CN113346116A - Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof - Google Patents

Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof Download PDF

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CN113346116A
CN113346116A CN202110550492.1A CN202110550492A CN113346116A CN 113346116 A CN113346116 A CN 113346116A CN 202110550492 A CN202110550492 A CN 202110550492A CN 113346116 A CN113346116 A CN 113346116A
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刘宏芳
饶壮
李广芳
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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 polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and a preparation method thereof, wherein the preparation method comprises the following steps: (1) reacting metal salt with ligand to obtain corresponding metal organic framework MOF; (2) placing the MOF in an acid aqueous solution for etching to obtain a hollow metal organic framework H-MOF; (3) putting H-MOF into a dopamine hydrochloride buffer solution, and stirring for reaction to obtain a polydopamine modified hollow metal organic framework H-MOF-D; (4) adding H-MOF-D into a sulfonated polymer solution to form a membrane casting solution and a membrane material, and soaking the membrane material in hydrogen peroxide, acid and deionized water to obtain the polydopamine modified hollow metal organic framework modified polymer hybrid proton exchange membrane. According to the invention, the structure and the composition of key functional components in the proton exchange membrane are improved, so that the obtained proton exchange membrane has excellent proton conductivity under high and low humidity conditions.

Description

Polydopamine-modified hollow metal organic framework-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 polydopamine modified hollow metal organic framework (H-MOF-D) modified polymer hybrid proton exchange membrane and a preparation method thereof. In the invention, the metal organic framework is marked as MOF, the hollow metal organic framework is marked as H-MOF, and the polydopamine modified hollow metal organic framework is marked as H-MOF-D.
Background
The pem fuel cell has the advantages of no pollution and high efficiency, has become one of the most competitive power sources for internal combustion engines, and is receiving wide attention from various aspects such as the industry and academia. As one of the core components of a proton exchange membrane fuel cell, the proton exchange membrane not only provides a passage for proton transfer and transfer, but also effectively blocks the leakage of fuel between the anode and the cathode. Among them, proton conductivity is one of the most important parameters for evaluating proton exchange membrane performance, and improving proton conductivity is an effective way to obtain high-performance proton exchange membranes.
The Metal Organic Frameworks (MOFs) have the characteristics of high porosity, large specific surface area and easily-adjustable structure. Therefore, the catalyst has ideal application prospect in the aspects of gas adsorption, catalysis, drug loading, separation and the like. Recently, the application of MOFs to proton conduction has received a high degree of attention. Studies have shown that hydrogen bonding networks or functional sites in the MOFs pores are able to efficiently transport protons. Therefore, more and more MOFs modified proton exchange membranes were developed. However, most of the developed MOFs modified proton exchange membranes show a significant increase in proton conductivity only under high or low humidity conditions. Such as: chemical Communication (2013, 49,143-145) reported that Fe-MIL-101-NH2Adding into sulfonated 2, 6-dimethyl-p-polyphenoxy (SPPO) to obtain Fe-MIL-101-NH2A/SPPO hybrid membrane having a proton conductivity of 0.25S/cm at 90 ℃ and 80% RH (relative humidity) is significantly improved over an unmodified SPPO membrane, but it has no significant improvement in proton conductivity under low humidity conditions. The Membrane Science (Journal of Membrane Science458(2014)86-95) reports Fe-MIL-101-NH to be encapsulated with 1- (3-aminopropyl) imidazole (NAPI)2Adding into SPPO to obtain (NAPI-Fe-MIL-101-NH)2) SPPO hybrid membranes, which have a proton conductivity of 0.04S/cm at 160 ℃, 0.15% RH, a significant improvement over unmodified SPPO membranes, but which have a limited increase in proton conductivity under high humidity conditions. Chemical (chemical)Science (Chemical Science 2013,4,983-2O)2]·2HO0.5}nAdding into polyvinylpyrrolidone (PVP) to obtain { [ Ca (D-Hpmpc) (H)2O)2]·2HO0.5}na/PVP hybrid membrane with a proton conductivity of 2.8 x 10-5S/cm, is much more elevated than the PVP membrane without the added particles, but its proton conductivity is not much elevated at lower and higher humidity. Energy (Journal of Power Sources 262(2014)372-379) reports that doping sulfonated MIL (101) Cr in sulfonated polyether ether ketone (SPEEK) to prepare an MIL (101) Cr/SPEEK hybrid membrane has the proton conductivity reaching 0.306S/cm at 75 ℃ and 100% RH, and is obviously improved compared with an unmodified SPEEK membrane, but has little improvement on the proton conductivity under a low humidity condition. Chemical material A (Journal of Materials Chemistry A2015, 3,15838-15842) reports that a ZIF-8@ GO compound of GO and ZIF-8 is doped into perfluorosulfonic acid resin Nafion to prepare a ZIF-8@ GO/Nafion hybrid membrane, the proton conductivity of the membrane reaches 0.28S/cm at 120 ℃ and 40% RH, and the improvement is great compared with that of an unmodified Nafion membrane, but the improvement of the proton conductivity of the membrane under a low humidity condition is not ideal. American society for chemical engineering applications Materials and interfaces&Interfaces 2017,9,26077-3The S-UiO-66@ GO of the H compound is doped into SPEEK to prepare an S-UiO-66@ GO/SPEEK hybrid membrane, the proton conductivity of the S-UiO-66@ GO/SPEEK hybrid membrane is respectively 0.268S/cm and 16.57mS/cm under the conditions of 70 ℃, 95% RH and 100 ℃ and 40% RH, and is respectively improved by 1.6 times and 5.0 times compared with the unmodified SPEEK membrane under the same conditions, however, the proton conductivity of the S-UiO-66@ GO hybrid membrane is not obviously improved under the low humidity condition. American society for chemical engineering applications Materials and interfaces&Interfaces 2017,9,35075-35085) reported that doping 2D ZIF-8/carbon nanotube composite (ZCN) in SPEEK produced ZCN/SPEEK hybrid membrane, which has proton conductivity of 50.24mS/cm at 120 ℃, 30% RH, and is significantly improved compared with unmodified SPEEK membrane. But it has limited improvement in proton conductivity under lower humidity conditions. The Journal of Membrane Science 565(2018)281-292 describes the reaction of Cr-MIL-101-NH2Passing through the heartThe Sbsberg reaction (Hinsberg reaction) is bonded on the aromatic skeleton of sulfonated polyether sulfone (SPES) to prepare SPES-Cr-MIL-101-NH2The proton conductivity of the composite membrane under the conditions of 160 ℃ and 0% RH is 0.041S/cm, which is obviously improved compared with that of an unmodified SPES membrane, but the proton conductivity of the composite membrane under the high humidity condition is improved to a limited extent. American society for chemical engineering applications Materials and interfaces&Interfaces 2019,11,39979-39990) reported that flower-like MIL-53(Al) -NH2Doping to SPES to produce MIL-53(Al) -NH2A/SPES hybrid membrane has a proton conductivity of 0.248S/cm at 80 deg.C, 100% RH, which is nearly 1.6 times higher than that of the unmodified SPES membrane, however, it has less proton conductivity improvement at low humidity. The Membrane Science (Journal of Membrane Science 601(2020)117914) reported that 3D network-like ZIF-8 complex (3DNWS) formed by modifying ZIF-8 on polymetaphenylene diamide nanofibers was doped into Nafion to obtain a 3DNWS/Nafion hybrid Membrane having a proton conductivity of 0.258S/cm at 80 ℃ and 100% RH which is 2.1 times that of the unmodified Nafion Membrane, but having little improvement in proton conductivity under low humidity conditions. Therefore, it is very important and urgent to prepare MOF-modified hybrid proton exchange membranes having excellent proton conductivity under both high and low humidity conditions.
