A responsive porous material, a preparation method and application thereof, and a smart membrane, a preparation method and application thereof

Abstract

The application belongs to the technical field of intelligent materials, and particularly relates to a responsive porous material, a preparation method and application thereof, and an intelligent membrane, a preparation method and application thereof. The responsive porous material provided by the application is a long-range ordered crystalline porous material, which is stable in structure, has ordered response groups / fragments in the ion channel, forms an ordered molecular array, makes ion transmission between an external stimulation signal and a response site more efficient, changes the charge density and nanofluid channel size in the stimulation structure in acid-base, temperature, solvent and ion recognition scenes, has excellent selectivity and permeability, can intelligently adjust ion flow in the ion channel, realizes a fine ion transmission function comparable to a biological body, selectively transmits ions, rapidly conducts specific ions, and responsively controls ion flow.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of intelligent materials, and particularly relates to a responsive porous material and a preparation method and application thereof, and an intelligent membrane and a preparation method and application thereof. BACKGROUND

[0002] Intelligent materials, also known as stimulus-responsive materials, are a class of materials that can produce reversible, visible and tangible responses to external stimuli, such as mechanical stress, heat, light, gas, electricity and pH value. At present, intelligent materials are widely concerned in many frontier fields such as sensors, actuators, optoelectronic devices, information storage and medical treatment. The key to the preparation of intelligent materials lies in the introduction of response groups or parts in the structure of the materials, which can respond to external stimuli to perform chemical / physical changes.

[0003] At present, the design and construction of intelligent materials mainly focus on polymers, carbon materials and hydrogels, etc. However, these materials have no ordered structure or only have low ordered structure (i.e. the response groups / parts are disordered in the structure), which inevitably produces defects such as relatively low response speed. SUMMARY

[0004] The application aims to provide a responsive porous material and a preparation method and application thereof, and an intelligent membrane and a preparation method and application thereof. The responsive porous material provided by the application has higher ion transmission efficiency and faster response speed.

[0005] In order to achieve the above-mentioned purpose, the application provides the following technical scheme:

[0006] The application provides a responsive porous material, and the crystal cell structure is shown in formula I or formula II; the responsive porous material contains a response group, and the response 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 structures shown in formula A-1 to formula A-10, and B is one of structures shown in formula B-1 to formula B-14.

[0009]

[0010]

[0011] The application further provides a preparation method of the responsive porous material, and the preparation method comprises the following steps:

[0012] The first monomer, the second monomer, the catalyst and the organic solvent are mixed to perform a polycondensation reaction, so as to obtain the responsive porous material.

[0013] Or, the first monomer, the second monomer and the catalyst are mixed with two-phase organic solvent respectively to form two-phase reaction liquid for carrying out interfacial polymerization reaction, so that the responsive porous material is obtained.

[0014] The first monomer is one of compounds shown in formula C-1 to formula C-10; and the second monomer is one of compounds shown in formula D-1 to formula D-14.

[0015]

[0016]

[0017] The application further provides application of the responsive porous material prepared by the preparation method in a stimulus-responsive device.

[0018] The application further provides an intelligent film, and components of the intelligent film include the responsive porous material prepared by the preparation method.

[0019] Preferably, the raw material of the intelligent film further includes a modified component; the modified component is a special engineering plastic; the special engineering plastic is modified polyether sulfone, and a structure of the modified polyether sulfone 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 formula E-1 and formula E-2.

[0022]

[0023] Preferably, the preparation method of the modified polyether sulfone includes the following steps: a third monomer, a fourth monomer, a fifth monomer, a water-carrying agent, a catalyst and an organic solvent are mixed to carry out polycondensation reaction, so that the modified polyether sulfone is obtained; and a structure of the third monomer is shown in formula F.

[0024]

[0025] A structure of the fourth monomer is shown in formula G.

[0026]

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

[0028]

[0029] Preferably, the intelligent membrane further comprises a modified component membrane; the modified component membrane is prepared from a modified component; the two sides of the modified component membrane are permeated 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 application further provides a preparation method of the intelligent membrane described in the above scheme, comprising the following steps:

[0031] mixing the responsive porous material and the organic solvent, and then sequentially performing suction filtration and solvent removal to obtain the intelligent membrane;

[0032] or, mixing the first monomer, the second monomer and the catalyst with two-phase organic solvents respectively to form two-phase reaction liquid for interfacial polymerization to obtain the intelligent membrane;

[0033] or, mixing the responsive porous material and the organic solvent, and then sequentially performing casting and solvent removal to obtain the intelligent membrane.

[0034] Preferably, when the intelligent membrane comprises a modified component, the preparation method of the intelligent membrane is: (1) mixing the modified component with the organic solvent, and then sequentially performing standing, suction filtration and drying to obtain a modified polyether sulfone membrane; (2) mixing the first monomer, the second monomer, the catalyst and the organic solvent on the two sides of the modified polyether sulfone membrane respectively and independently for polycondensation reaction.

[0035] The application further provides an application of the intelligent membrane described in the above scheme or the intelligent membrane obtained by the preparation method described in the above scheme in a permeation energy conversion and collection device.

[0036] The application provides a responsive porous material. The responsive porous material provided by the application is a long-range ordered crystalline porous material, which has stable structure, ordered response groups / fragments in the ion channel, forms an ordered molecular array, and makes ion transmission between external stimulus signals and response sites more efficient. In the scenes of acid-base, temperature, solvent and ion recognition, the charge density in the stimulated structure and the size of the nanofluid channel change, which has excellent selectivity and permeability, can intelligently adjust the ion flow in the ion channel, realize the fine ion transmission function comparable to the biological body, selectively transmit ions, rapidly conduct specific ions, and responsively control ion flow. In addition, the clear structure is conducive to in-situ characterization of the structure transformation at the molecular level by using various technologies and high-tech equipment, such as in-situ spectroscopy and single crystal / powder X-ray diffraction, and basic structure characterization means, so as to facilitate the research and understanding of the mechanism behind the stimulation response behavior and structure-property relationship, and finally realize the practical application of the multi-scene intelligent membrane in the fields of energy conversion or biochemical sensing.

[0037] The application further provides a preparation method of the responsive porous material.

[0038] The application further provides application of the responsive porous material or the responsive porous material prepared by the preparation method in a stimulus-responsive device.

[0039] The application further provides a smart membrane.

[0040] The application further provides a preparation method of the smart membrane.

[0041] The application further provides application of the smart membrane or the smart membrane prepared by the preparation method in a permeation energy conversion and collection device. BRIEF DESCRIPTION OF DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments. Obviously, the drawings in the following description are only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative effort.

[0043] Figure 1 X-ray diffraction spectrum of the powder of the smart membrane prepared for Example 1;

[0044] Figure 2 Infrared spectrum of the smart membrane prepared for Example 1;

[0045] Figure 3 Scanning electron microscope surface image of the smart membrane prepared for Example 1;

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

[0047] Figure 5 X-ray diffraction pattern of the powder of the smart membrane prepared in Example 2;

[0048] Figure 6 The infrared spectrum of the smart membrane prepared in Example 2;

[0049] Figure 7 A scanning electron microscope image of the surface of the smart membrane prepared in Example 2;

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

[0051] Figure 9 The IV curve is a test result of the ion transport performance of the smart membrane prepared in Example 1 in the same electrolyte solution.

