CN115584045A - Covalent organic framework structure modified polymer hybrid proton exchange membrane and preparation thereof - Google Patents

Covalent organic framework structure modified polymer hybrid proton exchange membrane and preparation thereof Download PDF

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CN115584045A
CN115584045A CN202211294756.2A CN202211294756A CN115584045A CN 115584045 A CN115584045 A CN 115584045A CN 202211294756 A CN202211294756 A CN 202211294756A CN 115584045 A CN115584045 A CN 115584045A
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exchange membrane
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刘宏芳
饶壮
朱德雨
李广芳
张爱荣
贺颖
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the technical field of membranes, and discloses a polymer hybrid proton exchange membrane modified by a covalent organic framework structure and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Reacting melamine, terephthalaldehyde and carboxylated carbon nanotubes to obtain a covalent organic framework structure CNT @ SNW-1 which is mutually connected; (2) Performing zwitterion functionalization on CNT @ SNW-1 to obtain CNT @ ZSNW-1; (3) Adding CNT @ ZSNW-1 into a sulfonated polymer solution to form a membrane casting solution and a membrane material, and soaking the membrane material by hydrogen peroxide, acid and deionized water to obtain the mutually-connected polymer hybrid proton exchange membrane modified by the zwitterion functionalized covalent organic framework structure. According to the invention, through introducing the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1) into the proton exchange membrane, the proton conductivity of the prepared proton exchange membrane can be effectively improved, and the use stability is extremely high.

Description

Covalent organic framework structure modified polymer hybrid proton exchange membrane and preparation thereof
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a polymer hybrid proton exchange membrane modified by a covalent organic framework structure and a preparation method thereof.
Background
Proton exchange membrane fuel cells have become one of the most promising energy conversion devices, can directly convert chemical energy into electric energy, have the advantages of high efficiency and environmental protection, and are widely concerned by the industry and academia. As one of the core components of the proton exchange membrane fuel cell, the proton exchange membrane not only transfers protons, but also blocks the leakage of fuel between the anode and the cathode. The proton conductivity is a key factor for determining the performance of the proton exchange membrane fuel cell, and the improvement of the proton conductivity is an effective way for obtaining a high-performance proton exchange membrane.
Covalent Organic Frameworks (COFs) have the characteristics of ordered structure, large specific surface area and adjustable periodic pores. Therefore, the catalyst has ideal application prospect in the aspects of gas separation, catalysis, organic photoelectricity and the like. Recently, the applications of COFs in proton conduction have received a high degree of attention. Research shows that the highly regular pore channel structure of COFs isThe proton migration provides a fast channel, and the high specific surface area and pore volume thereof enable the surface thereof to be chemically introduced into the proton transfer unit with high density, and in addition, the channels thereof can accommodate more guest molecules to enhance the proton transfer capability. Therefore, more and more COFs modified proton exchange membranes are being developed. Such as: a NW ZSINW-1/Nafion hybrid Membrane was prepared by adding a zwitterion-functionalized COF (ZSNOW-1) to Nafion, a perfluorosulfonic acid resin. Improved proto of sulfonated poly (ether ketone) membrane by sulfonated equivalent organic frame nano sheets (International Journal of Hydrogen Energy 46 (2021) 26550-26559) reports sulfonated COF (TpPa-SO) 3 H) Adding into sulfonated polyether ether ketone (SPEEK) to obtain TpPa-SO 3 H/SPEEK hybrid membranes. An Enhanced proton conductivity of Nafion composite membrane by adsorbed phosphoric acid-impregnated organic frame (Journal of Power Sources 332 (2016) 265-273) reports on COF impregnated with phosphoric acid (H 3 PO 4 @ SNW-1) to Nafion to obtain H 3 PO 4 @ SNW-1/Nafion hybrid membranes. An incorporated self-associated phosphorus acidic acid and a ternary-fused-functionalized organic frame intra-sulfonated poly (ether ether ketone) for enhanced proton conductivity (Solid State Ionics 349 (2020) 115316) reported that a phosphotungstic acid (HPW) supported COF (HPW @ COF) was added to SPEEK to produce a HPW @ COF/SPEEK hybrid membrane. These hybrid membranes all exhibit enhanced proton conductivity compared to non-hybrid membranes. However, they are all made by directly adding COF particles to a film matrix, which makes the inter-COF particles not coherent enough, thereby greatly limiting the proton conductive value of COF. Therefore, it is extremely important and urgent to prepare a coherent functionalized COF structure for modifying a hybrid proton exchange membrane.