The inventor of the invention obtained earlier research on a polymer hybrid proton exchange membrane modified by a metal organic framework structure and a preparation method thereof (see Chinese patent document with application number 201610552499), and although the invention also relates to a polymer hybrid proton exchange membrane and a preparation method thereof, the examples of the former patent show that the proton conductivity of the prepared proton exchange membrane at 90 ℃ and 95% RH is 0.303S/cm at most; the proton conductivity under anhydrous conditions at 120 ℃ is up to 3.403mS/cm, and there is still room for improvement. Moreover, since Graphene Oxide (GO) needs to be used in the previous research result, the preparation of GO requires oxidation of graphite by concentrated acid and the like and repeated cleaning after oxidation, and the cost of GO preparation is relatively high, which still has a great practical improvement demand.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention aims to provide a polydopamine modified hollow metal organic framework modified polymer hybrid proton exchange membrane and a preparation method thereof, wherein the structure and the composition of key functional components in the proton exchange membrane are improved, and based on the functional component, namely a polydopamine modified hollow metal organic framework (H-MOF-D), the polydopamine modified hollow metal organic framework (H-MOF-D) is prepared firstly and then doped into a polymer, the proton exchange membrane obtained correspondingly has excellent proton conductivity under high and low humidity conditions, meanwhile, the methanol fuel has the characteristics of low methanol permeability, excellent use stability, low fuel permeability, excellent proton conductivity under high and low humidity conditions, good stability and the like.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a polydopamine modified hollow metal organic framework modified polymer hybrid proton exchange membrane, comprising the following steps:
(1) adding metal salt and ligand into a reaction solvent, and performing ultrasonic treatment to fully dissolve the metal salt and the ligand to form a precursor solution; then, stirring the precursor solution at 5-100 ℃ for reaction for 1-74 h, separating the product, washing the separated product with a low-boiling-point solvent with a boiling point not higher than 80 ℃, and drying to obtain a corresponding metal organic framework;
wherein the metal salt is one or a mixture of more of transition metal salt and lanthanide metal salt; the ligand is one or a mixture of more of aromatic carboxylic acid compounds and nitrogen-containing heterocyclic compounds;
(2) placing the metal organic framework obtained in the step (1) in an acid water solution for etching for 1-200 min, then separating a product, cleaning the separated product with a low-boiling-point solvent with a boiling point not higher than 80 ℃, and drying to obtain a hollow metal organic framework;
(3) putting the hollow metal organic framework obtained in the step (2) into a dopamine hydrochloride buffer solution with the pH value of 7-12, stirring for 1-48 h at the temperature of 10-80 ℃, separating the product, washing the separated product with deionized water, and freeze-drying to obtain a polydopamine modified hollow metal organic framework;
(4) adding the polydopamine-modified hollow metal organic framework obtained in the step (3) into a sulfonated polymer solution, and performing ultrasonic treatment to obtain a uniformly dispersed membrane 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 polydopamine-modified hollow metal organic framework modified polymer hybrid proton exchange membrane.
As a further preferred aspect of the present invention, in the step (3), the buffer solution is a tris solution; the concentration of the dopamine hydrochloride in the dopamine hydrochloride buffer solution is 0.05-4 g/L, preferably 0.08-3.2 g/L.
As a further preferable mode of the present invention, in the step (2), the acid is one or a mixture of several of monohydroxybenzoic acid, bishydroxybenzoic acid, trihydroxybenzoic acid and tannic acid; the concentration of the acid water solution is 0.1-30 g/L, preferably 1-10 g/L.
In a further preferred aspect of the present invention, in the step (1), the molar ratio of the metal salt to the ligand is 1:7 to 1: 1.
In a further preferred embodiment of the present invention, in the step (1), the reaction solvent is N, N-dimethylformamide, N-diethylformamide, tetrahydrofuran, pyrrolidone, dimethylsulfoxide, or CH3OH、C2H5One or more of OH.
As a further preferred aspect of the present invention, in both of the step (1) and the step (2), the low-boiling solvent is CH3OH、C2H5OH、CHCl3、CH2Cl2、CH3One or more of Cl, acetone and butanone.
As a further preferred aspect of the present invention, in the step (4), 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 40 weight percent;
forming a film material by using the film casting solution, specifically coating the film casting solution to form a film;
the drying is to place the membrane material in a drying oven at 50-80 ℃, heat the membrane material to 110-150 ℃, and then keep the membrane material for 12-36 hours;
preferably, the heating rate of the heating is less than 0.5 ℃/min, and more preferably 0.1-0.5 ℃/min.
In a further preferred aspect of the present invention, in the step (4), the concentration of the hydrogen peroxide solution is 1 to 10 wt%; the concentration of the acid is 0.4-4 mol/L, and the acid is specifically one or a mixture of hydrochloric acid, sulfuric acid and phosphoric acid.
In a further preferred embodiment of the present invention, in 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 polydopamine modified hollow metal organic framework-based modified polymer hybrid proton exchange membrane prepared by the preparation method.
Through the technical scheme, compared with the traditional MOF modified polymer hybrid proton exchange membrane process, the preparation method disclosed by the invention has the advantages that the polydopamine modified hollow metal organic framework (H-MOF-D) is prepared firstly, and then is doped in the polymer to prepare the polydopamine modified hollow metal organic framework (H-MOF-D) modified polymer hybrid proton exchange membrane. Due to the high hydrophilicity and the hollow structure of the polydopamine-modified hollow metal organic framework (H-MOF-D), the water retention capacity of the hybrid proton exchange membrane is strong (namely, the proton conductivity of the hybrid membrane under a high-humidity condition is obviously improved); Polydopamine-NH modified on surface of metal organic framework structure2-SO-of a NH-functional group with a polymer3H can form effective acid-base pairs, so that protons can be effectively transferred between the formed acid-base pairs under the low-humidity condition, and the proton conductivity of the hybrid proton exchange membrane under the high-humidity and low-humidity conditions is remarkably improved. In addition, the hollow structure of the MOF has excellent capture effect on the fuel, so that the fuel permeability is effectively reduced. And is composed ofThe chemical, water and thermal stability and structural stability of the polydopamine modified hollow metal organic framework (H-MOF-D) are high, so that the hybrid proton exchange membrane has excellent use stability.