[0052] Figure 10 The graph shows the osmotic energy collection of the smart membrane prepared in Example 1 in an electrolyte solution with a concentration gradient of 50 times.

[0053] Figure 11 The open-circuit voltage and short-circuit current of the smart membrane prepared in Example 1 in an environment with multiple pH gradients;

[0054] Figure 12 The IV curve is a test graph of the ion transport performance of the smart membrane prepared in Example 2 in the same electrolyte solution.

[0055] Figure 13 The graph shows the osmotic energy collection of the smart membrane prepared in Example 2 in an electrolyte solution with a concentration gradient of 50 times.

[0056] Figure 14 The diagram shows the ionic conductivity of the smart membrane prepared in Example 2 in a multi-gradient concentration methanol organic solvent environment. Detailed Implementation

[0057] This invention provides a responsive porous material with a cell structure as shown in Formula I or Formula II; the responsive porous material contains responsive groups, which include at least one of carboxyl, hydroxyl and nitrogen-containing heterocycles;

[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 application, 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 (6 repeating units form a hexagonal macrocycle, topological design form "C2+C3", C2 refers to two reactive sites on the monomer participating in the reaction, C3 refers to three reactive sites on the monomer participating in the reaction, to form a pore structure unit) of the responsive porous material is shown in formula I-1:

[0063]

[0064] In the present application, 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 shown in formula I-2:

[0065]

[0066] In the present application, 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 shown in formula I-3:

[0067]

[0068] In the present application, 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 shown in formula I-4:

[0069]

[0070] In the present application, 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 spatial structure unit (4 repeating units are not in the same plane, three-dimensional COF-tetrahedron, body topological design form "C2+C4", C2 refers to two reactive sites on the monomer participating in the reaction, C4 refers to four reactive sites on the monomer participating in the reaction, to form a spatial structure unit) of the responsive porous material is shown in formula II-1:

[0071]

[0072] In the present application, 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 spatial structure unit of the responsive porous material is shown in formula II-2:

[0073]

[0074] In the present application, 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 stereoscopic structure unit of the responsive porous material is shown in formula II-3:

[0075]

[0076] In the present application, 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 stereoscopic structure unit of the responsive porous material is shown in formula II-4:

[0077]

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

[0079] The present application also provides a preparation method of the responsive porous material described in the above scheme, comprising the following steps:

[0080] The first monomer, the second monomer, the catalyst and the organic solvent are mixed to perform a polycondensation reaction, so as to obtain the responsive porous material;

[0081] Alternatively, the first monomer, the second monomer and the catalyst are mixed with two-phase organic solvents respectively to form two-phase reaction liquids for performing an interfacial polymerization reaction, and the catalyst is not in the two-phase reaction liquids at the same time, so as to obtain the responsive porous material;

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

[0083]

[0084]

[0085] The first preparation method is single-phase preparation: the first monomer, the second monomer, the catalyst (denoted as the first catalyst) and the organic solvent (denoted as the first organic solvent) are mixed (denoted as the first mixing) to perform a polycondensation reaction (denoted as the first polycondensation reaction), thereby obtaining the responsive porous material. In the present application, 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-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; and the monomer combination method of the remaining responsive porous materials is the same as that of the above responsive porous materials, which will not be described here.

[0086] In the present application, the molar ratio of the first monomer to the second monomer is preferably 0.8-1.4:0.8-1.4, and specifically can be 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 responsive group, the first monomer is added in excess, and when the second monomer carries a responsive group, the second monomer is added in excess; the excess addition of the first monomer or the second monomer is preferably 1-20% of the standard addition amount. By controlling the slight excess of a certain monomer in the present application, the sufficient reaction of the other monomer (the monomer carrying the responsive group) is ensured, thereby promoting the synthesis of the responsive porous material.

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

[0088] In the present application, the molar ratio of the total mole amount of the first monomer and the second monomer to the first catalyst is preferably 1:1~2, and can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1:2.

[0089] In the present application, 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 diethyl ether; the amide solvent preferably includes one or both 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; and the substituted methane preferably includes one or both of dichloromethane and chloroform. The use of the above-mentioned solvents in the present application can better dissolve the first monomer and the second monomer.

[0090] In the present application, the first organic solvent is preferably treated with anhydrous and oxygen-free before use. By treating the first organic solvent with anhydrous and oxygen-free, the present application avoids the reverse promotion of water on the polycondensation reaction and reduces the influence on the polycondensation reaction.

[0091] In the present application, the molar ratio of the total mole amount of the first monomer and the second monomer to the first organic solvent is preferably 0.01~0.05:1~5, and can be 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 application, the first mixing is preferably carried out in an inert atmosphere; the inert atmosphere is provided by an inert gas, which is preferably argon.

[0093] In the present application, the temperature of the first polycondensation reaction is preferably 25~180℃, and can be 25℃, 45℃, 65℃, 85℃, 100℃, 120℃, 150℃ or 180℃, and the holding reaction time is preferably 24~120h, and can be 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, which is preferably argon.

[0094] In the present application, the first polycondensation reaction preferably further includes first post-treatment of the obtained product; the first post-treatment is preferably soaking and drying the obtained product after taking it out.

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

[0096] In the present application, the drying pressure is preferably normal pressure; the drying temperature is preferably 80-120℃, and can be specifically 80℃, 90℃, 100℃, 110℃ or 120℃; the holding time of drying is preferably 12-24 h, and can be specifically 12 h, 15 h, 18 h, 21 h or 24 h.

[0097] The second preparation method is two-phase preparation: the first monomer, the second monomer and the catalyst (denoted as the first catalyst) are mixed with two-phase organic solvents respectively to form two-phase reaction liquid for interfacial polymerization reaction, and the catalyst is not in the two-phase reaction liquid at the same time, to obtain the responsive porous material. In the present application, the types and amount of the first monomer, the second monomer and the catalyst, and the amount of the two-phase organic solvents (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 application, the second organic solvent preferably comprises one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide, trimethyl toluene, acetonitrile, acetonitrile aqueous solution and acetic acid aqueous solution; the third organic solvent preferably comprises 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, and can be 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 application, the two-phase reaction liquid comprises 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, and can be 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, and can be 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 application, 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 herein again, except that the interfacial polymerization reaction is preferably carried out in an air atmosphere; a buffer layer is preferably arranged between the two-phase interface of the obtained system after the mixing to form the two-phase reaction liquid; the buffer layer preferably comprises one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide, acetonitrile and water; and the water is preferably deionized water. The present application can reduce the interfacial reaction rate and improve the crystallinity of the material through the buffer layer.

[0101] The responsive porous material provided by the present application is prepared by one-step method, and the responsive groups carried by the responsive porous material do not need to be subjected to post-modification treatment, thereby guaranteeing the ion channel of the constructed responsive porous material to have a responsive performance.

[0102] The present application also provides an application of the responsive porous material in a stimulus-responsive device.

[0103] The present application also provides an intelligent membrane, and the components of the intelligent membrane comprise the responsive porous material or the responsive porous material obtained by the preparation method.

[0104] In the present application, the raw material of the intelligent membrane preferably further comprises a modified component; the modified component is preferably a special engineering plastic; and the special engineering plastic is preferably a modified polyether sulfone, and the structure of the modified polyether sulfone is shown in formula III (m and n are the polymerization degree):

[0105]

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

[0107]

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

[0109] In the present application, the number average molecular weight of the polyether sulfone compound is preferably 30000-80000.