The inventor of the invention obtains the 'polymer hybrid proton exchange membrane modified by metal organic framework structure and the preparation method thereof' through earlier research (see application for reference)Chinese patent document No. 201610552499), although it also relates to a polymer hybrid proton exchange membrane and a method for preparing the same, the examples of the previous patent show that the proton conductivity of the prepared proton exchange membrane is up to 0.303S/cm at 90 ℃,95% RH, and still has room for improvement. Furthermore, since this previous work required a multi-step process to prepare a coherent amino-functionalized metal-organic framework structure, fresh CH was used after the first metal-organic framework preparation in the examples 3 OH solvent soaking for three days, changing fresh CH twice a day 3 The cleaning method of the OH solvent is relatively complicated in the whole preparation process, and still has a large actual improvement demand.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a polymer hybrid proton exchange membrane modified by a covalent organic framework structure and a preparation method thereof, wherein the structure and the composition of key functional components in the proton exchange membrane are improved, and a mutually coherent zwitterion functionalized covalent organic framework structure (namely CNT @ ZSNNW-1 is introduced into the proton exchange membrane, wherein SNW is the abbreviation of Schiff base networks, 1 is the name number of the Schiff base networks, and SNW-1 is a COF obtained by the reaction of melamine and terephthalaldehyde), so that the proton conductivity of the prepared proton exchange membrane can be effectively improved, and the use stability is extremely high.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a zwitterionic functionalized covalent organic framework modified polymer hybrid proton exchange membrane coherent with each other, comprising the following steps:
(1) Adding melamine, terephthalaldehyde and carboxylated carbon nanotubes into dimethyl sulfoxide (DMSO), and performing ultrasonic treatment to fully dissolve and disperse the melamine, the terephthalaldehyde and the carboxylated carbon nanotubes to form a precursor solution; then, stirring the precursor solution at 60-210 ℃ under the protective gas atmosphere for 6-45 h for reaction, then separating the product, washing the separated product with a solvent, and drying to obtain a corresponding mutually coherent covalent organic framework structure, which is marked as CNT @ SNW-1;
(2) Adding the CNT @ SNW-1 obtained in the step (1) into acetonitrile, performing ultrasonic treatment to fully disperse the acetonitrile, then adding 1,3-propane sultone, and performing stirring reaction for 10-30 h at 30-100 ℃ in a protective gas atmosphere; then separating the product, washing the separated product with a solvent, and drying to obtain a mutually coherent zwitterion functionalized covalent organic framework structure which is marked as CNT @ ZSNW-1;
(3) Adding the CNT @ ZSNW-1 obtained in the step (2) into a sulfonated polymer solution, and performing ultrasonic treatment to obtain a uniformly dispersed casting solution; and then, forming a membrane material by using the membrane casting solution, drying, and sequentially soaking by using a hydrogen peroxide solution, an acid and deionized water to obtain the mutually coherent polymer hybrid proton exchange membrane with the amphoteric ion functionalized covalent organic framework structure modified.
In a further preferred aspect of the present invention, in the step (1), the molar ratio of the melamine to the terephthalaldehyde is 1.5 to 1:6; the addition amount of the carboxylated carbon nano tube is 15.0 to 80.0wt percent of the mass of the melamine; the protective gas is one of nitrogen or argon.
In a further preferred aspect of the present invention, in the step (2), the mass ratio of CNT @ SNW-1 to 1,3-propanesultone is 1:3 to 1:7; the protective gas is one of nitrogen or argon.
In a further preferred embodiment of the present invention, in the step (3), the amount of CNT @ ZSNNW-1 added is 0.8 to 2.4wt% based on the mass of the sulfonated polymer matrix;
preferably, the amount of CNT @ ZSNNW-1 added is 1.2 to 2.0wt% based on the mass of the sulfonated polymer matrix.
In a further preferred embodiment of the present invention, in the step (1) and the step (2), the solvent used for the solvent washing is CH 3 OH、C 2 H 5 OH、CHCl 3 、CH 2 Cl 2 、CH 3 One or more of Cl, acetone, butanone and tetrahydrofuran.
As a further preferred aspect of the present invention, in the step (3), the sulfonated polymer solution is one of homogeneous solutions of perfluorinated sulfonic acid resin, sulfonated polyether ether ketone, sulfonated polybenzimidazole, sulfonated polyether sulfone, or sulfonated polyimide; the concentration of the sulfonated polymer solution is 1 to 40wt%;
forming a membrane material by using the membrane casting solution, specifically coating the membrane casting solution to form a membrane;
the drying is to put the membrane material into a baking oven with the temperature of 50-80 ℃, heat the membrane material to 110-150 ℃, and then keep the membrane material for 12-36 hours;
preferably, the temperature rise rate of the temperature rise is less than 0.5 ℃/min, more preferably 0.1-0.5 ℃/min.