The polydopamine modified hollow metal organic framework (H-MOF-D) modified polymer hybrid proton exchange membrane obtained by the invention has good performances in proton transfer, fuel barrier and use stability, and has very low fuel permeability and excellent stability.
In addition, the method has the advantages of extremely simple operation process, lower production cost, mild preparation conditions, easiness for batch and large-scale production, good industrial production basis and wide application prospect.
Compared with the previous research on the metal-organic framework structure modified polymer hybrid proton exchange membrane and the preparation method thereof (see Chinese patent document with application number 201610552499), the proton exchange membrane prepared in the embodiment of the invention has the proton conductivity of 0.318S/cm at 80 ℃ and 95% RH (which is higher than the highest proton conductivity of 0.303S/cm at 90 ℃ and 95% RH in the previous patent) and the proton conductivity of 4.47mS/cm at 120 ℃ and under the anhydrous condition (which is obviously higher than the highest proton conductivity of 3.403mS/cm at 120 ℃ and under the anhydrous condition in the previous patent). On the other hand, the hollow ZIF-8(DTZIF-8) modified by doped particle poly-dopamine used in the embodiment of the invention is the doped particle GO @ UiO-66-NH used in the embodiment of the invention relative to the polymer hybrid proton exchange membrane modified by metal organic framework structure and the preparation method thereof2The synthesis is simpler and the cost is lower. According to the invention, Graphene Oxide (GO) is not required, and the preparation of GO requires oxidation of graphite by concentrated acid and the like and repeated cleaning after oxidation, and the preparation cost of GO is relatively high; the invention can effectively avoid the defect, taking ZIF-8 adopted in the embodiment of the invention as an example, the synthesis of ZIF-8 is only carried out by stirring in methanol solvent at room temperature, and in the earlier results, UiO-66-NH explored by the earlier results2The synthesis of (A) is carried out in N, N-Dimethylformamide (DMF) at 120 ℃, is significantly more complicated than the synthesis of ZIF-8, and UiO-66-NH2The ligand and the metal salt of (A) are 2-aminoterephthalic acid and ZrCl4Compared with ZIF-8 ligand and metal salt (2-methylimidazole and Zn (NO)3)2·6H2O) is more expensive in price; compared with the earlier achievement of 'the polymer hybrid proton exchange membrane modified by the metal organic framework structure and the preparation method thereof', the synthesis process is simpler and the synthesis cost is lower.
In addition, although the synthesis of doped particles in the present invention and the previous studies both utilized polymerization of dopamine to form polydopamine, the effects of the two are different. The polydopamine is mainly used for surface functionalization modification of doped particles, after the polydopamine is modified, the hydrophilic group can further increase the water retention of the hollow metal organic framework, and in addition, the-SO of the sulfonated polymer3H can react with-NH on polydopamine2The NH-forms an effective acid-base pair. Whereas in previous studies polydopamine was mainly used as GO and UiO-66-NH2The bridging agent is UiO-66-NH2Modified on GO so that UiO-66-NH2The coupling between them is more excellent.