[0110] In the present application, the modified polyether sulfone is preferably a compound of formula III-1, and the structure is shown in formula III-1.

[0111]

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

[0113] In the present application, the structure of the third monomer is shown in formula F.

[0114]

[0115] In the present application, the structure of the fourth monomer is shown in formula G.

[0116]

[0117] In the present application, the molar ratio of the third monomer and the fourth monomer is preferably 0.8-1.4:0.8-1.4, and specifically can be 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 application, the fifth monomer comprises at least one of a monomer of formula H-1 and a monomer of formula H-2, and is preferably a monomer of formula H-1.

[0119]

[0120] In the present application, the molar ratio of the fourth monomer and the fifth monomer is preferably 0.8-1.4:0.8-1.4, and can be 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 application, the water-carrying agent is preferably a benzene homolog; the benzene homolog is preferably toluene.

[0122] In the present application, the molar ratio of the third monomer and the water-carrying agent is preferably 0.01-0.05:1-2, and can be 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 application, 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 application, the molar ratio of the third monomer and the second catalyst is preferably 1:1.3-1.5, and can be specifically 1:1.3, 1:1.35, 1:1.4, 1:1.45, or 1:1.5.

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

[0126] In the present application, the mass ratio of the third monomer and the fourth organic solvent is preferably 0.01-0.05:1-5, and can be 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 application, the second polycondensation reaction is preferably carried out under reflux conditions; the temperature of the second polycondensation reaction is preferably 175-185℃, and can be specifically 180℃; the holding reaction time is preferably 5-20h, and can be specifically 10h or 15h.

[0128] In the application, the second polycondensation reaction preferably further comprises water removal of the second mixed solution; the temperature of the water removal is preferably 145 DEG C. In the water removal process of the application, the water in the system is completely removed by the water carrying agent.

[0129] In the application, the second polycondensation reaction preferably further comprises second post-treatment of the obtained reaction solution; the second post-treatment preferably comprises: sequentially performing precipitation, solid-liquid separation, crushing, washing and drying on the obtained reaction solution.

[0130] In the application, the precipitation is preferably performed in water; the water is preferably deionized water; the solid-liquid separation is preferably filtration; the washing preferably comprises sequentially performing water washing and alcohol washing; the water used in the water washing is preferably boiling water; the alcohol used in the alcohol washing is preferably ethanol; the drying is preferably vacuum drying; the temperature of the drying is preferably 120 DEG C, and the heat preservation drying time is preferably 48 h.

[0131] The modified polyether sulfone with only carboxyl and amino modification modes can better form covalent bonds or strong bonds with the responsive porous material, so that the constructed membrane structure is better suitable for use in multiple scenes.

[0132] In the application, the intelligent membrane preferably further comprises a modified component, the modified component preferably exists in the form of a modified component membrane, the modified component membrane is prepared from the modified component; the two sides of the modified component membrane are permeated with the responsive porous material in the above scheme or the responsive porous material obtained by the preparation method in the above scheme; the thickness of the intelligent membrane is preferably 1-10 mu m, and specifically can be 1 mu m, 3 mu m, 5 mu m, 7 mu m or 10 mu m; the pore size of the intelligent membrane is preferably 50-200 nm, and specifically can be 50 nm, 80 nm, 100 nm, 150 nm or 200 nm.

[0133] In the application, the thickness of the intelligent membrane is preferably 0.1-10 mu m, and specifically can be 0.1 mu m, 0.3 mu m, 0.5 mu m, 0.7 mu m, 1 mu m, 3 mu m, 5 mu m, 7 mu m or 10 mu m.

[0134] In the application, the pore size of the intelligent membrane is preferably 0.3-2.5 nm, and specifically can be 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 application, the ion flux of the intelligent membrane is preferably 1-20 S / cm. The intelligent membrane allows the passage of positive and negative ions, only negative ions pass when the carboxyl is modified, only positive ions pass when the amino is modified, has excellent ion selectivity, and has high water and ion flux.

[0136] The application further provides a preparation method of the intelligent membrane.

[0137] The response type porous material and the organic solvent are mixed, and then filtration and solvent removal are sequentially performed to obtain the intelligent membrane.

[0138] Alternatively, the first monomer, the second monomer and the catalyst are mixed with two-phase organic solvents respectively to form two-phase reaction liquid for interfacial polymerization to obtain the intelligent membrane.

[0139] Alternatively, the response type porous material and the organic solvent are mixed, and then casting and solvent removal are sequentially performed to obtain the intelligent membrane.

[0140] In the first aspect, the response type porous material and the fifth organic solvent are mixed (denoted as third mixing) and then filtration and solvent removal (denoted as first solvent removal) are sequentially performed to obtain the intelligent membrane. In the application, the fifth organic solvent preferably comprises one or more of sulfolane, N,N-dimethylformamide and N,N-dimethylacetamide.

[0141] In the application, the mass ratio of the response type porous material to the fifth organic solvent is preferably 0.01-0.05:1-5, and can be 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 application, the third mixing is preferably stirring mixing, and the raw material of the third mixing preferably further comprises a modified component. The modified component is preferably a special engineering plastic, and the special engineering plastic is preferably modified polyether sulfone, the structure of which is shown in formula III. The molar ratio of the response type porous material to the modified component is preferably 1-5:1-5, and can be 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 material of the third mixing further comprises a modified component, the fifth organic solvent preferably comprises one or more of sulfolane, N,N-dimethylformamide and N,N-dimethylacetamide. The application introduces modified polyether sulfone, which is aimed at more extreme application scenarios, such as high-salinity electrolyte, high-temperature electrolyte, super-large application area and super-high mechanical strength, so that the response type porous material and the modified polyether sulfone synergize with each other to form an intelligent membrane which is easy to mass-produce, commercialize and has high use value, and can better realize stable, long-term and efficient permeation energy conversion and collection in multiple scenarios.

[0143] In the present application, the filtration is preferably suction filtration; the device for the suction filtration is preferably a suction pump; and the vacuum degree of the suction filtration is preferably 0.05-0.1 MPa, and can be specifically 0.05 MPa, 0.07 MPa, 0.09 MPa or 0.1 MPa.

[0144] In the present application, the first solvent removal is preferably heating; and the temperature of the heating is preferably 60-150 DEG C, and can be specifically 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C or 150 DEG C. The present application makes the solvent volatilize by heating.

[0145] In the present application, the first solvent removal is preferably further comprising solvent replacement of the obtained membrane product; the solvent replacement is preferably solvent immersion; the solvent used in the solvent immersion preferably comprises one or more of N, N-dimethylformamide, acetonitrile, methanol and acetone; and the time of the solvent immersion is preferably 8-12 h, and can be specifically 10 h.

[0146] In the present application, the first solvent removal is preferably further comprising product stripping. The present application obtains a defect-free, crack-free, flexible and independent intelligent membrane through the above preparation.

[0147] Secondly, the present application forms a two-phase reaction liquid by mixing the first monomer, the second monomer and the catalyst with two-phase organic solvents (denoted as the fourth mixing) respectively to perform interfacial polymerization reaction, and obtains the intelligent membrane. In the present application, the two-phase organic solvents comprise a sixth organic solvent and a seventh organic solvent; the sixth organic solvent preferably comprises one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N, N-dimethylformamide, acetonitrile, acetonitrile aqueous solution and acetic acid aqueous solution; and the seventh organic solvent preferably comprises one or more of cyclohexane, trimethyl toluene, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene and dichloromethane.