In a further preferred aspect of the present invention, in the step (3), the concentration of the hydrogen peroxide solution is 1 to 10wt%; the concentration of the acid is 0.4-4 mol/L, and the acid is one or a mixture of hydrochloric acid, sulfuric acid and phosphoric acid.
In a further preferred embodiment of the present invention, in both the step (1) and the step (2), the drying is performed in a vacuum oven at 30 to 140 ℃ for 0.5 to 30 hours.
According to another aspect of the invention, the invention provides a polymer hybrid proton exchange membrane modified based on mutually coherent zwitterion functionalized covalent organic framework structure obtained by the method.
Compared with the traditional COF modified polymer hybrid proton exchange membrane process, the preparation method has the advantages that the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1) is introduced into the proton exchange membrane, so that the hybrid proton exchange membrane has strong water retention capacity due to the high hydrophilicity of zwitterions of the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1), and meanwhile, the zwitterions provide an additional proton transfer site for the hybrid proton exchange membrane; more importantly, the excellent coherent structure of the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1) ensures that interstitial proton transfer channels of COF particles and proton transfer channels between COF particles and membrane matrix interfaces are more continuous, thereby greatly reducing the transfer resistance of protons in the hybrid proton exchange membrane; thereby significantly improving the proton conductivity of the hybrid proton exchange membrane (as demonstrated in figure 2, infra). In addition, due to the high chemical, aqueous, thermal and structural stability of the mutually coherent zwitterionic functionalized covalent organic framework structure (CNT @ ZSNW-1), the hybrid proton exchange membrane has excellent stability in use (as demonstrated in FIG. 4 hereinafter).
The preparation method comprises the steps of firstly preparing mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1), and doping the covalent organic framework structure (CNT @ ZSNW-1) into a polymer to prepare the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1) modified polymer hybrid proton exchange membrane; specifically, CNT @ ZSNNW-1 is prepared by first forming a covalent organic skeleton structure (CNT @ SNW-1) in which melamine, terephthalaldehyde and a carboxylated carbon nanotube are linked to each other by a solvothermal reaction, and then subjecting CNT @ SNW-1 to zwitterionization by using 1,3-propanesultone based on a ring-opening reaction to obtain a zwitterionic covalent organic skeleton structure (CNT @ ZSNNW-1) in which melamine and terephthalaldehyde are linked to each other.
The method has the advantages of extremely simple operation process, lower production cost, mild preparation conditions, easy batch and large-scale production, good industrial production basis and wide application prospect. Compared with the polymer hybrid proton exchange membrane modified by the metal organic framework structure and the preparation method thereof in the previous research of the inventor (see the Chinese patent document with the application number of 201610552499), the proton exchange membrane prepared in the embodiment of the invention has the maximum proton conductivity of 0.327S/cm at 90 ℃ and 95% RH (higher than the maximum proton conductivity of 0.303S/cm at 90 ℃ and 95% RH in the previous patent), on the other hand, although the performance of the partially prepared proton exchange membrane in the embodiment of the invention is inferior to the previous research result, the amphoteric ion functionalized covalent organic framework structure (CNT @ ZSNW-1) with mutually coherent doping particles used in the invention is relative to the GO @ UiO-66-NH-modified polymer hybrid proton exchange membrane modified by the metal organic framework structure and the preparation method thereof 2 The preparation process is simpler and more convenient, and specifically: the invention only needs two steps when preparing the CNT @ ZSNNW-1 (the CNT @ SNW-1 is prepared firstly,then CNT @ SNW-1 zwitterion is functionalized to prepare CNT @ ZSNNW-1), and GO @ UiO-66-NH is prepared in the previous patent example 2 All are three steps (first preparing UiO-66-NH) 2 Then preparing poly dopamine modified graphene oxide (PDA-coated GO), and then adding UO-66-NH 2 Reacted with PDA-coated GO to obtain GO @ UiO-66-NH 2 ) (ii) a In addition, in the previous patent examples GO @ UiO-66-NH was prepared 2 For the prepared UiO-66-NH in the first step of (1) 2 All adopt fresh CH 3 Soaking in OH solvent for three days, and changing fresh CH twice a day 3 OH solvent, which is a relatively cumbersome and time-consuming cleaning method; the invention can effectively avoid the defect, and by taking the mutually coherent covalent organic framework structure CNT @ SNW-1 adopted in the embodiment of the invention as an example, the CNT @ SNW-1 can be cleaned up within 6h at most after preparation, so that the preparation process is simpler and more convenient compared with the earlier stage of the polymer hybrid proton exchange membrane modified by the metal organic framework structure and the preparation method thereof.
