

[0075]

[0076] In the present invention, when A in the responsive porous material of formula II is a structure shown in formula A-6, and B is a structure shown in formula B-14, the three-dimensional structural unit of the responsive porous material is as shown in formula II-4:

[0077]

[0078] The responsive porous material provided by the present invention has inherent porosity, high specific surface area, high crystallinity and strong structural designability. The constructed ion channel can better realize the transmembrane transport of ions, reduce the internal resistance of the nanofluid device to a certain extent, and ensure the transmission of ions.

[0079] The present invention also provides a method for preparing the responsive porous material described in the above scheme, comprising the following steps:

[0080] Mixing the first monomer, the second monomer, the catalyst and the organic solvent for polycondensation to obtain the responsive porous material;

[0081] Or, the first monomer, the second monomer and the catalyst are mixed with two phases of organic solvents to form a two-phase reaction solution for interfacial polymerization, and the catalyst is not in the two-phase reaction solution at the same time, to obtain the responsive porous material;

[0082] The first monomer is one of the compounds represented by formula C-1 to formula C-10; the second monomer is one of the compounds represented by formula D-1 to formula D-14;

[0083]

[0084]

[0085] The first preparation method is single-phase preparation: the present invention mixes (referred to as the first mixture) the first monomer, the second monomer, the catalyst (referred to as the first catalyst) and the organic solvent (referred to as the first organic solvent) for polycondensation reaction (referred to as the first polycondensation reaction) to obtain the responsive porous material. In the present invention, the first monomer and the second monomer can be selected according to the structure of the target structure. Specifically, when the first monomer is a compound of formula A-1 and the second monomer is a compound of formula B-1, a responsive porous material of formula Ⅰ-1 is obtained; when the first monomer is a compound of formula A-2 and the second monomer is a compound of formula B-1, a responsive porous material of formula Ⅰ-2 is obtained; when the first monomer is a compound of formula A-3 and the second monomer is a compound of formula B-1, a responsive porous material of formula Ⅰ-3 is obtained; when the first monomer is a compound of formula A-4 and the second monomer is a compound of formula B-1, a responsive porous material of formula Ⅰ-4 is obtained; when the first monomer is a compound of formula A-5 and the second monomer is a compound of formula B-6, a responsive porous material of formula Ⅰ-7 is obtained. When one monomer is a compound of formula A-5 and the second monomer is a compound of formula B-13, a responsive porous material of formula II-1 is obtained; when the first monomer is a compound of formula A-5 and the second monomer is a compound of formula B-14, a responsive porous material of formula II-2 is obtained; when the first monomer is a compound of formula A-6 and the second monomer is a compound of formula B-13, a responsive porous material of formula II-3 is obtained; when the first monomer is a compound of formula A-6 and the second monomer is a compound of formula B-14, a responsive porous material of formula II-4 is obtained. The monomer combination method of the remaining responsive porous materials is the same as that of the above-mentioned responsive porous materials, and will not be repeated here one by one.

[0086] In the present invention, the molar ratio of the first monomer to the second monomer is preferably 0.8-1.4:0.8-1.4, specifically 0.8:0.8, 0.8:0.9, 0.8:1.1, 0.8:1.4, 0.9:0.8, 0.9:0.9, 0.9:1.1, 0.9:1.4, 1.1:0.8, 1.1:0.9, 1.1:1.1, 1.1:1.4, 1.4:0.8, 1.4:0.9, 1.1:1.1 or 1.4:1.4; when the first monomer carries a response group, the first monomer is added in excess, and when the second monomer carries a response group, the second monomer is added in excess; the first monomer or the second monomer is preferably added in excess of 1-20% of the standard addition amount. The present invention promotes the synthesis of the responsive porous material by controlling a certain monomer to be slightly excessive to ensure that another monomer (a monomer carrying a response group) fully reacts.

[0087] In the present invention, the first catalyst preferably includes one or more of an alkali metal organic salt and an organic acid; the alkali metal organic salt preferably includes sodium p-toluenesulfonate; and the organic acid preferably includes acetic acid.

[0088] In the present invention, the molar ratio of the total molar amount of the first monomer and the second monomer to the first catalyst is preferably 1:1-2, specifically 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1:2.

[0089] In the present invention, the first organic solvent is preferably a polar organic solvent; the polar organic solvent preferably includes one or more of nitrile, alcohol, ketone, ester, ether, amide solvent, oxygen heterocyclic solvent, furan solvent and substituted alkane; the nitrile is preferably acetonitrile; the alcohol preferably includes one or more of methanol, ethanol, propanol and n-butanol; the ketone is preferably acetone; the ester is preferably ethyl acetate; the ether is preferably ethyl ether; the amide solvent preferably includes one or two of N,N-dimethylformamide and N,N-dimethylacetamide; the oxygen heterocyclic solvent is preferably dioxane; the furan solvent is preferably tetrahydrofuran; the substituted alkane preferably includes one or more of substituted methane and trimethyltoluene; the substituted methane preferably includes one or two of dichloromethane and chloroform. The present invention adopts the above solvents to better dissolve the first monomer and the second monomer.

[0090] In the present invention, the first organic solvent is preferably subjected to anhydrous and oxygen-free treatment before use. The present invention avoids the reverse promotion of water on the polycondensation reaction by anhydrous and oxygen-free treatment, thereby reducing the influence on the polycondensation reaction.

[0091] In the present invention, the molar ratio of the total molar amount of the first monomer and the second monomer to the first organic solvent is preferably 0.01-0.05:1-5, specifically 0.01:1, 0.03:1, 0.05:1, 0.01:2, 0.03:2, 0.05:2, 0.01:3, 0.03:3, 0.05:3, 0.01:5, 0.03:5 or 0.05:5.

[0092] In the present invention, the first mixing is preferably performed in an inert atmosphere; the inert atmosphere is provided by an inert gas, and the inert gas is preferably argon.

[0093] In the present invention, the temperature of the first polycondensation reaction is preferably 25-180°C, specifically 25°C, 45°C, 65°C, 85°C, 100°C, 120°C, 150°C or 180°C, and the insulation reaction time is preferably 24-120h, specifically 24h, 48h, 72h, 80h, 96h or 120h; the first polycondensation reaction is preferably carried out in an inert atmosphere; the inert atmosphere is provided by an inert gas, and the inert gas is preferably argon.

[0094] In the present invention, after the first polycondensation reaction, the product obtained is preferably subjected to a first post-treatment; the first post-treatment is preferably: taking out the product obtained, soaking it, and then drying it.

[0095] In the present invention, the soaking reagent is preferably an organic soaking solvent, which can dissolve the first monomer and the second monomer, and does not dissolve the responsive porous material prepared by the present invention; the organic soaking solvent preferably includes soaking with N, N-dimethylformamide, acetonitrile, methanol and acetone in sequence; the number of times of soaking in a single solvent is preferably 1 to 6 times, specifically 3 times or 4 times; the time of a single soaking is preferably 6 to 18 hours, specifically 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours or 18 hours. The present invention performs solvent replacement by soaking to remove impurities such as unreacted monomers, small aggregates and particles.

[0096] In the present invention, the drying pressure is preferably normal pressure; the drying temperature is preferably 80-120°C, specifically 80°C, 90°C, 100°C, 110°C or 120°C; the drying insulation time is preferably 12-24h, specifically 12h, 15h, 18h, 21h or 24h.

[0097] The second preparation method is a two-phase preparation: the first monomer, the second monomer and the catalyst (referred to as the first catalyst) are respectively mixed with two-phase organic solvents to form a two-phase reaction liquid for interfacial polymerization, and the catalyst is not in the two-phase reaction liquid at the same time, to obtain the responsive porous material. In the present invention, the type and amount relationship of the first monomer, the second monomer and the catalyst, and the amount of the two-phase organic solvent (including the second organic solvent and the third organic solvent) are the same as those in the single-phase preparation method, and will not be repeated here.