[0148] In the present application, the mass ratio of the total mass of the first monomer and the second monomer to the mass of the sixth organic solvent is preferably 0.01-0.05:1-5, and can be 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; and the mass ratio of the total mass of the first monomer and the second monomer to the mass of the seventh organic solvent is preferably 0.01-0.05:1-5, and can be 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 application, the fourth mixing is preferably stirring mixing; the raw material of the fourth mixing preferably further comprises a modifying component; the modifying component is preferably a special engineering plastic; the special engineering plastic is preferably modified polyether sulfone, and the structure of the modified polyether sulfone is shown in Formula III; the molar ratio of the total moles of the first monomer and the second monomer to the moles of the modifying component is preferably 1-5:1-5, and specifically can be 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 material of the fourth mixing further comprises a modifying component, the sixth organic solvent preferably comprises one or more of methanol, ethanol, propanol, acetone, methyl butyl ketone, N,N-dimethylformamide and acetonitrile, and the seventh organic solvent preferably comprises one or more of cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene and dichloromethane.

[0150] In the present application, the temperature of the interfacial polymerization reaction is preferably 25-120℃, and specifically can be 25℃, 45℃, 75℃, 100℃ or 120℃, and the incubation reaction time is preferably 12-96h, and specifically can be 12h, 24h, 36h, 48h, 72h or 96h.

[0151] In the present application, other preparation parameters of the intelligent film are preferably the same as the interfacial polymerization preparation method of the responsive porous material, and will not be described here.

[0152] Thirdly, the present application mixes (recorded as the fifth mixing) the responsive porous material and an organic solvent (recorded as the eighth organic solvent) and then performs casting and solvent removal (recorded as the second solvent removal) in sequence to obtain the intelligent film. In the present application, the eighth organic solvent preferably comprises one or more of methyl butyl ketone, N,N-dimethylformamide and acetonitrile.

[0153] In the present application, the mass ratio of the responsive porous material to the eighth organic solvent is preferably 0.1-0.5:1-5, and specifically can be 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 application, the fifth mixing is preferably stirring mixing; the raw material of the fifth mixing preferably further comprises a modifying component; the modifying component is preferably a special engineering plastic; the special engineering plastic is preferably modified polyether sulfone, and the structure of the modified polyether sulfone is shown in formula III; the molar ratio of the responsive porous material and the modifying component is preferably 0.1-0.5:1-5, and specifically can be 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 material of the fifth mixing further comprises a modifying component, the eighth organic solvent preferably comprises one or more of sulfolane, N,N-dimethylformamide and N,N-dimethylacetamide.

[0155] In the present application, the pouring amount of the pouring is preferably 0.03-0.50 mL / cm 2 , and specifically can be 0.03 mL / cm 2 , 0.05 mL / cm 2 , 0.1 mL / cm 2 , 0.2 mL / cm 2 , 0.3 mL / cm 2 , 0.4 mL / cm 2 or 0.5 mL / cm 2 .

[0156] In the present application, the second solvent removal is preferably performed on the substrate of the pouring; the second solvent removal is preferably heating; the temperature of the heating is preferably 60-150℃, and specifically can be 60℃, 80℃, 100℃, 120℃ or 150℃. The present application makes the solvent volatilize through heating.

[0157] In the present application, the second solvent removal preferably further comprises solvent replacement of the obtained film product after the second solvent removal; the solvent replacement is preferably solvent soaking; the solvent used in the solvent soaking preferably comprises one or more of N,N-dimethylformamide, acetonitrile, methanol and acetone; the time of the solvent soaking is preferably 8-12 h, and specifically can be 10 h.

[0158] In the present application, when the intelligent film comprises a modifying component, the preparation method of the intelligent film preferably comprises the following steps: (1) mixing (denoted as the sixth mixing) the modifying component with an organic solvent (denoted as the ninth organic solvent) and then performing filtration and solvent removal (denoted as the third solvent removal) in sequence to obtain a modified polyether sulfone film; (2) mixing the first monomer, the second monomer, the catalyst and the organic solvent on both sides of the modified polyether sulfone film respectively and independently to perform polycondensation reaction.

[0159] In the present application, the ninth organic solvent preferably comprises one or more of methylbutyl ketone, N,N-dimethylformamide and acetonitrile.

[0160] In the present application, the mass ratio of the modification component and the ninth organic solvent is preferably 0.1-0.5:1-5, and can be 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 application, the temperature of the sixth mixing is preferably 60-150℃, and can be 60℃, 90℃, 120℃ or 150℃, and the time is preferably 0.5-3h, and can be 1h or 2h.

[0162] In the present application, the filtration is preferably suction filtration, the filter head used in the suction filtration is preferably an organic filter head, the device for the suction filtration is preferably a suction pump, and the vacuum degree of the suction filtration is preferably 0.05-0.1MPa, and can be 0.05MPa, 0.07MPa, 0.09MPa or 0.1MPa. By filtration, the present application reduces the undissolved monomers or particles in the membrane, and reduces the separation effect of the membrane.

[0163] In the present application, the temperature of the third solvent removal is preferably 50-150℃, and can be 50℃, 70℃, 90℃, 110℃, 120℃ or 150℃, and the time is preferably 12-36h, and can be 24h.

[0164] In the present application, the reaction conditions of step (2) are preferably the same as those in the preparation method of the responsive porous material, which will not be described herein. The responsive porous material provided by the present application can be synergized with the modified special engineering material to form an intelligent membrane which is easy to mass-produce, commercialize and has high use value.

[0165] The present application also provides the use of the intelligent membrane prepared by the preparation method described in the above scheme in a permeation energy conversion and collection device.

[0166] The application utilizes the designability of the responsive porous material, introduces acid-base, temperature, solvent or ion recognition response groups in the framework structure of the responsive porous material, and obtains intelligent membranes in multiple scenes: in the acid-base environment stimulation response, the charge density inside the ion channel can be fully regulated, so that the ion channel has certain ion selectivity, and the selective ability can change with the change of the environment acid-base; in the temperature environment stimulation response, it will affect the rate of ion transmembrane transport, the viscosity of the electrolyte solution decreases with the increase of the temperature, the rate of ion transmission in the nanochannel increases, which increases the permeability and also increases the selectivity to a certain extent; in the solvent environment stimulation response, the polarity of different solvents in the C4 structure of the responsive porous material of the application can change the stretching performance of the structure, change the size of the ion transmission space, and thus affect the ion transmission performance; for different ion environment stimulation response, it is particularly important to design specific recognition porous materials, and the corresponding electrochemical signal output is obtained by recognizing specific ions. The intelligent membrane provided by the application can be effectively designed according to the scene needs, the charge density and nanochannel size of the ion transmission space are changed, and excellent ion selectivity and permeability are realized.

[0167] In the application, the acid-base environment is preferably strong oxidizing acid and 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 1-14, and specifically can be 4 or 10.

[0168] In the application, the temperature of the temperature environment is preferably 0-100 DEG C, and specifically can be 25 DEG C or 85 DEG C; the temperature environment is the environment of the device, and specifically can be an electrolyte solution.

[0169] In the application, the solvent in the solvent environment is preferably a polar solvent, and 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, and more preferably acetonitrile, methanol, acetone and tetrahydrofuran.