In addition, the optimum proton conductivity was 0.220S/cm compared to the reported ZSNW-1 hybrid proton exchange Membrane operation (Journal of Membrane Science 568 (2018) 1-9), whereas the optimum proton conductivity of the inventive examples was significantly higher, 0.327S/cm. Furthermore, the prior art (Journal of Membrane Science 568 (2018) 1-9) in the preparation of a covalent organic framework (SNW-1) without zwitterionic functionalization, with a stirring reaction time of 72h, is significantly greater than the time (28 h) taken for the example of the best proton conductivity of the invention to prepare a coherent covalent organic framework structure without zwitterionic functionalization (CNT @ SNW-1), and greater than the maximum time (45 h) taken for the example of the invention to prepare a coherent covalent organic framework structure without zwitterionic functionalization (CNT @ SNW-1). In addition, the proton conductivity of the proton exchange Membrane prepared in the example of the present invention, which takes the maximum time (45 h) for preparing CNT @ SNW-1, is 0.290S/cm, which is significantly greater than the optimum proton conductivity (0.220S/cm) of the proton exchange Membrane prepared in the prior art (Journal of Membrane Science 568 (2018) 1-9). Furthermore, the doping ratio of the doped particles ZSNW-1 (10 wt% of the mass of the polymer matrix) under the optimum proton conductivity in the example of the present invention in which the doped particles CNT @ ZSNW-1 account for 1.6wt% of the mass of the polymer matrix is significantly smaller than that in the prior art (Journal of Membrane Science 568 (2018) 1-9).
In conclusion, the modified proton exchange membrane obtained by the invention through the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1) modified polymer hybrid proton exchange membrane has good performance in the aspects of proton transfer and use stability.
Drawings
FIG. 1 is a schematic representation of the preparation of the mutually coherent zwitterionic functionalized covalent organic framework structure (CNT @ ZSNW-1) of example 1.
FIG. 2 is a graph showing the temperature dependence proton conductivity comparison (95% RH, RH: relative humidity) between mutually coherent zwitterionic functionalized covalent organic framework structure (CNT @ ZSNW-1) hybrid proton exchange membrane (doping amounts of 0.8,1.6 and 2.4wt% respectively based on the mass of Nafion matrix) and unhybridized proton exchange membrane obtained in examples 1, 2 and 3 of the present invention. Wherein, a legend "RN" represents an unhybridized proton exchange membrane, "CNT @ ZSQNW-1/RN-0.8" represents a CNT @ ZSNW-1 hybrid proton exchange membrane, and the doping amount of CNT @ ZSNW-1 accounts for 0.8wt% of the mass of Nafion matrix, "CNT @ ZSNW-1/RN-1.6" represents a CNT @ ZSNW-1 hybrid proton exchange membrane, and the doping amount of CNT @ ZSNW accounts for 1.6wt% of the mass of Nafion matrix, "CNT @ ZSNW-1/RN-2.4" represents a CNT @ ZSNW-1 hybrid proton exchange membrane, and the doping amount of CNT @ ZSNW-1 accounts for 2.4wt% of the mass of Nafion matrix.
FIG. 3 is a comparison graph of temperature-dependent proton conductivity (95% RH) of an unmodified COF (SNW-1), a carboxylated multi-walled carbon nanotube (abbreviated as CNT), a mutually coherent covalent organic framework structure (CNT @ SNW-1), a zwitterionic functionalized covalent organic framework (ZSNNW-1) and a mutually coherent zwitterionic functionalized covalent organic framework structure (CNT @ ZSNNW-1) respectively for a hybrid proton exchange membrane (the doping amount accounts for 1.6wt% of the mass of a Nafion matrix) and an unhybridized proton exchange membrane. Wherein the legend "RN" indicates an unhybridized proton exchange membrane, "SNW-1/RN-1.6" indicates an SNW-1 hybrid proton exchange membrane, and the SNW-1 doping accounts for 1.6wt% of the mass of Nafion matrix, "CNT/RN-1.6" indicates a CNT hybrid proton exchange membrane, and the CNT doping accounts for 1.6wt% of the mass of Nafion matrix, "CNT @ SNW-1/RN-1.6" indicates a CNT @ SNW-1 hybrid proton exchange membrane, and the CNT @ SNW-1 doping accounts for 1.6wt% of the mass of Nafion matrix, "ZNW-1/RN-1.6" indicates a ZNW-1 hybrid proton exchange membrane, and the NW-1 doping accounts for 1.6wt% of the mass of Nafion matrix, "ZNW-1/RN-1.6" indicates a @ ZNW-1 ZS-1 and the NW-1 doping accounts for the mass of Nafion matrix (i.6 wt% of the sample obtained by example, namely, 1.6wt% of hybrid CNT).