[0098] In the present invention, the second organic solvent preferably includes one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide, trimethyltoluene, acetonitrile, acetonitrile aqueous solution and acetic acid aqueous solution; the third organic solvent preferably includes one or more of cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene and dichloromethane; the mass ratio of the second organic solvent to the third organic solvent is preferably 0.8-1.6:0.8-1.6, specifically 0.8:0.8, 0.8:1, 0.8:1.3, 0.8:1.6, 1:0.8, 1:1, 1:1.3, 1:1.6, 1.2:0.8, 1.2:1, 1.2:1.3, 1.2:1.6, 1.6:0.8, 1.6:1, 1.6:1.3 or 1.6:1.6.

[0099] In the present invention, the two-phase reaction liquid includes a first-phase reaction liquid and a second-phase reaction liquid; the molar ratio of the first monomer in the first-phase reaction liquid to the second monomer in the second-phase reaction liquid is preferably 0.6-1.2:0.6-1.2, specifically 0.6:0.6, 0.6:0.8, 0.6:1, 0.6:1.2, 0.8:0.6, 0.8:0.8, 0.8:1, 0.8:1.2, 1:0.6, 1:0.8, 1:1, 1:1.2, 1.2:0.6, 1.2:0.8 , 1.2:1 or 1.2:1.2; the molar ratio of the second monomer in the first phase reaction liquid to the first monomer in the second phase reaction liquid is preferably 0.6-1.2:0.6-1.2, specifically 0.6:0.6, 0.6:0.8, 0.6:1, 0.6:1.2, 0.8:0.6, 0.8:0.8, 0.8:1, 0.8:1.2, 1:0.6, 1:0.8, 1:1, 1:1.2, 1.2:0.6, 1.2:0.8, 1.2:1 or 1.2:1.2.

[0100] In the present invention, the reaction conditions and post-treatment of the interfacial polymerization reaction are the same as those of the single-phase preparation method, which will not be described in detail here. The difference is that the interfacial polymerization reaction is preferably carried out in an air atmosphere; after the two-phase reaction liquid is mixed to form a two-phase reaction liquid, a buffer layer is preferably set between the two-phase interfaces in the obtained system; the buffer layer preferably includes one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide, acetonitrile and water; the water is preferably deionized water. The present invention can reduce the interfacial reaction rate and improve the crystallinity of the material through the buffer layer.

[0101] The responsive porous materials provided by the present invention are all prepared by a one-step method, and the responsive groups carried by the materials do not need to be post-modified, thereby ensuring that the ion channels of the constructed responsive porous materials have responsive properties.

[0102] The present invention also provides the use of the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme in a stimulus-responsive device.

[0103] The present invention also provides a smart membrane, the components of which include the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme.

[0104] In the present invention, the raw material of the smart membrane preferably further includes a modified component; the modified component is preferably a special engineering plastic; the special engineering plastic is preferably modified polyethersulfone, and the structure of the modified polyethersulfone is shown in Formula III (m and n are the degree of polymerization):

[0105]

[0106] In Formula III, m is 200 to 400, n is 200 to 400, and E is one of the structures of Formula E-1 and Formula E-2;

[0107]

[0108] In the present invention, m in Formula III is preferably 250-350, and n is preferably 250-350.

[0109] In the present invention, the number average molecular weight of the polyethersulfone compound is preferably 30,000 to 80,000.

[0110] In the present invention, the modified polyethersulfone is preferably a compound of formula III-1, and the structure is shown in formula III-1:

[0111]

[0112] In the present invention, the preparation method of the modified polyether sulfone preferably includes the following steps: mixing (referred to as the second mixing, to obtain the second mixture) the third monomer, the fourth monomer, the fifth monomer, the water-carrying agent, the catalyst (referred to as the second catalyst) and the organic solvent (referred to as the fourth organic solvent) for polycondensation reaction (referred to as the second polycondensation reaction) to obtain the modified polyether sulfone.

[0113] In the present invention, the structure of the third monomer is shown in Formula F:

[0114]

[0115] In the present invention, the structure of the fourth monomer is shown in Formula G:

[0116]

[0117] In the present invention, the molar ratio of the third monomer to the fourth monomer is preferably 0.8-1.4:0.8-1.4, specifically 0.8:0.8, 0.8:1.0, 0.8:1.2, 0.8:1.4, 1.0:0.8, 1.0:1.0, 1.0:1.2, 1.0:1.4, 1.2:0.8, 1.2:1.0, 1.2:1.2, 1.2:1.4, 1.4:0.8, 1.4:1.0, 1.4:1.2 or 1.4:1.4.

[0118] In the present invention, the fifth monomer comprises at least one of the monomer of formula H-1 and the monomer of formula H-2, preferably the monomer of formula H-1:

[0119]

[0120] In the present invention, the molar ratio of the fourth monomer to the fifth monomer is preferably 0.8-1.4:0.8-1.4, specifically 0.8:0.8, 0.8:1.0, 0.8:1.2, 0.8:1.4, 1.0:0.8, 1.0:1.0, 1.0:1.2, 1.0:1.4, 1.2:0.8, 1.2:1.0, 1.2:1.2, 1.2:1.4, 1.4:0.8, 1.4:1.0, 1.4:1.2 or 1.4:1.4.

[0121] In the present invention, the water-carrying agent is preferably a benzene homologue; and the benzene homologue is preferably toluene.

[0122] In the present invention, the molar ratio of the third monomer to the water-carrying agent is preferably 0.01-0.05:1-2, specifically 0.01:1, 0.01:1.5, 0.01:2, 0.02:1, 0.02:1.5, 0.02:2, 0.03:1, 0.03:1.5, 0.03:2, 0.04:1, 0.04:1.5, 0.04:2, 0.05:1, 0.05:1.5 or 0.05:2.

[0123] In the present invention, the second catalyst is preferably an alkali metal inorganic salt; the alkali metal inorganic salt preferably includes one or more of potassium carbonate, sodium carbonate, potassium chloride and sodium chloride.

[0124] In the present invention, the molar ratio of the third monomer to the second catalyst is preferably 1:1.3-1.5, specifically 1:1.3, 1:1.35, 1:1.4, 1:1.45 or 1:1.5.

[0125] In the present invention, the fourth organic solvent preferably includes one or more of sulfolane, N,N-dimethylformamide and N,N-dimethylacetamide.

[0126] In the present invention, the mass ratio of the third monomer to the fourth organic solvent is preferably 0.01-0.05:1-5, specifically 0.01:1, 0.01:2, 0.01:3, 0.01:5, 0.03:1, 0.03:2, 0.03:3, 0.03:5, 0.05:1, 0.05:2, 0.05:3 or 0.05:5.

[0127] In the present invention, the second polycondensation reaction is preferably carried out under reflux conditions; the temperature of the second polycondensation reaction is preferably 175-185°C, specifically 180°C, and the insulation reaction time is preferably 5-20h, specifically 10h or 15h.

[0128] In the present invention, the second mixed solution is preferably dehydrated before the second polycondensation reaction; the dehydration temperature is preferably 145° C. In the dehydration process of the present invention, the water-carrying agent completely removes the water in the system.

[0129] In the present invention, after the second polycondensation reaction, the obtained reaction liquid is preferably subjected to a second post-treatment; the second post-treatment preferably includes: sequentially subjecting the obtained reaction liquid to precipitation, solid-liquid separation, pulverization, washing and drying.

[0130] In the present invention, the precipitation is preferably carried out in water; the water is preferably deionized water; the solid-liquid separation is preferably filtration; the washing preferably includes water washing and alcohol washing in sequence; the water used for the water washing is preferably boiling water; the alcohol used for the alcohol washing is preferably ethanol; the drying is preferably vacuum drying; the drying temperature is preferably 120°C, and the heat preservation and drying time is preferably 48h.