Compared with the prior art, the preparation process mainly comprises the steps of synthesizing a Metal Organic Framework (MOF), and etching the metal organic framework into a hollow metal organic framework (H-MOF) through acid; forming a polydopamine modified hollow metal organic framework (H-MOF-D) by self-polymerization of dopamine on the outer layer of the hollow metal organic framework; and adding H-MOF-D into the sulfonated polymer solution to be uniformly dispersed to form a membrane casting solution and further form a membrane material, and soaking the membrane casting solution, the membrane material and the membrane material by using hydrogen peroxide, acid and deionized water to prepare the hybrid proton exchange membrane. The hybrid proton exchange membrane has mild preparation conditions and simple preparation process, strengthens the water retention of the membrane by utilizing the hollow structure of the H-MOF-D, further strengthens the water retention of the membrane by utilizing the absorption of hydrophilic groups of polydopamine on the surface of the H-MOF-D on the surrounding water, and also utilizes-SO of a sulfonated polymer3-NH of polydopamine on H and H-MOF-D surfaces2And the effective acid-base pair formed by NH-ensures that the proton conductivity of the prepared hybrid proton exchange membrane is obviously improved under high and low humidity conditions. Taking methanol as a non-aqueous solvent as an example, the hollow structure of H-MOF-D is alsoIs beneficial to the capture of methanol, and the methanol permeability of the obtained hybrid proton exchange membrane is lower. In addition, templates such as Graphene Oxide (GO), Carbon Nano Tubes (CNT), nano fibers and the like are not needed in the structure regulation of the doped particle MOF, and the doped particle MOF is obtained by directly etching with peracid in one step under mild conditions, which shows that the operation of the doped particle MOF structure regulation of the invention is simpler and more convenient, and the cost is lower. According to the invention, a ligand of a specific group is not required to be used in advance in the functionalization of the doped particle MOF, and the specific group is not required to be functionalized after the MOF is synthesized, but the poly-dopamine is formed through the self-polymerization of the dopamine, so that the degree of the functionalization can be easily controlled through the self-polymerization time of the dopamine, and the operation condition is milder, which shows that the operation condition is milder and simpler on the functionalization regulation and control of the doped particle MOF.
In conclusion, compared with the prior art, the invention can prepare functionalized particles with lower cost by a simpler process for doping a polymer to prepare a corresponding hybrid proton exchange membrane, and the proton conductivity of the obtained hybrid proton exchange membrane has better performance under high-humidity conditions (the relative humidity is not lower than 80%) and low-humidity conditions (the relative humidity is not higher than 20%, especially under anhydrous conditions).
Drawings
Fig. 1 is a comparison graph (95% RH) of temperature dependent proton conductivity of polydopamine modified hollow ZIF-8(DTZIF-8) hybrid proton exchange membranes (doping amounts of 1,3 and 5 wt% of Nafion matrix mass, respectively) and non-hybrid proton exchange membranes obtained in examples 2, 3 and 4 of the present invention. Wherein, the legend "RN" represents an unhybridized proton exchange membrane, "DTZIF-8/RN-1" represents a DTZIF-8 hybridized proton exchange membrane, the doping amount of DTZIF-8 accounts for 1 wt% of the mass of Nafion matrix, "DTZIF-8/RN-3" represents a DTZIF-8 hybridized proton exchange membrane, the doping amount of DTZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "DTZIF-8/RN-5" represents a DTZIF-8 hybridized proton exchange membrane, and the doping amount of DTZIF-8 accounts for 5 wt% of the mass of Nafion matrix.
FIG. 2 is a comparison graph of proton conductivity of a hollow ZIF-8(TZIF-8), a polydopamine modified ZIF-8(DZIF-8) and a polydopamine modified hollow ZIF-8(DTZIF-8) respectively hybridized proton exchange membrane (the doping amount accounts for 3 wt% of the mass of a Nafion matrix) after being etched by ZIF-8, a tannic acid aqueous solution and an unhybridized proton exchange membrane at 120 ℃ under an anhydrous condition. Wherein, the legend "RN" represents an unhybridized proton exchange membrane, "TZIF-8/RN-3" represents a TZIF-8 hybridized proton exchange membrane, and the doping amount of TZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "ZIF-8/RN-3" represents a ZIF-8 hybridized proton exchange membrane, and the doping amount of ZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "DZIF-8/RN-3" represents a DZIF-8 hybridized proton exchange membrane, and the doping amount of DZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "DTZIF-8/RN-3" represents a DTZIF-8 hybridized proton exchange membrane, and the doping amount of DTF-8 accounts for 3 wt% of the mass of NaZIon matrix.
FIG. 3 is a comparison graph (95% RH) of temperature dependent proton conductivity of hollow ZIF-8(TZIF-8), polydopamine modified ZIF-8(DZIF-8) and polydopamine modified hollow ZIF-8(DTZIF-8) respectively hybridized proton exchange membranes (the doping amount is 3 wt% of the mass of the Nafion matrix) and unhybridized proton exchange membranes after being etched by aqueous solution of ZIF-8, tannic acid. Wherein, the legend "RN" represents an unhybridized proton exchange membrane, "TZIF-8/RN-3" represents a TZIF-8 hybridized proton exchange membrane, and the doping amount of TZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "ZIF-8/RN-3" represents a ZIF-8 hybridized proton exchange membrane, and the doping amount of ZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "DZIF-8/RN-3" represents a DZIF-8 hybridized proton exchange membrane, and the doping amount of DZIF-8 accounts for 3 wt% of the mass of Nafion matrix, "DTZIF-8/RN-3" represents a DTZIF-8 hybridized proton exchange membrane, and the doping amount of DTF-8 accounts for 3 wt% of the mass of NaZIon matrix.