[0170] In the application, the ion in the ion environment is preferably one or more of transition state metal ions and alkali metal ions, and more preferably alkali metal ions; the alkali metal ion preferably includes one or more of lithium ion, sodium ion, potassium ion, magnesium ion and calcium ion.

[0171] In the application, the permeation energy conversion and collection device is preferably a salt difference power generation device. The application does not have special requirements for the specific method of the application, and the method familiar to those skilled in the art can be used.

[0172] In the present application, the salt difference power generation device preferably comprises a double-chamber electrolytic cell, a double electrode and a picoammeter connected with the double electrode; the intelligent membrane is placed in the double-chamber electrolytic cell.

[0173] In the present application, the preparation method of the salt difference power generation device is preferably as follows: the intelligent membrane is placed in a double-chamber electrolytic cell, different concentrations of electrolyte are respectively added into two electrolytic chambers of the double-chamber electrolytic cell, then a double electrode is inserted, and the double electrode is connected with a picoammeter.

[0174] In the present application, the electrode of the double electrode preferably comprises 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 application, the electrolyte is preferably a sodium chloride aqueous solution or a potassium chloride aqueous solution, and more preferably a potassium chloride aqueous solution; the concentration of the electrolyte is preferably 1-10000 mmol / L, and specifically can be 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 application, the schemes of the present application are described in detail below in combination with the drawings and examples, but they should not be understood as limiting the scope of protection of the present application.

[0177] Example 1

[0178] The present example provides a pH-responsive intelligent membrane prepared from a responsive porous material of formula I-1. The intelligent membrane is prepared by interfacial polymerization, and 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'-dipyridyl-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 (acetonitrile 30 mL / deionized water 70 mL), and acetic acid (20 μL) was added to obtain a second phase solution.

[0181] The two-phase solution is stirred for 30 min, and the interfacial reaction system is placed in a beaker (300 mL). Acetonitrile and deionized water (acetonitrile 18 mL / deionized water 42 mL) are added as a buffer layer between the two phases. After adding the above components, the reaction is carried out at room temperature (25°C) for 96 h. After the reaction, the two-phase solution is removed, and the product is subjected to solvent replacement by sequentially immersing in N,N-dimethylformamide, acetonitrile, methanol, and acetone, each for 3 times, each time for 12 h, and dried at 100°C for 18 h to obtain the smart film, which is denoted as TB-COF (2D COF).

[0182] The powder of the smart film prepared in Example 1 is subjected to X-ray diffraction analysis, and the results are shown in Table 1. Figure 1 Figure 1 It can be seen that a good crystalline porous material is obtained, and the crystallinity is strong.

[0183] The smart film prepared in Example 1 is subjected to infrared analysis, and the results are shown in Table 2. Figure 2 Figure 2 It can be seen that the monomer characteristic peaks disappear, and the TB-COF smart film is successfully prepared.

[0184] The surface of the smart film prepared in Example 1 is subjected to scanning electron microscope test, and the results are shown in Table 3. Figure 3 Figure 3 It can be seen that there is no obvious defect or crack on the surface, which proves that the independent and complete film structure can be obtained by interfacial polymerization.

[0185] The smart film prepared in Example 1 is subjected to thermogravimetric analysis, and the results are shown in Table 4. Figure 4 Figure 4 It can be seen that the smart film frame decomposes only at 400°C, which proves that the smart film has good thermal stability.

[0186] Example 2

[0187] The present embodiment provides a solvent-responsive smart film prepared from the responsive porous material of formula II-1. The smart film is prepared by interfacial polymerization, and the specific steps are as follows:

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

[0189] p-Phthalaldehyde (TPAL, 48 mg) is dissolved in 8 mL of trimethylbenzene to obtain the upper organic phase.

[0190] ​​​​5mL acetic acid aqueous solution was added as a buffer layer between the two-phase interface, and after the above components were added, the reaction was carried out at room temperature (25℃) for 96h, and a COF film was formed at the interface; after the reaction, the two-phase solution was removed, and the product was subjected to solvent replacement with N,N-dimethylformamide, acetonitrile, methanol and acetone in turn, 3 times for each solvent, each time for 12h, and dried at 100℃ for 18h to obtain an intelligent film, which is recorded as COF-300 (3D COF).

[0191] The powder of the intelligent film prepared in Example 2 was subjected to X-ray diffraction analysis, and the results are shown in Table 1. Figure 5 Figure 5 It can be seen that a good crystalline porous material is obtained, and the crystallinity is strong.

[0192] The intelligent film prepared in Example 2 was subjected to infrared analysis, and the results are shown in Table 2. Figure 6 Figure 6 It can be seen that the characteristic peaks of the monomer disappear, and new bonds of COF appear, proving that the material is successfully prepared.

[0193] The surface of the intelligent film prepared in Example 2 was subjected to scanning electron microscope test, and the results are shown in Table 3. Figure 7 Figure 7 It can be seen that an independent and complete film structure can be obtained by interfacial polymerization.

[0194] The intelligent film prepared in Example 2 was subjected to thermogravimetric analysis, and the results are shown in Table 4. Figure 8 Figure 8 It can be seen that the intelligent film frame only decomposes at 500℃, proving that the intelligent film has good thermal stability.

[0195] Example 3

[0196] This example provides a carboxylic acid modified polyether sulfone polymer of formula III-1, and the preparation method comprises the following specific steps:

[0197] ​​​​In anhydrous and anaerobic environment, 4,4'-difluorodiphenyl sulfone 40.0 mmol (10.18 g), 4,4'-dihydroxydiphenyl 32.0 mmol (5.96 g), 4,4'-dihydroxybenzoic acid 30.0 mmol (9.00 g), potassium carbonate 8.0 g, toluene 28 mL and cyclobutane sulfone 60 mL were added into a three-necked flask, and the resulting mixture was heated to 145°C under stirring and refluxed for 4 h. During the reaction, toluene was used to carry out the water generated in the system. After the reaction, the resulting system was heated to 180°C and reacted for 9 h. After the reaction was completed, it was observed that the viscosity of the product system no longer changed. The resulting product system was poured into deionized water to precipitate solid material, which was filtered through a membrane filter. The resulting solid material was crushed and washed with boiling water three times and then with ethanol three times. After washing, it was dried at 120°C under vacuum to constant weight to obtain a carboxylic acid modified polyether sulfone compound of formula III-1 with a specific 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 example provides a smart membrane constructed by a responsive porous material of formula I-1 and a carboxylic acid modified polyether sulfone polymer of formula III-1. The preparation method comprises the following specific steps:

[0200] The carboxylic acid modified polyether sulfone polymer prepared in Example 3 was mixed with N,N-dimethylformamide 10 mL at room temperature (25°C) for 1 h. After ultrasonic treatment, the resulting mixture was allowed to stand for 1 h. The supernatant was collected in a filter flask using a dropper, and then filtered through an organic filter membrane. The filter membrane with the carboxylic acid modified polyether sulfone membrane was dried at 50°C under vacuum for 24 h to obtain a modified polyether sulfone membrane.