[0131] The modified polyethersulfone used in the present invention has only two modification methods, namely, carboxyl and amino groups, which can better form covalent bonds or strengthen with the responsive porous material, thereby ensuring that the constructed membrane structure is better suitable for work in multiple scenarios.

[0132] In the present invention, when the smart membrane preferably also includes a modifying component, the modifying component is preferably present in the form of a modified component membrane, and the modified component membrane is prepared from the modified component; both sides of the modified component membrane are infiltrated with the responsive porous material described in the above scheme or the responsive porous material obtained by the preparation method described in the above scheme; the thickness of the smart membrane is preferably 1 to 10 μm, specifically 1 μm, 3 μm, 5 μm, 7 μm or 10 μm; the pore size of the smart membrane is preferably 50 to 200 nm, specifically 50 nm, 80 nm, 100 nm, 150 nm or 200 nm.

[0133] In the present invention, the thickness of the smart film is preferably 0.1-10 μm, specifically 0.1 μm, 0.3 μm, 0.5 μm, 0.7 μm, 1 μm, 3 μm, 5 μm, 7 μm or 10 μm.

[0134] In the present invention, the pore size of the smart membrane is preferably 0.3-2.5 nm, specifically 0.3 nm, 0.6 nm, 0.8 nm, 1 nm, 1.3 nm, 1.6 nm, 2 nm, 2.3 nm or 2.5 nm.

[0135] In the present invention, the ion flux of the smart membrane is preferably 1-20 S / cm. The smart membrane of the present invention allows cations and anions to pass through, only anions pass through when the carboxyl group is modified, and only cations pass through when the amino group is modified, has excellent ion selectivity, and high water and ion flux.

[0136] The present invention also provides a method for preparing the smart membrane described in the above scheme, comprising the following steps:

[0137] The responsive porous material and the organic solvent are mixed, filtered and desolventized in sequence to obtain the smart membrane;

[0138] Alternatively, the first monomer, the second monomer and the catalyst are mixed with two phases of organic solvents to form a two-phase reaction solution to perform an interfacial polymerization reaction to obtain the smart membrane;

[0139] Alternatively, the responsive porous material and the organic solvent are mixed, and then cast and the solvent is removed in sequence to obtain the smart membrane.

[0140] First, the present invention mixes the responsive porous material and the organic solvent (referred to as the fifth organic solvent) (referred to as the third mixing), and then successively filters and removes the solvent (referred to as the first solvent removal) to obtain the smart membrane. In the present invention, the fifth organic solvent preferably includes one or more of sulfolane, N,N-dimethylformamide and N,N-dimethylacetamide.

[0141] In the present invention, the mass ratio of the responsive porous material to the fifth organic solvent is preferably 0.01-0.05:1-5, specifically 0.01:1, 0.01:2, 0.01:3, 0.01:5, 0.03:1, 0.03:2, 0.03:3, 0.03:5, 0.05:1, 0.05:2, 0.05:3 or 0.05:5.

[0142] In the present invention, the third mixing is preferably stirring mixing; the raw materials of the third mixing preferably also include a modified component; the modified component is preferably a special engineering plastic; the special engineering plastic is preferably modified polyethersulfone, and the structure of the modified polyethersulfone is shown in Formula III; the molar ratio of the responsive porous material and the modified component is preferably 1 to 5:1 to 5, specifically 1:1, 1:2, 1:3, 1:4, 1:5, 3:1, 3:2, 3:3, 3:4, 3:5, 5:1, 5:2, 5:3, 5:4 or 5:5; when the raw materials of the third mixing also include a modified component, the fifth organic solvent preferably includes one or more of cyclopentane sulfone, N,N-dimethylformamide and N,N-dimethylacetamide. The present invention introduces modified polyethersulfone to target more extreme application scenarios, such as high-salinity electrolytes, high-temperature electrolytes, ultra-large application areas, and ultra-high mechanical strength scenarios, so that the responsive porous material and the modified polyethersulfone work together to form an intelligent membrane that is easy to prepare on a large scale, commercially produced, and has a high use value, which can better perform stable, long-term, and efficient osmotic energy conversion and collection in multiple scenarios.

[0143] In the present invention, the filtration is preferably vacuum filtration; the equipment for the vacuum filtration is preferably a vacuum pump; the vacuum degree of the vacuum filtration is preferably 0.05-0.1MPa, specifically 0.05MPa, 0.07MPa, 0.09MPa or 0.1MPa.

[0144] In the present invention, the first solvent removal is preferably heated; the heating temperature is preferably 60-150° C., specifically 60° C., 80° C., 100° C., 120° C. or 150° C. In the present invention, the solvent is volatilized by heating.

[0145] In the present invention, after the first solvent removal, it is preferred that the solvent of the obtained membrane product be replaced; the solvent replacement is preferably solvent immersion; the solvent used for the solvent immersion preferably includes one or more of N,N-dimethylformamide, acetonitrile, methanol and acetone; the time for the solvent immersion is preferably 8 to 12 hours, specifically 10 hours.

[0146] In the present invention, the first solvent removal preferably includes peeling the obtained product. The present invention obtains a defect-free, crack-free, flexible, and independent smart film through the above preparation.

[0147] Second, the present invention mixes the first monomer, the second monomer and the catalyst with two-phase organic solvents respectively (recorded as the fourth mixture) to form a two-phase reaction liquid for interfacial polymerization to obtain the smart membrane. In the present invention, the two-phase organic solvent includes a sixth organic solvent and a seventh organic solvent; the sixth organic solvent preferably includes one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide, acetonitrile, acetonitrile aqueous solution and acetic acid aqueous solution; the seventh organic solvent preferably includes one or more of cyclohexane, trimethyltoluene, cyclohexanone, toluenecyclohexanone, chlorobenzene, dichlorobenzene and dichloromethane.

[0148] In the present invention, the mass ratio of the total mass of the first monomer and the second monomer to the sixth organic solvent is preferably 0.01-0.05:1-5, specifically 0.01:1, 0.01:2, 0.01:3, 0.01:5, 0.03:1, 0.03:2, 0.03:3, 0.03:5, 0.05:1, 0.05:2, 0.05:3 or 0.05:5; the mass ratio of the total mass of the first monomer and the second monomer to the seventh organic solvent is preferably 0.01-0.05:1-5, specifically 0.01:1, 0.01:2, 0.01:3, 0.01:5, 0.03:1, 0.03:2, 0.03:3, 0.03:5, 0.05:1, 0.05:2, 0.05:3 or 0.05:5.

[0149] In the present invention, the fourth mixing is preferably stirring mixing; the raw materials of the fourth mixing preferably also include a modifying component; the modifying component is preferably a special engineering plastic; the special engineering plastic is preferably modified polyethersulfone, and the structure of the modified polyethersulfone is shown in Formula III; the molar ratio of the total molar number of the first monomer and the second monomer to the modifying component is preferably 1-5:1-5, specifically 1:1, 1:2, 1:3, 1:4, 1:5, 3:1, 3:2, 3:3, 3:4, 3:5, 5:1, 5:2, 5:3, 5:4 or 5:5; when the raw materials of the fourth mixing also include a modifying component, the sixth organic solvent preferably includes one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide and acetonitrile, and the seventh organic solvent preferably includes one or more of cyclohexane, cyclohexanone, toluenecyclohexanone, chlorobenzene, dichlorobenzene and dichloromethane.

[0150] In the present invention, the temperature of the interfacial polymerization reaction is preferably 25-120°C, specifically 25°C, 45°C, 75°C, 100°C or 120°C, and the insulation reaction time is preferably 12-96h, specifically 12h, 24h, 36h, 48h, 72h or 96h.

[0151] In the present invention, other preparation parameters of the smart membrane are preferably the same as those of the interfacial polymerization preparation method of the responsive porous material, and will not be described in detail herein.

[0152] Thirdly, the present invention mixes the responsive porous material and the organic solvent (referred to as the eighth organic solvent) (referred to as the fifth mixing), and then sequentially casts and removes the solvent (referred to as the second solvent removal) to obtain the smart membrane. In the present invention, the eighth organic solvent preferably includes one or more of methyl butyl ketone, N,N-dimethylformamide and acetonitrile.