FIG. 4 is a graph of the stability of a polydopamine modified hollow ZIF-8(DTZIF-8) hybrid proton exchange membrane (the mass of the particles contained in the membrane is 3 wt% of the mass of the Nafion matrix) at 80 ℃ 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 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 polydopamine-modified hollow metal organic framework modified polymer hybrid proton exchange membrane comprises the steps of preparing a polydopamine-modified hollow metal organic framework (H-MOF-D), and doping the polydopamine-modified hollow metal organic framework into a polymer to obtain the polydopamine-modified hollow metal organic framework modified polymer hybrid proton exchange membrane.
Example 1
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8); (since the main hydrolysis product of tannic acid is trihydroxybenzoic acid, monohydroxybenzoic acid, bishydroxybenzoic acid or trihydroxybenzoic acid may be used instead of tannic acid in addition to tannic acid)
3. Weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 0.5 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the solution; the dispersion was carefully poured offPouring into a mold, quickly placing in a 70 ℃ oven, slowly heating to 120 ℃ after 2h from 70 ℃ and keeping for 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.111S/cm at 80 ℃ and 95% RH and the proton conductivity of 2.27 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.07 and 0.99 times higher (0.104S/cm and 1.14X 10) than unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 7.23X 10-8cm2s-1Is reduced by 55.1 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 2
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 1 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.125S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 2.93 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.20 and 1.57 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). The methanol permeability at 40 ℃ is 6.82X 10-8cm2s-1Is reduced by 57.7 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 3
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.255S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 3.66 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.45 and 2.21 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 5.32X 10-8cm2s-1Is reduced by 67.0 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
The DTZIF-8/RN-3 hybrid proton exchange membrane obtained in the embodiment shows, as shown in FIG. 2, the advantage of the DTZIF-8 in improving proton conductivity of the hybrid proton exchange membrane under low humidity compared with ZIF-8/RN-3, TZIF-8/RN-3 and DZIF-8/RN-3.
The DTZIF-8/RN-3 hybrid proton exchange membrane obtained in the embodiment shows the advantage of improving the proton conductivity of the DTZIF-8 hybrid proton exchange membrane under high humidity compared with ZIF-8/RN-3, TZIF-8/RN-3 and DZIF-8/RN-3, as shown in FIG. 3.
Example 4
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 5 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.219S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 3.28 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, respectively cross-linking with unmodified Nafion protonThe film change height was about 1.11 and 1.88 times (0.104S/cm and 1.14X 10-3S/cm). Methanol permeability at 40 ℃ of 6.12X 10-8cm2s-1Is reduced by 62.0 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 5
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 7 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+Type, then use to removeSoaking in sub water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.207S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 3.06 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.99 and 1.68 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). The methanol permeability at 40 ℃ is 6.68X 10-8cm2s-1Is reduced by 58.6 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 6
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 9.84g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 0.5 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the solution; will be provided withThe 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.165S/cm at 80 ℃ and 95% RH and the proton conductivity of 3.09X 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.59 and 1.71 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 5.53X 10-8cm2s-1Is reduced by 65.7 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 7
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 9.84g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 1 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.252S/cm at 80 ℃ and 95% RH and the proton conductivity of 3.53 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.42 and 2.10 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 4.86X 10-8cm2s-1Is reduced by 69.9 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 8
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 9.84g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.318S/cm at 80 ℃ and 95% RH and the proton conductivity of 4.47 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 2.06 and 2.92 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). The methanol permeability at 40 ℃ is 3.95X 10-8cm2s-1Is reduced by 75.5 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 9
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 9.84g of 2-methylimidazole into 400mL of methanol, ultrasonically dispersing the mixture into a uniform ZIF-8 precursor solution, transferring the solution into a flask, continuously stirring the solution at 25 ℃ for reacting for 16 hours, centrifugally separating a reaction product, cleaning the reaction product with fresh methanol solvent (cleaning the reaction product for multiple times according to actual conditions), and placing the reaction product at 50 DEG CKeeping the temperature in the vacuum oven for 6 hours to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 5 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.286S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 4.04 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.75 and 2.54 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 4.27X 10-8cm2s-1Is reduced by 73.5 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 10
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 9.84g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 7 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.263S/cm at 80 ℃ and 95% RH and the proton conductivity of 3.75 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.53 and 2.29 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 4.78X 10-8cm2s-1Specific to unmodified NafionThe proton exchange membrane is reduced by 70.3 percent (16.12 multiplied by 10)-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 11