[0201] The modified polyether sulfone film was placed in the middle of the H-shaped test tube, and the reaction conditions of the smart film prepared in reference example 1 were used on both sides of the electrolytic cell. 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'-dipyridyl-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 (acetonitrile 15 mL / deionized water 35 mL), while acetic acid (10 μL) was added, and placed on the right side of the H-shaped test tube; after adding the above components, the reaction was carried out at room temperature for 96 h, and the monomers on both sides diffused into the modified polyether sulfone film to form a film; after the reaction, the two-phase solution was removed, and solvent replacement was carried out by sequentially immersing in N,N-dimethylformamide, acetonitrile, methanol and acetone, each solvent was replaced for 3 times, each time for 12 h, and dried at 100°C for 18 h to obtain a smart film, which is denoted as TB-COF@COOH-PES.

[0202] Example 5

[0203] The present example provides a smart film constructed by a responsive porous material of formula II-1 and a carboxylic acid modified polyether sulfone polymer of formula III-1, and the preparation method comprises the following specific steps:

[0204] The carboxylic acid modified polyether sulfone polymer prepared in example 3 was mixed with N,N-dimethylformamide 10 mL, ultrasonicated at 75°C for 1 h, and the obtained mixture was allowed to stand for 1 h after ultrasonication to observe the dissolution of the polymer. The upper clear liquid was taken out and filtered by an organic filter to obtain a carboxylic acid modified polyether sulfone polymer solution, which was ready for use.

[0205] The COF-300 smart film prepared in example 2 was subjected to solvent replacement by sequentially immersing in N,N-dimethylformamide, acetonitrile, methanol and acetone, each solvent was replaced for 3 times, each time for 12 h. The COF-300 smart film was ground to obtain fine COF-300 smart film powder, which was mixed with the carboxylic acid modified polyether sulfone polymer solution ready for use by stirring. The COF-300 smart film powder and the carboxylic acid modified polyether sulfone polymer solution were mixed and cast on a flat glass, and dried at 50°C under vacuum for 24 h to obtain a smart film, which is denoted as COF-300@COOH-PES.

[0206] Example 6

[0207] The present example provides a pH-responsive smart film prepared from a responsive porous material combined by formula A-1 and formula B-10. The smart film is prepared by interfacial polymerization, and 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) while adding acetic acid (10 μL) to obtain a second phase solution.

[0210] 5 mL of an aqueous acetic acid solution was added as a buffer layer between the two-phase interface, and after adding the above components, the reaction was carried out at 50°C for 48 h, and a COF film was formed at the interface; after the reaction, the two-phase solutions were removed, and the product was subjected to solvent replacement with N,N-dimethylformamide, acetonitrile, methanol and acetone in turn, 3 times for each solvent, each time for 12 h, and dried at 100°C for 18 h to obtain an intelligent film, which was recorded as TPDA-COF (2D COF).

[0211] Example 7

[0212] This example provides a pH-responsive intelligent film prepared from a responsive porous material combined by formula A-1 and formula B-11, and the intelligent film is prepared by interfacial polymerization, and 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-benzene tetramine 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 an aqueous acetic acid solution was added as a buffer layer between the two-phase interface, and after adding the above components, the reaction was carried out at 50°C for 48 h, and a COF film was formed at the interface; after the reaction, the two-phase solutions were removed, and the product was subjected to solvent replacement with N,N-dimethylformamide, acetonitrile, methanol and acetone in turn, 3 times for each solvent, each time for 12 h, and dried at 100°C for 18 h to obtain an intelligent film, which was recorded as TPTB-COF (2D COF).

[0216] Example 8

[0217] This example provides a temperature-responsive intelligent film prepared from a responsive porous material combined by formula A-1 and formula B-12, and the intelligent film is prepared by interfacial polymerization, and the specific steps are as follows:

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

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

[0220] Add 5 mL of an aqueous acetic acid solution as a buffer layer between the two phase interfaces, and after adding the above components, react at room temperature for 48 h to form a COF film at the interface; after the reaction, remove the two phase solutions, and perform solvent replacement of the product with N,N-dimethylformamide, acetonitrile, methanol and acetone, 3 times for each solvent, each time soaking for 12 h, and dry at 100 °C for 18 h to obtain a smart film, which is recorded as TPPD-COF (2D COF).

[0221] Example 9

[0222] This example provides a smart film constructed from the responsive porous material prepared in Example 6 and the carboxylic acid modified polyether sulfone polymer of formula III-1, and the preparation method comprises the following specific steps:

[0223] Mix 6.250 mg of the carboxylic acid modified polyether sulfone polymer prepared in Example 3 with 10 mL of N,N-dimethylformamide, and ultrasonicate at 75 °C for 1 h; after ultrasonication, place the resulting mixture for 1 h, and use a dropper to take the supernatant and perform suction filtration through an organic filter membrane to obtain a carboxylic acid modified polyether sulfone polymer solution, which is ready for use.

[0224] Use the TPDA-COF smart film prepared in Example 6 to perform solvent replacement with N,N-dimethylformamide, acetonitrile, methanol and acetone, 3 times for each solvent, each time soaking for 12 h. Grind the COF-300 smart film to obtain fine TPDA-COF smart film powder, and mix the TPDA-COF smart film powder with the carboxylic acid modified polyether sulfone polymer solution ready for use by stirring thoroughly. Pour the mixture of the TPDA-COF smart film powder and the carboxylic acid modified polyether sulfone polymer solution onto a flat glass, and dry at 50 °C under vacuum conditions for 24 h to obtain a smart film, which is recorded as TPDA-COF@COOH-PES.

[0225] Example 10

[0226] This example provides a smart film constructed from the responsive porous material prepared in Example 8 and the carboxylic acid modified polyether sulfone polymer of formula III-1, and the preparation method comprises the following specific steps:

[0227] The carboxylic acid modified polyether sulfone polymer prepared in Example 3 was mixed with N,N-dimethylformamide 10 mL at 75°C for 1 h, and the obtained mixture was allowed to stand for 1 h after ultrasonication. The supernatant was taken with a dropper and filtered through an organic filter to obtain a carboxylic acid modified polyether sulfone polymer solution, which was used as needed.

[0228] The TPPD-COF smart film prepared in Example 8 was subjected to solvent replacement with N,N-dimethylformamide, acetonitrile, methanol and acetone in turn, and each solvent was replaced 3 times with 12 h of immersion each time. The COF-300 smart film was ground to obtain fine TPPD-COF smart film powder, which was mixed with the carboxylic acid modified polyether sulfone polymer solution prepared in Example 3 by stirring. The mixture of the TPPD-COF smart film powder and the carboxylic acid modified polyether sulfone polymer solution was poured onto a flat glass and dried at 50°C under vacuum for 24 h to obtain a smart film, which was denoted as TPPD-COF@COOH-PES.

[0229] Example 11

[0230] This example provides a solvent and pH multi-response smart film prepared from a combination of Formula A-9 and Formula B-5 responsive porous materials. The smart film is prepared by interfacial polymerization, and the specific steps are as follows: The smart film is constructed with the carboxylic acid modified polyether sulfone polymer of Formula III-1, and the preparation method comprises the following specific steps:

[0231] Tetraaldehyde tetraphenylmethane (TFMA, 86.4 mg, 0.2 mmol) and 2,2'-carboxyl-4,4'-diaminobiphenyl (DMP, 126.8 mg, 0.4 mmol) were dissolved in toluene (40 mL) and placed in a 50 mL polytetrafluoroethylene-lined reaction kettle at a temperature of 120°C for 24 h to prepare a powder (COF-320). The powder was subjected to solvent replacement with N,N-dimethylformamide, acetonitrile, methanol and acetone in turn, and each solvent was replaced 3 times with 12 h of immersion each time. The powder was dried at 120°C under vacuum for 12 h and used as needed.