[0153] In the present invention, the mass ratio of the responsive porous material to the eighth organic solvent is preferably 0.1-0.5:1-5, specifically 0.1:1, 0.1:2, 0.1:3, 0.1:5, 0.3:1, 0.3:2, 0.3:3, 0.3:5, 0.5:1, 0.5:2, 0.5:3 or 0.5:5.

[0154] In the present invention, the fifth mixing is preferably stirring mixing; the raw materials of the fifth mixing preferably also include a modified component; the modified component is preferably a special engineering plastic; the special engineering plastic is preferably modified polyethersulfone, and the structure of the modified polyethersulfone is shown in Formula III; the molar ratio of the responsive porous material and the modified component is preferably 0.1-0.5:1-5, specifically 0.1:1, 0.1:2, 0.1:3, 0.1:5, 0.3:1, 0.3:2, 0.3:3, 0.3:5, 0.4:1, 0.4:2, 0.4:3 or 0.4:5, 0.5:1, 0.5:2, 0.5:3 or 0.5:5; when the raw materials of the fifth mixing also include a modified component, the eighth organic solvent preferably includes one or more of cyclobutane sulfone, N,N-dimethylformamide and N,N-dimethylacetamide.

[0155] In the present invention, the pouring volume of the pouring is preferably 0.03 to 0.50 mL / cm 2 , specifically 0.03mL / cm 2 , 0.05mL / cm 2 , 0.1mL / cm 2 , 0.2mL / cm 2 , 0.3mL / cm 2 , 0.4mL / cm 2 or 0.5mL / cm 2 .

[0156] In the present invention, the second solvent removal is preferably carried out on the cast substrate; the second solvent removal is preferably heated; the heating temperature is preferably 60 to 150° C., specifically 60° C., 80° C., 100° C., 120° C. or 150° C. In the present invention, the solvent is volatilized by heating.

[0157] In the present invention, the second solvent removal preferably also includes replacing the solvent of the obtained membrane product; the solvent replacement is preferably solvent immersion; the solvent used for the solvent immersion preferably includes one or more of N,N-dimethylformamide, acetonitrile, methanol and acetone; the time of the solvent immersion is preferably 8 to 12 hours, specifically 10 hours.

[0158] In the present invention, when the smart membrane includes a modified component, the preparation method of the smart membrane preferably includes the following steps: (1) mixing the modified component with an organic solvent (referred to as the ninth organic solvent) (referred to as the sixth mixing), and then filtering and removing the solvent (referred to as the third solvent removal) in sequence to obtain a modified polyethersulfone membrane; (2) on both sides of the modified polyethersulfone membrane, independently mixing the first monomer, the second monomer, the catalyst and the organic solvent for a condensation reaction.

[0159] In the present invention, the ninth organic solvent preferably includes one or more of methyl butyl ketone, N,N-dimethylformamide and acetonitrile.

[0160] In the present invention, the mass ratio of the modified component to the ninth organic solvent is preferably 0.1-0.5:1-5, specifically 0.1:1, 0.1:2, 0.1:3, 0.1:5, 0.3:1, 0.3:2, 0.3:3, 0.3:5, 0.4:1, 0.4:2, 0.4:3 or 0.4:5, 0.5:1, 0.5:2, 0.5:3 or 0.5:5.

[0161] In the present invention, the temperature of the sixth mixing is preferably 60-150° C., specifically 60° C., 90° C., 120° C. or 150° C., and the time is preferably 0.5-3 h, specifically 1 h or 2 h.

[0162] In the present invention, the filtration is preferably suction filtration; the filter head used for the suction filtration is preferably an organic filter head; the equipment for the suction filtration is preferably a vacuum pump; the vacuum degree of the suction filtration is preferably 0.05-0.1MPa, specifically 0.05MPa, 0.07MPa, 0.09MPa or 0.1MPa. The present invention reduces the undissolved monomers or particles in the subsequent membrane through filtration, which reduces the separation effect of the membrane.

[0163] In the present invention, the temperature of the third solvent removal is preferably 50-150°C, specifically 50°C, 70°C, 90°C, 110°C, 120°C or 150°C, and the time is preferably 12-36h, specifically 24h.

[0164] In the present invention, the reaction conditions of step (2) are preferably the same as those of the preparation method of the responsive porous material, which will not be described in detail herein. The responsive porous material provided by the present invention can cooperate with the modified special engineering material to form an intelligent membrane that is easy to prepare on a large scale, commercially produced, and has a high use value.

[0165] The present invention also provides the use of the smart membrane described in the above scheme or the smart membrane obtained by the preparation method described in the above scheme in an osmotic energy conversion and collection device.

[0166] The present invention utilizes the designability of responsive porous materials, introduces response groups such as acid-base, temperature, solvent or ion recognition into the framework structure of responsive porous materials, and obtains smart membranes for multiple scenarios: in the acid-base environment stimulus response, the charge density inside the ion channel can be fully regulated, so that the ion channel has a certain ion selectivity, and the selectivity can change with the change of environmental acid-base; in the temperature environment stimulus response, the rate of ion transmembrane transport will be affected, the viscosity of the electrolyte solution decreases with the increase of temperature, and the rate of ion transmission inside the nanochannel increases, while increasing the permeability, it also increases the selectivity to a certain extent; in the solvent environment stimulus response, in the C4 structure of the responsive porous material of the present invention, the polarity of different solvents can change the elasticity of the structure, change the size of the ion transmission space, and thus affect the ion transmission performance; for different ion environment stimulus responses, designing specific identification porous materials is a particularly important link, and by identifying specific ions, the corresponding electrochemical signal output is obtained. The smart membrane provided by the present invention can be effectively designed according to the needs of the scene, changing the charge density and nanochannel size of the ion transmission space, and achieving excellent ion selectivity and permeability.

[0167] In the present invention, the acid-base environment is preferably a strong oxidizing acid and a strong oxidizing base; the strong oxidizing acid is preferably hydrochloric acid; the strong oxidizing base is preferably sodium hydroxide; the pH value of the acid-base environment is preferably 1 to 14, specifically 4 or 10.

[0168] In the present invention, the temperature of the temperature environment is preferably 0-100° C., specifically 25° C. or 85° C.; the temperature environment is the environment where the device is located, specifically an electrolyte solution.

[0169] In the present invention, the solvent in the solvent environment is preferably a polar solvent, more preferably a polar organic solvent; the polar organic solvent preferably includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, methanol, ethanol, propanol, acetone, dioxane and tetrahydrofuran, more preferably acetonitrile, methanol, acetone and tetrahydrofuran.

[0170] In the present invention, the ions in the ionic environment are preferably one or more of transition metal ions and alkali metal ions, more preferably alkali metal ions; the alkali metal ions preferably include one or more of lithium ions, sodium ions, potassium ions, magnesium ions and calcium ions.

[0171] In the present invention, the osmotic energy conversion and collection device is preferably a salt difference power generation device. The present invention has no special requirements for the specific method of the application, and a method well known to those skilled in the art can be used.

[0172] In the present invention, the salt difference power generation device preferably comprises a double-chamber electrolytic cell, double electrodes and a picoammeter connected to the double electrodes; the smart membrane is placed in the double-chamber electrolytic cell.

[0173] In the present invention, the preparation method of the salt difference power generation device is preferably: placing the smart membrane in a double-chamber electrolytic cell, adding electrolytes of different concentrations into the two electrolytic chambers of the double-chamber electrolytic cell respectively, then inserting double electrodes, and connecting the double electrodes to a picoammeter.

[0174] In the present invention, the electrodes of the dual electrode preferably include a silver / silver chloride electrode, a saturated calomel electrode, a graphite (C) electrode, a platinum (Pt) electrode or a copper electrode.