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 1min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in this example has proton transfer at 80 ℃ and 95% RHThe conductivity is as high as 0.201S/cm, and the proton conductivity is 2.67X 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.93 and 1.34 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). The methanol permeability at 40 ℃ is 6.93X 10-8cm2s-1Is reduced by 57.0 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 12
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 200min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.214S/cm at 80 ℃ and 95% RH and the proton conductivity of 2.79X 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.06 and 1.45 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 6.21X 10-8cm2s-1Is reduced by 61.5 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 13
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the weighed TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 10mg of dopamine hydrochloride (the concentration of the dopamine hydrochloride is 0.05g/L), putting the mixture into an ice water bath, performing ultrasonic treatment for 30min, stirring the mixture at 25 ℃ for 24h, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of commercial Nafion solution (5 wt%) was taken and rotary evaporatedAbout half of the solvent was removed and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.236S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 2.42 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.27 and 1.12 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 6.14X 10-8cm2s-1Is reduced by 61.9 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 14
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 800mg of dopamine hydrochloride (the concentration of the dopamine hydrochloride is 4g/L), putting the mixture into an ice water bath, performing ultrasonic treatment for 30min, stirring the mixture at 25 ℃ for 24h, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.209S/cm at 80 ℃ and 95% RH and the proton conductivity of 3.14 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.01 and 1.75 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). The methanol permeability at 40 ℃ is 6.39X 10-8cm2s-1Is reduced by 60.4 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 15
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (0.1g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the example is as high as 0.197S/cm at 80 ℃ and 95% RH, and the proton conductivity of the proton exchange membrane prepared in the example is 2.65 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.89 and 1.32 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). The methanol permeability at 40 ℃ is 6.98X 10-8cm2s-1Is reduced by 56.7 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 16
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2O and 4.92g of 2-methylimidazole, adding the mixture into 400mL of methanol, and ultrasonically dispersing the mixture into a uniform ZIF-8 precursorAnd transferring the solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (for many times according to actual conditions), and keeping in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (30g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product for 5h in a vacuum oven at 50 ℃ to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 24h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.181S/cm at 80 ℃ and 95% RH and the proton conductivity of 2.27 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 0.74 and 0.99 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 7.14X 10-8cm2s-1Is reduced by 55.7 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). At 80 ℃ 95%Constant at RH for about 1508min, there was little decrease in proton conductivity.
Example 17
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution for 1h at 25 ℃, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidification at 80 ℃ for 1H converts the membrane to H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.239S/cm at 80 ℃ and 95% RH and the proton conductivity of 2.51 multiplied by 10-3S/cm, minAbout 1.30 and 1.20 times higher (0.104S/cm and 1.14X 10) than that of the unmodified Nafion proton exchange membrane-3S/cm). Methanol permeability at 40 ℃ of 6.23X 10-8cm2s-1Is reduced by 61.4 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
Example 18
1. 5.94g of Zn (NO) were weighed out separately3)2·6H2Adding O and 4.92g of 2-methylimidazole into 400mL of methanol, performing ultrasonic dispersion to obtain a uniform ZIF-8 precursor solution, transferring the uniform ZIF-8 precursor solution into a flask, continuously stirring at 25 ℃ for reacting for 16h, centrifugally separating a reaction product, cleaning with a fresh methanol solvent (cleaning for multiple times according to actual conditions), and then placing in a vacuum oven at 50 ℃ for 6h to obtain the metal organic framework ZIF-8.
2. Weighing 400mg of ZIF-8, placing the ZIF-8 in 300mL of tannic acid aqueous solution (4g/L) for etching for 15min, centrifugally separating a product, cleaning the product by using a fresh methanol solvent, and drying the product in a vacuum oven at 50 ℃ for 5h to obtain hollow ZIF-8 (TZIF-8);
3. weighing 100mg of TZIF-8, putting the TZIF-8 into 200mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment to uniformly disperse the TZIF-8, adding 50mg of dopamine hydrochloride into the solution, putting the solution into an ice water bath for ultrasonic treatment for 30min, stirring the solution at 25 ℃ for 48h, performing centrifugal separation to obtain a product, completely washing the product with deionized water, and performing freeze drying to obtain a polydopamine modified hollow metal organic framework (DTZIF-8);
4. 5mL of a commercial Nafion solution (5 wt%) was taken, about half of the solvent was removed by rotary evaporation, and 1.5mL of DMF was added and rotary evaporation was continued for 10 min. Adding DTZIF-8 accounting for 3 wt% of solute of the Nafion solution into the Nafion solution, and performing ultrasonic treatment for 1 hour to uniformly disperse the 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 24 h. Finally, the membrane was first treated with 3 wt% H2O2The solution was soaked at 70 ℃ for 2h and subsequently 1M H2SO4Acidifying at 80 deg.C for 1h to convert the membraneIs H+And (3) soaking the membrane in deionized water to obtain the DTZIF-8 hybrid proton exchange membrane.