FIG. 4 is a graph of stability of a zwitterionic functionalized covalent organic framework structure (CNT @ ZSNW-1) hybrid proton exchange membrane (mass of particles contained in the membrane is 1.6wt% of the mass of the Nafion matrix, i.e., the sample obtained in example 2) coherent with each other at 90 deg.C and 95% RH.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the mutually coherent zwitterion functionalized covalent organic framework structure modified polymer hybrid proton exchange membrane comprises the steps of firstly preparing the mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1), and then doping the covalent organic framework structure into a polymer to obtain the mutually coherent zwitterion functionalized covalent organic framework structure modified polymer hybrid proton exchange membrane.
Example 1
1. Respectively weighing 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) into 25mL of dimethyl sulfoxide (DMSO), ultrasonically dissolving and dispersing the nanotubes into a uniform CNT @ SNW-1 precursor solution, transferring the CNT @ SNW-1 precursor solution into a flask, continuously stirring and reacting for 28 hours at 180 ℃ under an argon atmosphere, centrifugally separating a reaction product, sequentially cleaning the reaction product by using fresh Tetrahydrofuran (THF) and a methanol solvent (the total cleaning time is-3 hours), and then placing the reaction product in a vacuum oven at 70 ℃ for 12 hours to obtain the mutually-connected covalent organic framework structure (CNT @ SNW-1).
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 which accounts for 0.8wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidifying at 80 deg.C for 1H to convert the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example was as high as 0.190S/cm at 90 deg.C and 95% RH, which is about 0.45 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane, as shown in FIG. 2. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 2
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the film was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example was as high as 0.287S/cm at 90 deg.C and 95% RH, which is about 1.19 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane, as shown in FIG. 2. The proton conductivity was almost not decreased at 90 ℃ and 95% RH constantly for about 1570 min.
The hybrid proton exchange membrane of CNT @ ZSNNW-1/RN-1.6 obtained in this example, as shown in FIG. 3, exhibits the advantage of improving proton conductivity of CNT @ ZSNNW-1 to the hybrid proton exchange membrane compared with SNW-1/RN-1.6, CNT @ SNW-1/RN-1.6 and ZSNNW-1/RN-1.6 (the preparation processes of these samples are shown below). The proton conductivity of each membrane in FIG. 3 reached its highest at 90 deg.C, 95% RH, with CNT/RN-1.6 being 0.214S/cm, which is about 0.63 times higher than RN (0.131S/cm); ZSNW-1/RN-1.6 is 0.239S/cm, which is about 0.82 times higher than RN; the CNT @ ZSNW-1/RN-1.6 is 0.287S/cm, which is about 1.19 times higher than RN, and the promotion effect is obviously higher than that of CNT/RN-1.6 and ZSNW-1/RN-1.6; furthermore, as can be seen from FIG. 3, the proton conductivity of the CNT @ ZSNOW-1/RN-1.6 sample obtained by the present invention was more significantly increased with the temperature increase in the range of 80 to 90 ℃ (as shown in FIG. 3, the increase slope was the highest for the CNT @ ZSNOW-1/RN-1.6 sample in the range of 80 to 90 ℃).
In addition, the samples SNW-1/RN-1.6, CNT @ SNW-1/RN-1.6 and ZSNW-1/RN-1.6 to which FIG. 3 is directed were formed in the same manner as in step (3) of the method of forming CNT @ ZSNW-1/RN-1.6 of this example, wherein the method of producing the doped particles SNW-1 of SNW-1/RN-1.6 was similar to the step of producing CNT @ SNW-1 of step 1 of this example (except that CNT was not added); doped particle CNT of CNT/RN-1.6 CNT is directly obtained by market; the preparation method of the doped particle CNT @ SNW-1 of CNT @ SNW-1/RN-1.6 is similar to the step of preparing CNT @ SNW-1 in step 1 of the present example; ZSNNW-1/RN-1.6 doped particles ZSNNW-1 were prepared by first preparing SNW-1, similar to the procedure of example step 1 to prepare CNT @ SNW-1 (except that CNT was not added), and then functionalizing SNW-1 zwitterions to obtain ZSNNW-1, similar to the procedure of example step 2 to prepare CNT @ ZSNNW-1 (only the reactant CNT @ SNW-1 in step 2 was replaced with SNW-1).