[0175] In the present invention, the electrolyte is preferably a sodium chloride aqueous solution or a potassium chloride aqueous solution, more preferably a potassium chloride aqueous solution; the concentration of the electrolyte is preferably 1 to 10000 mmol / L, specifically 5 mmol / L, 10 mmol / L, 50 mmol / L, 100 mmol / L, 500 mmol / L, 1000 mmol / L or 5000 mmol / L.

[0176] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0177] Example 1

[0178] This embodiment provides a pH-responsive smart membrane prepared from a responsive porous material of Formula I-1. This embodiment uses an interfacial polymerization reaction to prepare the smart membrane. The specific steps are as follows:

[0179] 2,4,6-Triformylphloroglucinol (4.20 mg, 0.02 mmol) was dissolved in dichloromethane (100 mL) and placed at the bottom of a 300 mL beaker to obtain a first phase solution.

[0180] 2,2'-Bipyridine-5,5'-diamine (5.60 mg, 0.03 mmol) and sodium p-toluenesulfonate (11.40 mg, 0.06 mmol) were dissolved in acetonitrile and deionized water (30 mL of acetonitrile / 70 mL of deionized water), and acetic acid (20 μL) was added to obtain a second phase solution.

[0181] The above two-phase solution was stirred for 30 minutes, and the interfacial reaction system was placed in a beaker (300 mL); acetonitrile and deionized water (18 mL of acetonitrile / 42 mL of deionized water) were added between the two-phase interface as a buffer layer; after adding the above components, the reaction was carried out at room temperature (25°C) for 96 hours, and the two-phase solution was removed after the reaction. The product was sequentially soaked in N,N-dimethylformamide, acetonitrile, methanol and acetone for solvent replacement. Each solvent was replaced 3 times, each soaking for 12 hours, and dried at 100°C for 18 hours to obtain a smart membrane, which was recorded as TB-COF (2DCOF).

[0182] The powder of the smart film prepared in Example 1 was subjected to X-ray diffraction analysis, and the results were as follows: Figure 1 As shown. Figure 1 It can be seen that the present invention obtains a good crystalline porous material with strong crystallinity.

[0183] The smart film prepared in Example 1 was subjected to infrared analysis, and the results were as follows: Figure 2 As shown. Figure 2 It can be seen that the characteristic peak of the monomer disappears and the TB-COF smart membrane is successfully prepared.

[0184] The surface of the smart membrane prepared in Example 1 was tested by scanning electron microscope. The results are as follows: Figure 3 As shown. Figure 3 It can be seen that there are no obvious defects or cracks on the surface, which proves that the present invention can obtain an independent and complete membrane structure through interfacial polymerization.

[0185] Thermogravimetric analysis of the smart membrane prepared in Example 1 showed the following results: Figure 4 As shown. Figure 4 It can be seen that the smart membrane frame decomposes at 400°C, which proves that the smart membrane has good thermal stability.

[0186] Example 2

[0187] This embodiment provides a solvent-responsive smart membrane prepared from a responsive porous material of formula II-1. This embodiment uses interfacial polymerization to prepare the smart membrane. The specific steps are as follows:

[0188] Tetrakis(4-aminophenyl)methane (TAM, 80 mg) was dissolved in 20 mL of aqueous acetic acid solution (6.4 mL of 36 wt% acetic acid + 13.6 mL of deionized water) to obtain a lower aqueous phase.

[0189] Terephthalaldehyde (TPAL, 48 mg) was dissolved in 8 mL of trimethyltoluene to obtain an upper organic phase.

[0190] 5 mL of acetic acid aqueous solution was added between the two phases as a buffer layer. After adding the above components, the reaction was carried out at room temperature (25°C) for 96 hours to form a COF membrane at the interface. After the reaction, the two-phase solution was removed, and the product was solvent replaced with N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence. Each solvent was replaced 3 times, each time soaking for 12 hours, and dried at 100°C for 18 hours to obtain a smart membrane, which was recorded as COF-300 (3D COF).

[0191] The powder of the smart film prepared in Example 2 was subjected to X-ray diffraction analysis, and the results were as follows: Figure 5 As shown. Figure 5 It can be seen that the present invention obtains a good crystalline porous material with strong crystallinity.

[0192] The infrared analysis of the smart film prepared in Example 2 showed the following results: Figure 6 As shown. Figure 6 It can be seen that the characteristic peak of the monomer disappears and new bonds of COF appear, proving that the material was successfully prepared.

[0193] The surface of the smart membrane prepared in Example 2 was tested by scanning electron microscope. The results are as follows: Figure 7 As shown. Figure 7 It can be seen that the present invention can obtain an independent and complete membrane structure through interfacial polymerization.

[0194] Thermogravimetric analysis of the smart membrane prepared in Example 2 showed the following results: Figure 8 As shown. Figure 8 It can be seen that the smart membrane frame decomposes at 500°C, which proves that the smart membrane has good thermal stability.

[0195] Example 3

[0196] This embodiment provides a carboxylic acid-modified polyethersulfone polymer of formula III-1, and the specific steps of the preparation method are as follows:

[0197] In an anhydrous and oxygen-free environment, under the protection of argon, 40.0mmol (10.18g) of 4,4'-difluorodiphenyl sulfone, 32.0mmol (5.96g) of 4,4'-dihydroxybiphenyl, 30.0mmol (9.00g) of 4,4'-dihydroxydibenzoic acid, 8.0g of potassium carbonate, 28mL of toluene and 60mL of cyclopentane sulfone were added into a three-necked flask, and the obtained mixed system was heated to 145°C under stirring and refluxed for 4h. During the reaction, toluene will fully remove the water generated in the system; The obtained system was then heated to 180°C for reaction for 9 hours. After the reaction was completed, it could be clearly observed that the viscosity of the product system no longer changed. The obtained product system was poured into deionized water to precipitate solid material, which was filtered through a membrane filter. The obtained solid material was crushed and washed 3 times with boiling water in a single-necked flask and then washed 3 times with ethanol. After washing, it was vacuum dried at 120°C to constant weight to obtain a carboxylic acid-modified polyethersulfone compound of formula III-1 with a logarithmic viscosity of 0.87, a number average molecular weight of 112.8 kDa, and a dispersity index of 1.4.

[0198] Example 4

[0199] This embodiment provides a smart membrane constructed of a responsive porous material of Formula I-1 and a carboxylic acid-modified polyethersulfone polymer of Formula III-1. The specific steps of the preparation method are as follows:

[0200] 6.250 mg of the carboxylic acid modified polyethersulfone polymer prepared in Example 3 was mixed with 10 mL of N,N-dimethylformamide, and ultrasonicated at room temperature (25°C) for 1 hour. After ultrasonication, the resulting mixed system was allowed to stand for 1 hour, and the supernatant was taken with a dropper and poured into a filter bottle. The supernatant was then filtered through an organic filter membrane, and the filter membrane with the carboxylic acid modified polyethersulfone membrane was then placed under vacuum conditions at 50°C and dried for 24 hours to obtain a modified polyethersulfone membrane.

[0201] The modified polyethersulfone membrane was placed in the middle of an H-shaped test tube. The reaction conditions of the smart membrane prepared in Example 1 were referred to in the electrolytic cells on both sides. 2,4,6-triformylphloroglucinol (2.10 mg, 0.01 mmol) was dissolved in dichloromethane (50 mL) and placed on the left side of the H-shaped test tube; 2,2'-bipyridine-5,5'-diamine (2.80 mg, 0.015 mmol) and sodium p-toluenesulfonate (5.70 mg, 0.03 mmol) were dissolved in acetonitrile and deionized water. (15 mL of acetonitrile / 35 mL of deionized water), acetic acid (10 μL) was added at the same time, and placed on the right side of the H-type test tube; after adding the above components, the reaction was carried out at room temperature for 96 hours, and the monomers on both sides diffused into a membrane in the modified polyethersulfone membrane; after the reaction, the two-phase solution was removed, and the solvents were replaced by soaking with N,N-dimethylformamide, acetonitrile, methanol and acetone in turn. Each solvent was replaced 3 times, each time soaking for 12 hours, and dried at 100°C for 18 hours to obtain a smart membrane, which was recorded as TB-COF@COOH-PES.