The proton exchange membrane prepared in the example has the proton conductivity of 0.252S/cm at 80 ℃ and 95% RH and the proton conductivity of 3.62 multiplied by 10 under the anhydrous condition at 120 DEG C-3S/cm, about 1.42 and 2.18 times higher (0.104S/cm and 1.14X 10) than the unmodified Nafion proton exchange membrane, respectively-3S/cm). Methanol permeability at 40 ℃ of 5.36X 10-8cm2s-1Is reduced by 66.7 percent (16.12 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2 s-1). The proton conductivity was almost not decreased at 80 ℃ and 95% RH for about 1508 min.
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.
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 (10)

1. A preparation method of a polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane is characterized by comprising the following steps:
(1) adding metal salt and ligand into a reaction solvent, and performing ultrasonic treatment to fully dissolve the metal salt and the ligand to form a precursor solution; then, stirring the precursor solution at 5-100 ℃ for reaction for 1-74 h, separating the product, washing the separated product with a low-boiling-point solvent with a boiling point not higher than 80 ℃, and drying to obtain a corresponding metal organic framework;
wherein the metal salt is one or a mixture of more of transition metal salt and lanthanide metal salt; the ligand is one or a mixture of more of aromatic carboxylic acid compounds and nitrogen-containing heterocyclic compounds;
(2) placing the metal organic framework obtained in the step (1) in an acid water solution for etching for 1-200 min, then separating a product, cleaning the separated product with a low-boiling-point solvent with a boiling point not higher than 80 ℃, and drying to obtain a hollow metal organic framework;
(3) putting the hollow metal organic framework obtained in the step (2) into a dopamine hydrochloride buffer solution with the pH value of 7-12, stirring for 1-48 h at the temperature of 10-80 ℃, separating the product, washing the separated product with deionized water, and freeze-drying to obtain a polydopamine modified hollow metal organic framework;
(4) adding the polydopamine-modified hollow metal organic framework obtained in the step (3) into a sulfonated polymer solution, and performing ultrasonic treatment to obtain a uniformly dispersed membrane 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 polydopamine-modified hollow metal organic framework modified polymer hybrid proton exchange membrane.
2. The method according to claim 1, wherein in the step (3), the buffer solution is a tris solution; the concentration of the dopamine hydrochloride in the dopamine hydrochloride buffer solution is 0.05-4 g/L, preferably 0.08-3.2 g/L.
3. The method according to claim 1, wherein in the step (2), the acid is one or more of monohydroxybenzoic acid, bishydroxybenzoic acid, trihydroxybenzoic acid and tannic acid; the concentration of the acid water solution is 0.1-30 g/L, preferably 1-10 g/L.
4. The method according to claim 1, wherein in the step (1), the molar ratio of the metal salt to the ligand is 1:7 to 1: 1.
5. The process according to claim 1, wherein in the step (1), the reaction solvent is N, N-dimethylformamide, N-diethylformamide, tetrahydrofuran, pyrrolidone, dimethylsulfoxide, CH3OH、C2H5One or more of OH.
6. The method according to claim 1, wherein in the step (1) and the step (2), the low-boiling solvent is CH3OH、C2H5OH、CHCl3、CH2Cl2、CH3One or more of Cl, acetone and butanone.
7. The method according to claim 1, wherein in the step (4), 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 40 weight percent;
forming a film material by using the film casting solution, specifically coating the film casting solution to form a film;
the drying is to place the membrane material in a drying oven at 50-80 ℃, heat the membrane material to 110-150 ℃, and then keep the membrane material for 12-36 hours;
preferably, the heating rate of the heating is less than 0.5 ℃/min, and more preferably 0.1-0.5 ℃/min.
8. The preparation method according to claim 1, wherein in the step (4), the concentration of the hydrogen peroxide solution is 1 to 10 wt%; the concentration of the acid is 0.4-4 mol/L, and the acid is specifically one or a mixture of hydrochloric acid, sulfuric acid and phosphoric acid.
9. 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.
10. The polydopamine-modified hollow metal organic framework-based modified polymer hybrid proton exchange membrane prepared by the preparation method of any one of claims 1 to 9.
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