[0232] The carboxylic acid modified polyether sulfone polymer prepared in Example 3 was mixed with N,N-dimethylformamide 10 mL at 75°C for 1 h, and the obtained mixture was allowed to stand for 1 h after ultrasonication. The supernatant was taken with a dropper and filtered through an organic filter to obtain a carboxylic acid modified polyether sulfone polymer solution, which was used as needed.

[0233] The COF-320@COOH smart membrane powder is mixed with the carboxylic acid modified polyether sulfone polymer solution to be used above by stirring, and the mixed COF-320@COOH smart membrane powder and carboxylic acid modified polyether sulfone polymer solution are poured on a flat glass and dried at 50°C under vacuum for 24h to obtain a smart membrane, which is denoted as COF-320@COOH@COOH-PES.

[0234] Example 12

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

[0236] Tetraformyltetraphenylmethane (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 reaction kettle at a temperature of 100°C for a time of 18h to prepare a powder (COF-320). Solvent replacement was performed sequentially using N,N-dimethylformamide, acetonitrile, methanol and acetone, with each solvent being replaced 3 times and each time being soaked for 12h. Vacuum drying at 120°C for 12h, and the powder is ready for use.

[0237] The carboxylic acid modified polyether sulfone polymer prepared in Example 3, 6.250 mg, is mixed with N,N-dimethylformamide, 10 mL, and ultrasonicated at 75°C for 1h. After ultrasonication, the resulting mixture is allowed to stand for 1h. The supernatant is taken using a dropper and filtered using an organic filter membrane to obtain a carboxylic acid modified polyether sulfone polymer solution, which is ready for use.

[0238] The COF-320 smart membrane powder is mixed with the carboxylic acid modified polyether sulfone polymer solution to be used above by stirring, and the mixed COF-320 smart membrane powder and carboxylic acid modified polyether sulfone polymer solution are poured on a flat glass and dried at 50°C under vacuum for 24h to obtain a smart membrane, which is denoted as COF-320@COOH-PES.

[0239] Test Example 1

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

[0241] The smart membrane prepared in Example 1 is placed in a double-chamber electrolytic cell, and 10 mmol / L and 10 mmol / L aqueous potassium chloride solutions are added to the two electrolytic chambers as electrolytes, respectively, a pair of Ag / AgCl electrodes are inserted, and the electrodes are connected with a picoammeter (i.e., an ammeter with a precision of 10-12 A), to form an ion transport performance monitoring device; a voltage is applied by using the Ag / AgCl electrodes, and the current under different voltage conditions is tested by using the picoammeter, and the results show that the above-mentioned smart membrane can obtain a linear I-V curve with a zero point under the condition, and the specific curve is shown in Figure 9 .

[0242] According to Figure 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 is subjected to osmotic energy collection test, and an osmotic energy collection device is assembled in a mature manner, and the specific steps are as follows:

[0245] The smart membrane prepared in Example 1 is placed in a double-chamber electrolytic cell, and 10 mmol / L and 500 mmol / L aqueous potassium chloride solutions are added to the two electrolytic chambers as electrolytes, respectively, a pair of Ag / AgCl electrodes are inserted, and the electrodes are connected with a picoammeter, to form a salt difference power device; a voltage is applied by using the Ag / AgCl electrodes, and the current under different voltage conditions is tested by using the picoammeter, and the results show that the above-mentioned smart membrane reads an open circuit voltage of 50 mV and a short circuit current of 5 μA under a 50-fold gradient concentration condition, and the specific curve is shown in Figure 10 .

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

[0247] Test Example 3

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

[0249] The smart membrane prepared in Example 1 is placed in a double-chamber electrolytic cell, and 10 mmol / L and 500 mmol / L potassium chloride aqueous solutions are respectively added to two electrolytic chambers as electrolytes, and the pH values of the two electrolytes are respectively 4, 7 and 10, and a pair of Ag / AgCl electrodes are inserted, and the electrodes are connected with a picoammeter to form a salt difference power generation device; the Ag / AgCl electrode is used to apply a voltage, and the picoammeter is used to test the current under different voltage conditions, and the results show that the smart membrane can obtain a linear I-V curve without passing through the origin under the condition of 50 times gradient concentration, as shown in FIG. 6, when the pH value is 4, the open circuit voltage is read as 110 mV, and the short circuit current is 12 μA; when the pH value is 7, the open circuit voltage is read as 50 mV, and the short circuit current is 5 μA; when the pH value is 10, the open circuit voltage is read as 78 mV, and the short circuit current is 8 μA.

[0250] Test Example 4

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

[0252] The smart membrane prepared in Example 1 is placed in a double-chamber electrolytic cell, and 10 mmol / L and 500 mmol / L potassium chloride aqueous solutions are respectively added to two electrolytic chambers as electrolytes, and the pH values of the two electrolytes are respectively 4, 7 and 10, and a pair of Ag / AgCl electrodes are inserted, and the electrodes are connected with a picoammeter to form a salt difference power generation device; the Ag / AgCl electrode is used to apply a voltage, and the picoammeter is used to test the current under different voltage conditions, and the results show that the smart membrane can obtain a linear I-V curve without passing through the origin under the condition of 50 times gradient concentration, as shown in FIG. 6, when the pH value is 4, the open circuit voltage is read as 110 mV, and the short circuit current is 12 μA; when the pH value is 7, the open circuit voltage is read as 50 mV, and the short circuit current is 5 μA; when the pH value is 10, the open circuit voltage is read as 78 mV, and the short circuit current is 8 μA. Figure 11

[0253] According to Figure 11 It can be seen that the change trend of open circuit voltage and short circuit current confirms that the charge density of 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 is tested for ion transport, and a transmembrane ion transport performance monitoring device is assembled in a mature manner, and the specific steps are as follows:

[0256] ​The smart film prepared in Example 2 is placed in a double-chamber electrolytic cell, and 10 mmol / L and 10 mmol / L aqueous potassium chloride solutions are added to the two electrolytic chambers as electrolytes, a pair of Ag / AgCl electrodes is inserted, and the electrodes are connected to a picoammeter to form an ion transport performance monitoring device; a voltage is applied using the Ag / AgCl electrodes, and the current under different voltage conditions is tested using the picoammeter, and the results show that the above-mentioned TB-COF film can obtain a linear I-V curve with a point of origin under the above conditions, as shown in Figure 12 .

[0257] According to Figure 12 It can be seen that the I-V curve passes through the origin, proving that the smart film of Example 2 has a certain uniformity.

[0258] Test Example 6

[0259] The smart film prepared in Example 2 is subjected to osmotic energy collection testing, and an osmotic energy collection device is assembled in a mature manner, and the specific steps are as follows:

[0260] The smart film prepared in Example 2 is placed in a double-chamber electrolytic cell, and 10 mmol / L and 500 mmol / L aqueous potassium chloride solutions are added to the two electrolytic chambers as electrolytes, a pair of Ag / AgCl electrodes is inserted, and the electrodes are connected to a picoammeter to form a salt difference power generation device; a voltage is applied using the Ag / AgCl electrodes, and the current under different voltage conditions is tested using the picoammeter, and the results show that the above-mentioned smart film can obtain a current density and a power density under a 50-fold gradient concentration condition, as shown in Figure 13 .