[0202] Example 5

[0203] This embodiment provides a smart membrane constructed of a responsive porous material of Formula II-1 and a carboxylic acid-modified polyethersulfone polymer of Formula III-1. The specific steps of the preparation method are as follows:

[0204] 6.250 mg of the carboxylic acid-modified polyethersulfone polymer prepared in Example 3 was mixed with 10 mL of N,N-dimethylformamide, and ultrasonicated at 75°C for 1 h. After ultrasonication, the resulting mixed system was allowed to stand for 1 h to observe the dissolution of the polymer. The supernatant was taken with a dropper and filtered through an organic filter membrane to obtain a carboxylic acid-modified polyethersulfone polymer solution for standby use.

[0205] The COF-300 smart membrane prepared in Example 2 was subjected to solvent replacement using N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence, and each solvent was replaced 3 times, and each soaking was 12 hours. The COF-300 smart membrane was ground to obtain fine COF-300 smart membrane powder, which was fully stirred and mixed with the above-mentioned carboxylic acid-modified polyethersulfone polymer solution to be used. The COF-300 smart membrane powder and the carboxylic acid-modified polyethersulfone polymer solution were mixed and cast on a flat glass, and dried under vacuum conditions at 50°C for 24 hours to obtain a smart membrane, which was recorded as COF-300@COOH-PES.

[0206] Example 6

[0207] This embodiment provides a pH-responsive smart membrane prepared from a responsive porous material of a combination of Formula A-1 and Formula B-10. This embodiment uses an interfacial polymerization reaction to prepare the smart membrane. The specific steps are as follows:

[0208] 2,4,6-Triformylphloroglucinol (TP, 4.20 mg, 0.02 mmol) was dissolved in dichloromethane (500 mL) and placed at the bottom of a 200 mL beaker to obtain a first phase solution.

[0209] 2,5-Diaminoterephthalic acid (DA, 5.90 mg, 0.03 mmol) was dissolved in acetonitrile and deionized water (acetonitrile 15 mL / deionized water 30 mL), and acetic acid (10 μL) was added to obtain a second phase solution.

[0210] 5 mL of acetic acid aqueous solution was added between the two phase interfaces as a buffer layer. After adding the above components, the mixture was reacted at 50°C for 48 hours to form a COF membrane at the interface. After the reaction, the two phase solutions were removed and the product was solvent replaced with N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence. Each solvent was replaced 3 times, each time with immersion for 12 hours and drying at 100°C for 18 hours to obtain a smart membrane, which was recorded as TPDA-COF (2D COF).

[0211] Example 7

[0212] This embodiment provides a pH-responsive smart membrane prepared from a responsive porous material of a combination of Formula A-1 and Formula B-11. This embodiment uses an interfacial polymerization reaction to prepare the smart membrane. The specific steps are as follows:

[0213] 2,4,6-Triformylphloroglucinol (TP, 4.20 mg, 0.02 mmol) was dissolved in dichloromethane (500 mL) and placed at the bottom of a 200 mL beaker to obtain a first phase solution.

[0214] 1,2,4,5-Benzenetetramine tetrahydrochloride (TB, 8.52 mg, 0.03 mmol) was dissolved in acetonitrile and deionized water (acetonitrile 15 mL / deionized water 30 mL) to obtain a second phase solution.

[0215] 5 mL of acetic acid aqueous solution was added between the two phase interfaces as a buffer layer. After adding the above components, the mixture was reacted at 50°C for 48 hours to form a COF membrane at the interface. After the reaction, the two phase solutions were removed and the product was solvent replaced with N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence. Each solvent was replaced 3 times, each time with immersion for 12 hours and drying at 100°C for 18 hours to obtain a smart membrane, which was recorded as TPTB-COF (2D COF).

[0216] Example 8

[0217] This embodiment provides a temperature-responsive smart membrane prepared from a responsive porous material of a combination of Formula A-1 and Formula B-12. This embodiment uses an interfacial polymerization reaction to prepare the smart membrane. The specific steps are as follows:

[0218] 2,4,6-Triformylphloroglucinol (TP, 4.20 mg, 0.02 mmol) was dissolved in dichloromethane (500 mL) and placed at the bottom of a 200 mL beaker to obtain a first phase solution.

[0219] p-phenylenediamine (PD, 3.00 mg, 0.03 mmol) was dissolved in acetonitrile and deionized water (acetonitrile 15 mL / deionized water 30 mL), and acetic acid (10 μL) was added to obtain a second phase solution.

[0220] 5 mL of acetic acid aqueous solution was added between the two phase interfaces as a buffer layer. After adding the above components, the reaction was carried out at room temperature for 48 hours to form a COF membrane at the interface. After the reaction, the two-phase solution was removed, and the product was solvent replaced with N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence. Each solvent was replaced 3 times, each time soaking for 12 hours, and dried at 100°C for 18 hours to obtain a smart membrane, which was recorded as TPPD-COF (2D COF).

[0221] Example 9

[0222] This example provides a smart membrane constructed by the responsive porous material prepared in Example 6 and the carboxylic acid-modified polyethersulfone polymer of formula III-1. The specific steps of the preparation method are as follows:

[0223] 6.250 mg of the carboxylic acid-modified polyethersulfone polymer prepared in Example 3 was mixed with 10 mL of N,N-dimethylformamide, and ultrasonicated at 75° C. for 1 h. After ultrasonication, the resulting mixed system was allowed to stand for 1 h. The supernatant was taken with a dropper and filtered through an organic filter membrane to obtain a carboxylic acid-modified polyethersulfone polymer solution for standby use.

[0224] The TPDA-COF smart membrane prepared in Example 6 was subjected to solvent replacement using N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence, and each solvent was replaced 3 times, and each soaking was 12 hours. The COF-300 smart membrane was ground to obtain fine TPDA-COF smart membrane powder, which was fully stirred and mixed with the above-mentioned carboxylic acid modified polyethersulfone polymer solution to be used. The TPDA-COF smart membrane powder and the carboxylic acid modified polyethersulfone polymer solution were mixed and cast on a flat glass, and dried under vacuum conditions at 50°C for 24 hours to obtain a smart membrane, which was recorded as TPDA-COF@COOH-PES.

[0225] Example 10

[0226] This example provides a smart membrane constructed by the responsive porous material prepared in Example 8 and the carboxylic acid-modified polyethersulfone polymer of formula III-1. The specific steps of the preparation method are as follows:

[0227] 6.250 mg of the carboxylic acid-modified polyethersulfone polymer prepared in Example 3 was mixed with 10 mL of N,N-dimethylformamide, and ultrasonicated at 75° C. for 1 h. After ultrasonication, the resulting mixed system was allowed to stand for 1 h. The supernatant was taken with a dropper and filtered through an organic filter membrane to obtain a carboxylic acid-modified polyethersulfone polymer solution for standby use.

[0228] The TPPD-COF smart membrane prepared in Example 8 was subjected to solvent replacement using N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence, and each solvent was replaced 3 times, and each soaking was 12 hours. The COF-300 smart membrane was ground to obtain fine TPPD-COF smart membrane powder, which was fully stirred and mixed with the above-mentioned carboxylic acid modified polyethersulfone polymer solution to be used. The TPPD-COF smart membrane powder and the carboxylic acid modified polyethersulfone polymer solution were mixed and cast on a flat glass, and dried under vacuum conditions at 50°C for 24 hours to obtain a smart membrane, which was recorded as TPPD-COF@COOH-PES.