Example 3
1. Respectively weighing 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) into 25mL of dimethyl sulfoxide (DMSO), ultrasonically dissolving and dispersing the nanotubes into a uniform CNT @ SNW-1 precursor solution, transferring the CNT @ SNW-1 precursor solution into a flask, continuously stirring and reacting for 28 hours at 180 ℃ under an argon atmosphere, centrifugally separating a reaction product, sequentially cleaning the reaction product by using fresh Tetrahydrofuran (THF) and a methanol solvent (the total cleaning time is-3 hours), and then placing the reaction product in a vacuum oven at 70 ℃ for 12 hours to obtain the mutually-connected covalent organic framework structure (CNT @ SNW-1).
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 2.4wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example was as high as 0.224S/cm at 90 deg.C and 95% RH, which is about 0.71 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane, as shown in FIG. 2. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 4
1. Respectively weighing 0.47g of melamine, 0.25g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1: 0.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine), adding the materials into 25mL of dimethyl sulfoxide (DMSO), ultrasonically dissolving and dispersing the materials into a uniform CNT @ SNW-1 precursor solution, transferring the precursor solution into a flask, continuously stirring and reacting for 28 hours at 180 ℃ under an argon atmosphere, centrifugally separating a reaction product, sequentially cleaning the solution by using fresh Tetrahydrofuran (THF) and a methanol solvent (the total cleaning time is-5.5 hours), and placing the solution in a vacuum oven at 70 ℃ for 12 hours to obtain the mutually-connected covalent organic framework structure (CNT @ SNW-1).
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-3.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.258S/cm at 90 deg.C and 95% RH, which is about 0.97 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 5
1. 0.47g of melamine, 3.00g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is 1:6) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, the reaction product is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totaling to 6 hours), and the mixture is placed in a vacuum oven at 70 ℃ for 12 hours to obtain the mutually-connected covalent organic framework structure (CNT @ SNW-1).
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reacting for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the cleaning time is totally-4 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutual coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.327S/cm at 90 deg.C and 95% RH, which is about 1.50 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 6
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.071g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 15.0 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), ultrasonically dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution, transferred into a flask, continuously stirred and reacted for 28 hours at 180 ℃ under an argon atmosphere, a reaction product is separated by centrifugation, sequentially cleaned by fresh Tetrahydrofuran (THF) and a methanol solvent (the total cleaning time is-6 hours), and then placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework structure (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-4 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNNW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.247S/cm at 90 c and 95% RH, which is about 0.89 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH constantly for about 1570 min.
Example 7
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.376g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 80.0 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totaling to-5 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-3.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.257S/cm at 90 deg.C and 95% RH, which is about 0.96 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 8
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the atmosphere of argon at 60 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totaling to-5 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-4 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNNW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.253S/cm at 90 deg.C and 95% RH, which is about 0.93 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH constantly for about 1570 min.
Example 9
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the atmosphere of argon at 210 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.289S/cm at 90 deg.C and 95% RH, which is about 1.21 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 10
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are ultrasonically dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution, the CNT @ SNW-1 precursor solution is transferred into a flask, then the stirring reaction is continuously carried out for 6 hours under the atmosphere of argon at 180 ℃, a reaction product is centrifugally separated, fresh Tetrahydrofuran (THF) and a methanol solvent are sequentially used for cleaning (the total cleaning time is-5.5 hours), and the solution is placed in a vacuum oven at 70 ℃ for 12 hours to obtain the mutually-connected covalent organic framework structure (CNT @ SNW-1).
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-4 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNNW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ over 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.246S/cm at 90 deg.C and 95% RH, which is about 0.88 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 11
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 45 hours under the atmosphere of argon at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidifying the membrane at 80 ℃ for 1hConversion to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.290S/cm at 90 deg.C and 95% RH, which is about 1.21 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 12
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 30 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-4 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNNW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.249S/cm at 90 deg.C and 95% RH, which is about 0.90 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 13
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 100 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 24 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, and after about half of the solvent was removed by rotary evaporation, 2mL of DMF was added and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in an oven at 70 ℃After 2h from 70 ℃ the temperature was slowly raised to 120 ℃ and maintained for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.290S/cm at 90 deg.C and 95% RH, which is about 1.21 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH constantly for about 1570 min.