[0261] According to Figure 13 It can be seen that the current density of the smart film of Example 2 is 352 A / m 2 , and the maximum output power density is 9.66 W / m 2 .

[0262] Test Example 7

[0263] The smart film prepared in Example 2 is subjected to ion transport testing in a methanol solvent, and a transmembrane ion transport performance monitoring device is assembled in a mature manner, and the specific steps are as follows:

[0264] The smart membrane prepared in Example 2 is placed in a double-chamber electrolytic cell, and lithium chloride methanol organic solutions with concentrations of 10 mmol / L and 10 mmol / L are added into two electrolytic chambers as electrolytes (lithium chloride salt is selected because the solubility of sodium salt and potassium salt in methanol solvent is not high), a pair of Ag / AgCl electrodes are inserted, and the electrodes are connected with a picoammeter to form an ion transmission performance monitoring device; a voltage is applied by using the Ag / AgCl electrode, and a current under different voltage conditions is tested by using the picoammeter, and the results show that the smart membrane can obtain a linear I-V curve with a point above the origin under the condition, and the internal structure of the smart membrane in Example 2 does not change under the condition of methanol organic solvent as electrolyte, and maintains a uniform state, as shown in Figure 14

[0265] According to Figure 14 It can be seen that the ion transmission performance of the smart membrane in Example 2 in the methanol solvent is that the current signal decreases, and the COF-300 smart membrane in 100% water solvent shows a high current value of 3 μA at +2 V, but the current signal decreases by nearly 380% in 100% methanol solvent, which is the response of the methanol solvent, and increasing the size of the nano-channel reduces the probability of interaction between ions and channels.

[0266] Test Example 8

[0267] The smart membrane prepared in Example 2 is subjected to osmotic energy collection test in methanol solvent, and an osmotic energy collector is assembled in a mature manner, and the specific steps are as follows:

[0268] The smart membrane prepared in Example 2 is placed in a double-chamber electrolytic cell, and lithium chloride methanol organic solutions with concentrations of 10 mmol / L and 500 mmol / L are added into two electrolytic chambers as electrolytes (lithium chloride salt is selected because the solubility of sodium salt and potassium salt in methanol solvent is not high), a pair of Ag / AgCl electrodes are inserted, and the electrodes are connected with a picoammeter to form a salt difference power device; a voltage is applied by using the Ag / AgCl electrode, and a current under different voltage conditions is tested by using the picoammeter, and the results show that the TB-COF membrane can obtain a linear I-V curve without a point above the origin under the condition of 50 times gradient concentration, an open circuit voltage and a short circuit current value are read, and a current density and a power density are calculated. The results show that there is a certain change compared with the water electrolyte condition, which indicates that the ion channel in the smart membrane in Example 2 increases in size with the presence of organic solvent.

[0269] It can be seen from the above examples that the smart membrane provided by the application has excellent selectivity and permeability, can intelligently adjust the ion flow in the ion channel, can realize fine ion transmission function equivalent to that of a biological body, can selectively transmit ions, can quickly conduct specific ions, and can responsively control ion flow.

[0270] ​Although the above embodiments have been described in detail, it should be understood that these are only some embodiments of the present application, but not all embodiments. Other embodiments can be obtained on the basis of the above embodiments without creativity, and these embodiments all belong to the protection scope of the present application.

Claims

1. An intelligent film, characterized in that, The components include a responsive porous material and a modified component; The responsive porous material has a crystal cell structure as 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; Formula I; Formula II; In Formula I and Formula II, A is one of structures as shown in Formula A-1 to Formula A-10, and B is one of structures as shown in Formula B-1 to Formula B-14; Formula A-1 ; Formula A-2; Formula A-3; Formula A-4; Formula A-5; Formula A-6; Formula A-7; Formula A-8; Formula A-9; Formula A-10; Formula B-1; Formula B-2; Formula B-3; Formula B-4; Formula B-5; Formula B-6; Formula B-7; Formula B-8; Formula B-9; Formula B-10; Formula B-11; Formula B-12; Formula B-13; Formula B-14; The modified component is a special engineering plastic; the special engineering plastic is a modified polyether sulfone, and the structure of the modified polyether sulfone is as shown in Formula III: Formula III; In Formula III, m is 200 to 400, n is 200 to 400, and E is one of structures as shown in Formula E-1 and Formula E-2; Formula E-1 ; Formula E-2.

2. The smart film of claim 1, wherein, The preparation method of the responsive porous material includes the following steps: The first monomer, the second monomer, the catalyst and the organic solvent are mixed to perform a polycondensation reaction to obtain the responsive porous material; Or, the first monomer, the second monomer and the catalyst are respectively mixed with two-phase organic solvents to form two-phase reaction liquids to perform an interfacial polymerization reaction to obtain the responsive porous material; The first monomer is one of compounds as shown in Formula C-1 to Formula C-10; and the second monomer is one of compounds as shown in Formula D-1 to Formula D-14; Formula C-1 ; Formula C-2; Formula C-3; Formula C-4; Formula C-5; Formula C-6; Formula C-7; Formula C-8; Formula C-9; Formula C-10; Formula D-1 ; Formula D-2; Formula D-3; Formula D-4; Formula D-5; Formula D-6; Formula D-7; Formula D-8; Formula D-9; Formula D-10; Formula D-11 ; Formula D-12; Formula D-13; Formula D-14.

3. The smart film of claim 1, wherein, The preparation method of the modified polyether sulfone includes the following steps: the third monomer, the fourth monomer, the fifth monomer, a water-carrying agent, a catalyst and an organic solvent are mixed to perform a polycondensation reaction to obtain the modified polyether sulfone; and the structure of the third monomer is as shown in Formula F: Formula F; The structure of the fourth monomer is as shown in Formula G: Formula G; The fifth monomer includes at least one of a monomer as shown in Formula H-1 and a monomer as shown in Formula H-2: Formula H-1 ; Formula H-2.

4. The smart film of claim 1, wherein, The intelligent membrane further includes a modified component membrane; the modified component membrane is prepared from a modified component; and the two sides of the modified component membrane are permeated with the responsive porous material.

5. A method of producing the smart film according to any one of claims 1 to 4, characterized by, The method includes the following steps: The responsive porous material and the organic solvent are mixed, and then filtration and solvent removal are sequentially performed to obtain the intelligent membrane; Or, the first monomer, the second monomer and the catalyst are respectively mixed with two-phase organic solvents to form two-phase reaction liquids to perform an interfacial polymerization reaction to obtain the intelligent membrane; Or, the responsive porous material and the organic solvent are mixed, and then casting and solvent removal are sequentially performed to obtain the intelligent membrane.

6. The method of making the smart film of claim 5, wherein, The method includes the following steps: (1) The modified component and the organic solvent are mixed, and then standing, filtration and drying are sequentially performed to obtain a modified polyether sulfone membrane; (2) The first monomer, the second monomer, the catalyst and the organic solvent are mixed to perform a polycondensation reaction on the two sides of the modified polyether sulfone membrane respectively and independently to obtain the intelligent membrane.

7. Use of the intelligent membrane of any one of claims 1 to 4 or the intelligent membrane obtained by the preparation method of any one of claims 5 to 6 in a permeation energy conversion and collection device.

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