[0229] Embodiment 11

[0230] This embodiment provides a solvent and pH multi-responsive smart membrane prepared by a responsive porous material of a combination of formula A-9 and formula B-5. This embodiment uses interfacial polymerization to prepare the smart membrane. The specific steps are as follows: A smart membrane constructed with a carboxylic acid-modified polyethersulfone polymer of formula III-1, the specific steps of the preparation method are as follows:

[0231] Dissolve tetraaldehyde tetraphenylmethane (TFMA, 86.4 mg, 0.2 mmol) and 2,2'-carboxy-4,4'-diaminobiphenyl (DMP, 126.8 mg, 0.4 mmol) in toluene (40 mL) and place in a 50 mL polytetrafluoroethylene-lined reactor at 120 ° C for 24 h to prepare powder (COF-320). Solvent replacement was performed using N,N-dimethylformamide, acetonitrile, methanol and acetone in sequence, and each solvent was replaced 3 times, with each soaking for 12 h. Vacuum dry at 120 ° C for 12 h, and the powder was set aside.

[0232] 6.250 mg of the carboxylic acid-modified polyethersulfone polymer prepared in Example 3 was mixed with 10 mL of N,N-dimethylformamide, and ultrasonicated at 75° C. for 1 h. After ultrasonication, the resulting mixed system was allowed to stand for 1 h. The supernatant was taken with a dropper and filtered through an organic filter membrane to obtain a carboxylic acid-modified polyethersulfone polymer solution for standby use.

[0233] The COF-320@COOH smart membrane powder was fully stirred and mixed with the above-mentioned carboxylic acid-modified polyethersulfone polymer solution to be used. The COF-320@COOH smart membrane powder and the carboxylic acid-modified polyethersulfone polymer solution were mixed and cast on a flat glass, and dried under vacuum conditions at 50° C. for 24 hours to obtain a smart membrane, which was recorded as COF-320@COOH@COOH-PES.

[0234] Example 12

[0235] This embodiment provides a solvent-responsive smart membrane prepared from a responsive porous material of a combination of formula A-9 and formula B-7. This embodiment uses interfacial polymerization to prepare the smart membrane. The specific steps are as follows: A smart membrane constructed with a carboxylic acid-modified polyethersulfone polymer of formula III-1. The specific steps of the preparation method are as follows:

[0236] Tetraaldehyde tetraphenylmethane (TFMA, 86.4 mg, 0.2 mmol) and 4,4'-diaminobiphenyl (DMP, 73.6 mg, 0.4 mmol) were dissolved in toluene (36 mL) and placed in a 50 mL polytetrafluoroethylene-lined reactor at 100 ° C for 18 h to prepare powder (COF-320). Solvent replacement was performed using N, N-dimethylformamide, acetonitrile, methanol and acetone in sequence, and each solvent was replaced 3 times, with each soaking for 12 h. The powder was dried at 120 ° C in a vacuum for 12 h and then set aside.

[0237] 6.250 mg of the carboxylic acid-modified polyethersulfone polymer prepared in Example 3 was mixed with 10 mL of N,N-dimethylformamide, and ultrasonicated at 75° C. for 1 h. After ultrasonication, the resulting mixed system was allowed to stand for 1 h. The supernatant was taken with a dropper and filtered through an organic filter membrane to obtain a carboxylic acid-modified polyethersulfone polymer solution for standby use.

[0238] The COF-320 smart membrane powder was fully stirred and mixed with the above-mentioned carboxylic acid modified polyethersulfone polymer solution to be used. The COF-320 smart membrane powder and the carboxylic acid modified polyethersulfone polymer solution were mixed and cast on a flat glass, and dried under vacuum conditions at 50° C. for 24 hours to obtain a smart membrane, which was recorded as COF-320@COOH-PES.

[0239] Test Example 1

[0240] The smart membrane prepared in Example 1 was subjected to an ion transport test, and a transmembrane ion transport performance monitoring device was assembled in a mature manner. The specific steps are as follows:

[0241] The smart membrane prepared in Example 1 was placed in a double-chamber electrolytic cell, and potassium chloride aqueous solutions with concentrations of 10 mmol / L and 10 mmol / L were added to the two electrolytic chambers as electrolytes, respectively. A pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter (i.e., an ammeter with an accuracy of picoammeter (10-12A)) to form an ion transport performance monitoring device; voltage was applied using the Ag / AgCl electrodes, and the current was tested under different voltage conditions using the picoammeter. The results showed that the above-mentioned smart membrane could obtain a linear IV curve having a point passing through the origin under this condition, as shown in FIG. Fig. 9 shown.

[0242] according to Fig. 9 It can be seen that the curve passes through the origin, indicating that the internal ion channel structure of the smart membrane of Example 1 is uniform.

[0243] Test Example 2

[0244] The smart membrane prepared in Example 1 was subjected to an osmotic energy collection test, and an osmotic energy collection device was assembled in a mature manner. The specific steps are as follows:

[0245] The smart membrane prepared in Example 1 was placed in a double-chamber electrolytic cell, and potassium chloride aqueous solutions with concentrations of 10 mmol / L and 500 mmol / L were added to the two electrolytic chambers as electrolytes, respectively. A pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter to form a salt difference power generation device. Voltage was applied using the Ag / AgCl electrodes, and the current under different voltage conditions was tested using a picoammeter. The results showed that the open circuit voltage of the smart membrane under 50 times the gradient concentration condition was 50 mV, and the short circuit current was 5 μA. Specifically, Fig.10 As shown, calculate its current density and output power density.

[0246] according to Fig.10 It can be seen that the current density of the smart membrane in Example 1 is 658 A / m 2 , the maximum output power density is 19.81W / m 2 .

[0247] Test Example 3

[0248] The smart membrane prepared in Example 1 was subjected to an ion transport test under pH response. According to the transmembrane ion transport performance monitoring device of Test Example 1, the specific steps are as follows:

[0249] The smart membrane prepared in Example 1 was placed in a dual-chamber electrolytic cell, and potassium chloride aqueous solutions with concentrations of 10 mmol / L and 10 mmol / L were added to the two electrolytic chambers as electrolytes, respectively. The pH values ​​of the electrolytes were 4, 7 and 10, respectively. A pair of Ag / AgCl electrodes were inserted into the electrolytes of the three components, and the electrodes were connected to a picoammeter to form an ion transport performance monitoring device. Voltage was applied using the Ag / AgCl electrodes, and the current was tested under different voltage conditions using a picoammeter. The results showed that the TB-COF membrane could obtain a linear IV curve passing through the origin under this condition, proving that under pH smart response conditions, the smart membrane of the present invention can maintain stable operation.

[0250] Test Example 4

[0251] The smart membrane prepared in Example 1 was tested for osmotic energy collection under pH response, and an osmotic energy collection device was assembled in a mature manner. The specific steps are as follows:

[0252] The smart membrane prepared in Example 1 was placed in a double-chamber electrolytic cell, and potassium chloride aqueous solutions with concentrations of 10 mmol / L and 500 mmol / L were added to the two electrolytic chambers as electrolytes, respectively. The pH values ​​of the two electrolytes at the above concentrations were 4, 7 and 10, respectively. A pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter to form a salt difference power generation device. Voltage was applied using the Ag / AgCl electrodes, and the current under different voltage conditions was tested using a picoammeter. The results showed that the above-mentioned smart membrane could obtain a linear IV curve that did not pass through the origin under a 50-fold gradient concentration condition, as shown in FIG. Fig.11 As shown, when the pH value is 4, the open circuit voltage is read as 110mV and the short circuit current is 12μA; when the pH value is 7, the open circuit voltage is read as 50mV and the short circuit current is 5μA; when the pH value is 10, the open circuit voltage is read as 78mV and the short circuit current is 8μA.

[0253] according to Fig.11 It can be seen that the changing trends of the open circuit voltage and the short circuit current confirm that the charge density on the nanochannel surface of the smart membrane increases when the pH value is 4.