Example 14
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 10 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-4 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZSNNW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, 2mL of DMF was added, and rotary evaporation was continued for 10min. Adding CNT @ ZSNW accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution1, and performing ultrasonic treatment for 1h to uniformly disperse the mixture; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidification at 80 ℃ for 1H converts the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.261S/cm at 90 deg.C and 95% RH, which is about 0.99 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 15
1. 0.47g of melamine, 0.75g of terephthalaldehyde (the molar ratio of the melamine to the terephthalaldehyde is-1.5) and 0.25g of carboxylated multi-walled carbon nanotubes (abbreviated as CNT, accounting for 53.2 mass percent of the melamine) are respectively weighed and added into 25mL of dimethyl sulfoxide (DMSO), the solutions are dissolved and dispersed into a uniform CNT @ SNW-1 precursor solution by ultrasonic treatment, the precursor solution is transferred into a flask, then the mixture is continuously stirred and reacted for 28 hours under the argon atmosphere at 180 ℃, a reaction product is separated by centrifugation, is sequentially cleaned by fresh Tetrahydrofuran (THF) and methanol solvent (the cleaning time is totally-3 hours), and is placed in a vacuum oven at 70 ℃ for 12 hours, so that the mutually-connected covalent organic framework (CNT @ SNW-1) is obtained.
2. Weighing 100mg of CNT @ SNW-1, placing the CNT @ SNW-1 in 15mL of acetonitrile, performing ultrasonic treatment to uniformly disperse the CNT @ SNW-1, transferring the CNT @ SNW-1 into a flask, heating the flask to 70 ℃ under a nitrogen atmosphere, dropwise adding a mixture of 0.5g of 1, 3-propane sultone and 5mL of acetonitrile within half an hour, keeping stirring for reaction for 30 hours, performing centrifugal separation to obtain a product, cleaning the product with a fresh acetone solvent (the total cleaning time is-2.5 hours), and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain a mutually coherent zwitterion functionalized covalent organic framework structure (CNT @ ZS NW-1).
3. 4mL of a commercial Nafion solution (5 wt%) was taken, and after removing about half of the solvent by rotary evaporation, the solution was added2mL of DMF was added and rotary evaporation was continued for 10min. Adding CNT @ ZSNW-1 accounting for 1.6wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1h to uniformly disperse the Nafion solution; the dispersion was carefully poured into a mould and quickly placed in a 70 ℃ oven, slowly warmed to 120 ℃ after 2h from 70 ℃ and held for 24h. Finally, the membrane was first treated with 3wt% H 2 O 2 The solution was soaked at 70 ℃ for 2h and then 1M H was used 2 SO 4 Acidifying at 80 deg.C for 1H to convert the membrane to H + And soaking the membrane in deionized water to obtain the CNT @ ZSNNW-1 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in this example is as high as 0.288S/cm at 90 deg.C and 95% RH, which is about 1.20 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 16
This example is substantially the same as example 2 except that the protective atmosphere in step 1 was replaced with nitrogen from argon.
Accordingly, the proton conductivity of the proton exchange membrane prepared in this example was as high as 0.285S/cm at 90 deg.C and 95% RH, which is about 1.18 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 17
This example is substantially the same as example 2 except that the protective atmosphere in step 2 was replaced with argon from nitrogen.
Accordingly, the proton conductivity of the proton exchange membrane prepared in this example is as high as 0.289S/cm at 90 ℃ and 95% RH, which is about 1.21 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
Example 18
This example is substantially the same as example 2 except that the protective atmosphere in step 1 was replaced with argon and the protective atmosphere in step 2 was replaced with nitrogen and argon.
Accordingly, the proton conductivity of the proton exchange membrane prepared in this example is as high as 0.286S/cm at 90 deg.C and 95% RH, which is about 1.18 times (0.131S/cm) higher than that of the unmodified Nafion proton exchange membrane. The proton conductivity was almost not decreased at 90 ℃ and 95% RH for about 1570min, which was constant.