[0254] Test Example 5

[0255] The smart membrane prepared in Example 2 was tested for ion transport, and a transmembrane ion transport performance monitoring device was assembled in a mature manner. The specific steps were as follows:

[0256] The smart membrane prepared in Example 2 was placed in a dual-chamber electrolytic cell, and potassium chloride aqueous solutions with concentrations of 10 mmol / L and 10 mmol / L were added to the two electrolytic chambers as electrolytes, respectively. A pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter to form an ion transport performance monitoring device. Voltage was applied using the Ag / AgCl electrodes, and the current was tested under different voltage conditions using a picoammeter. The results showed that the TB-COF membrane could obtain a linear IV curve with a passing origin under this condition, as shown in FIG. Fig.12 shown.

[0257] according to Fig.12 It can be seen that the IV curve passes through the origin, proving that the smart membrane of Example 2 has a certain uniformity.

[0258] Test Example 6

[0259] The smart membrane prepared in Example 2 was tested for osmotic energy collection, and an osmotic energy collection device was assembled in a mature manner, with the specific steps being:

[0260] The smart membrane prepared in Example 2 was placed in a double-chamber electrolytic cell, and potassium chloride aqueous solutions with concentrations of 10 mmol / L and 500 mmol / L were added to the two electrolytic chambers as electrolytes, respectively. A pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter to form a salt difference power generation device. Voltage was applied using the Ag / AgCl electrodes, and the current under different voltage conditions was tested using a picoammeter. The results showed that the smart membrane could obtain current density and power density under 50 times the gradient concentration condition, as shown in FIG. Fig.13 shown.

[0261] according to Fig.13 It can be seen that the current density of the smart membrane in Example 2 is 352 A / m 2 , the maximum output power density is 9.66W / m 2 .

[0262] Test Example 7

[0263] The smart membrane prepared in Example 2 was subjected to an ion transport test in a methanol solvent, and a transmembrane ion transport performance monitoring device was assembled in a mature manner. The specific steps were as follows:

[0264] The smart membrane prepared in Example 2 was placed in a double-chamber electrolytic cell, and lithium chloride methanol organic solutions with concentrations of 10 mmol / L and 10 mmol / L were added to the two electrolytic chambers as electrolytes, respectively (lithium chloride salt was selected because the solubility of sodium salt and potassium salt in methanol solvent was not high), a pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter to form an ion transport performance monitoring device; voltage was applied using the Ag / AgCl electrodes, and the current under different voltage conditions was tested using a picoammeter. The results showed that the above-mentioned smart membrane could obtain a linear IV curve with a passing origin under this condition. Under the condition that methanol organic solvent was used as the electrolyte, the internal structure of the smart membrane in Example 2 did not change and remained uniform, as shown in FIG. Fig.14 shown.

[0265] according to Fig.14 It can be seen that in the ion transport performance of the smart membrane of Example 2 in methanol solvent, the current signal decreases. At +2V, the COF-300 smart membrane shows a higher current value of 3μA in 100% water solvent. However, in 100% methanol solvent, the current signal decreases by nearly 380%, which is a response of the methanol solvent, increasing the size of the nanochannel and reducing the probability of interaction between ions and channels.

[0266] Test Case 8

[0267] The smart membrane prepared in Example 2 was subjected to an osmotic energy collection test in a methanol solvent, and an osmotic energy collection device was assembled in a mature manner, with the specific steps being:

[0268] The smart membrane prepared in Example 2 was placed in a dual-chamber electrolytic cell, and lithium chloride methanol organic solutions with concentrations of 10mmol / L and 500mmol / L were added to the two electrolytic chambers as electrolytes (lithium chloride salt was selected because the solubility of sodium salt and potassium salt in methanol solvent was not high), and a pair of Ag / AgCl electrodes were inserted, and the electrodes were connected to a picoammeter to form a salt difference power generation device; voltage was applied using the Ag / AgCl electrodes, and the current was tested under different voltage conditions using a picoammeter. The results showed that the above TB-COF membrane could obtain a linear IV curve that did not pass the origin under 50 times the gradient concentration condition, read the open circuit voltage and short circuit current values, and calculate its current density and power density. The results showed that there was a certain change compared to the water electrolyte conditions, indicating that the size of the ion channel inside the smart membrane of Example 2 increased with the appearance of the organic solvent.

[0269] It can be seen from the above embodiments that the smart membrane provided by the present invention has excellent selectivity and permeability, intelligently regulates the ion flow in the ion channel, realizes the fine ion transmission function comparable to that of a living organism, selectively transmits ions, rapidly conducts specific ions, and responsively controls the ion flow.

[0270] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A responsive porous material, characterized in that: The unit cell structure is shown in Formula I or Formula II; the responsive porous material contains a responsive group, and the responsive group includes at least one of a carboxyl group, a hydroxyl group and a nitrogen-containing heterocycle; In Formula I and Formula II, A is one of the structures shown in Formula A-1 to Formula A-10, and B is one of the structures shown in Formula B-1 to Formula B-14; 2. The method for preparing the responsive porous material according to claim 1, characterized in that: The following steps are involved: Mixing the first monomer, the second monomer, the catalyst and the organic solvent for polycondensation to obtain the responsive porous material; Alternatively, the first monomer, the second monomer and the catalyst are mixed with two phases of organic solvents to form a two-phase reaction solution to perform an interfacial polymerization reaction to obtain the responsive porous material; The first monomer is one of the compounds represented by formula C-1 to formula C-10; the second monomer is one of the compounds represented by formula D-1 to formula D-14; 3. Use of the responsive porous material according to claim 1 or the responsive porous material obtained by the preparation method according to claim 2 in a stimulus-responsive device.

4. A smart membrane, characterized in that: The components include the responsive porous material according to claim 1 or the responsive porous material obtained by the preparation method according to claim 2.

5. The smart membrane according to claim 4, characterized in that: The raw materials of the smart membrane also include a modified component; the modified component is a special engineering plastic; the special engineering plastic is modified polyethersulfone, and the structure of the modified polyethersulfone is shown in Formula III: In Formula III, m is 200 to 400, n is 200 to 400, and E is one of the structures of Formula E-1 and Formula E-2; 6. The smart membrane according to claim 5, characterized in that: The preparation method of the modified polyether sulfone comprises the following steps: mixing a third monomer, a fourth monomer, a fifth monomer, a water-carrying agent, a catalyst and an organic solvent for polycondensation to obtain the modified polyether sulfone; the structure of the third monomer is shown in Formula F: The structure of the fourth monomer is shown in Formula G: The fifth monomer includes at least one of the monomers of formula H-1 and formula H-2:

7. The smart membrane according to claim 4, characterized in that: The smart membrane also includes a modified component membrane; the modified component membrane is prepared from a modified component; both sides of the modified component membrane are infiltrated with the responsive porous material according to claim 1 or the responsive porous material obtained by the preparation method according to claim 2.

8. The method for preparing the smart membrane according to any one of claims 4 to 6, characterized in that: The following steps are involved: The responsive porous material and the organic solvent are mixed, and then filtered and the solvent is removed in sequence to obtain the smart membrane; Alternatively, the first monomer, the second monomer and the catalyst are mixed with two phases of organic solvents to form a two-phase reaction solution to perform an interfacial polymerization reaction to obtain the smart membrane; Alternatively, the responsive porous material and the organic solvent are mixed, and then cast and the solvent is removed in sequence to obtain the smart membrane.

9. The method for preparing the smart membrane according to claim 7, characterized in that: The following steps are involved: (1) mixing the modified component with an organic solvent, and then sequentially standing, filtering and drying to obtain a modified polyethersulfone membrane; (2) On both sides of the modified polyethersulfone membrane, the first monomer, the second monomer, the catalyst and the organic solvent are independently mixed to carry out a condensation polymerization reaction to obtain the smart membrane.

10. Use of the smart membrane according to any one of claims 4 to 7 or the smart membrane obtained by the preparation method according to any one of claims 8 to 9 in an osmotic energy conversion and collection device.

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