In addition to the above examples, the sulfonated polymer solution (sulfonated polymer, i.e., matrix material constituting the proton exchange membrane) may be one of other homogeneous solutions of perfluorosulfonic acid resin, sulfonated polyetheretherketone, sulfonated polybenzimidazole, sulfonated polyethersulfone, or sulfonated polyimide, in addition to the above commercially available Nafion solution, and the solvent in the sulfonated polymer solution is a solvent capable of forming the sulfonated polymer into a homogeneous solution. In addition, the cleaning operations in step 1 and step 2 in the above embodiment may also include C 2 H 5 OH、CHCl 3 、CH 2 Cl 2 、CH 3 Other low boiling point solvents with a boiling point of not higher than 80 ℃ such as Cl and butanone.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. A preparation method of a mutually coherent zwitterion functionalized covalent organic framework structure modified polymer hybrid proton exchange membrane is characterized by comprising the following steps:
(1) Adding melamine, terephthalaldehyde and carboxylated carbon nanotubes into dimethyl sulfoxide (DMSO), and performing ultrasonic treatment to fully dissolve and disperse the melamine, the terephthalaldehyde and the carboxylated carbon nanotubes to form a precursor solution; then, stirring the precursor solution at 60-210 ℃ under the protective gas atmosphere for reaction for 6-45 h, then separating the product, washing the separated product with a solvent, and drying to obtain a corresponding mutually coherent covalent organic framework structure, which is marked as CNT @ SNW-1;
(2) Adding the CNT @ SNW-1 obtained in the step (1) into acetonitrile, performing ultrasonic treatment to fully disperse the acetonitrile, then adding 1,3-propane sultone, and performing stirring reaction for 10-30 h at 30-100 ℃ in a protective gas atmosphere; then separating the product, washing the separated product with a solvent, and drying to obtain a mutually coherent zwitterion functionalized covalent organic framework structure which is marked as CNT @ ZSNW-1;
(3) Adding the CNT @ ZSNW-1 obtained in the step (2) into a sulfonated polymer solution, and performing ultrasonic treatment to obtain a uniformly dispersed casting solution; and then, forming a membrane material by using the membrane casting solution, drying, and sequentially soaking by using a hydrogen peroxide solution, an acid and deionized water to obtain the mutually coherent polymer hybrid proton exchange membrane with the amphoteric ion functionalized covalent organic framework structure modified.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the melamine to the terephthalaldehyde is 1; the addition amount of the carboxylated carbon nano tube is 15.0 to 80.0wt percent of the mass of the melamine; the protective gas is one of nitrogen or argon.
3. The method according to claim 1, wherein in the step (2), the mass ratio of CNT @ SNW-1 to 1,3-propanesultone is 1:3 to 1:7; the protective gas is one of nitrogen or argon.
4. The method of claim 1, wherein in step (3), the amount of cnt @ zsnw-1 added is 0.8 to 2.4wt% based on the mass of the sulfonated polymer matrix;
preferably, the amount of CNT @ ZSNNW-1 added is 1.2 to 2.0wt% based on the mass of the sulfonated polymer matrix.
5. The method according to claim 1, wherein in the step (1) and the step (2), the solvent used for the solvent washing is CH 3 OH、C 2 H 5 OH、CHCl 3 、CH 2 Cl 2 、CH 3 One or more of Cl, acetone, butanone and tetrahydrofuran.
6. The method according to claim 1, wherein in the step (3), the sulfonated polymer solution is one of homogeneous solutions of perfluorosulfonic acid resin, sulfonated polyether ether ketone, sulfonated polybenzimidazole, sulfonated polyether sulfone, or sulfonated polyimide; the concentration of the sulfonated polymer solution is 1 to 40wt%;
forming a film material by using the film casting solution, specifically coating the film casting solution to form a film;
the drying is to put the membrane material into a baking oven with the temperature of 50-80 ℃, heat the membrane material to 110-150 ℃, and then keep the membrane material for 12-36 hours;
preferably, the temperature rise rate of the temperature rise is less than 0.5 ℃/min, and more preferably 0.1 to 0.5 ℃/min.
7. The method according to claim 1, wherein in the step (3), the concentration of the aqueous hydrogen peroxide solution is 1 to 10wt%; the concentration of the acid is 0.4-4 mol/L, and the acid is one or a mixture of hydrochloric acid, sulfuric acid and phosphoric acid.
8. The preparation method according to claim 1, wherein in the step (1) and the step (2), the drying is performed in a vacuum oven at 30-140 ℃ for 0.5-30 h.
9. A polymer hybrid proton exchange membrane modified based on a mutually coherent zwitterionic functionalized covalent organic framework structure obtained by the method of any one of claims 1 to 8.
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