CN111718504A - ZIF-67-based polyaryletherketone anion exchange membrane and preparation method thereof - Google Patents
ZIF-67-based polyaryletherketone anion exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ZIF-67-based polyaryletherketone anion exchange membrane and a preparation method thereof, belonging to the field of polymer chemistry and anion exchange membrane fuel cells, wherein the anion exchange membrane is obtained by reacting polyaryletherketone bromide (Br-PAEKS) with a metal organic framework material (ZIF-67) containing coordination imidazole. The method provided by the invention is characterized in that a nucleophilic polycondensation reaction is utilized to prepare a polyaryletherketone polymer, a solvothermal synthesis method is utilized to prepare ZIF-67, and a bromo-grafting reaction is utilized to prepare a ZIF-67-based polyaryletherketone anion exchange membrane. The ZIF-67-based polyaryletherketone anion-exchange membrane has the highest ionic conductivity of 0.087S/cm at the temperature of 80 ℃.
Description
Technical Field
The invention belongs to the field of polymer chemistry and anion exchange membrane fuel cells, and particularly relates to a ZIF-67-based polyaryletherketone anion exchange membrane and a preparation method thereof.
Background
In recent years, in order to pursue rapid economic development, fossil energy has been excessively used, and problems such as energy depletion and environmental pollution have been caused. At present, most of research focuses on the field of proton exchange membrane fuel cells, but because the catalysts of the proton exchange membrane fuel cells need to adopt expensive metals, the popularization and the development of the proton exchange membrane fuel cells are greatly limited. In contrast, the anion exchange membrane fuel cell has the advantages of fast fuel oxidation rate, low liquid alcohol fuel permeability, capability of using non-noble metal catalysts and the like, and has a wide application prospect, so that research on the anion exchange membrane fuel cell is widely concerned by researchers.
The performance of an anion exchange membrane as a core component of an anion exchange membrane fuel cell directly determines the performance of the anion exchange membrane fuel cell. The types of anion exchange membrane materials researched at present are quite various, and polyether sulfone, polyether ketone, polyvinyl alcohol, polyphenyl ether and the like can be used as the anion exchange membrane matrix materials. The anion exchange membrane also has a plurality of advantages, the catalyst with low price can be selected to replace the noble metal catalyst, the use cost of the fuel cell is greatly reduced, the application in a large range can not depend on the existing resource reserves, the popularization and the application in a large area are facilitated, and the anion exchange membrane is undoubtedly a great breakthrough for promoting the rapid development of the fuel cell.
Zeolitic imidazolate framework materials (ZIFs) are porous crystalline materials with organic imidazolate crosslinks to transition metals forming a tetrahedral framework. Belongs to a metal-organic framework compound (MOFs) and becomes a hot spot in the research field of new functional materials at present. Since the end of the 90 s of the 20 th century, MOFs opened up a completely new field for their electrochemical applications as proton conducting materials, while their applications in anion conducting materials have been gradually expanding in recent two years. The main problems faced in introducing MOFs structures into anion exchange membranes are low film-forming properties and low ionic conductivity.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the ZIF-67-based polyaryletherketone anion exchange membrane and the preparation method thereof.
The invention firstly provides a ZIF-67-based polyaryletherketone anion exchange membrane and a preparation method thereof, and the ZIF-67-based polyaryletherketone anion exchange membrane is obtained by reacting polyaryletherketone bromide (Br-PAEKS) with a metal organic framework material (ZIF-67) containing coordination imidazole. Wherein the metal organic framework material (ZIF-67) containing coordination imidazole accounts for 2-10% of the mass percent of the polyaryletherketone bromide (Br-PAEKS).
In the above technical solution, the polyaryletherketone bromide (Br-PAEKS) in step one has a structural formula shown as follows:
a preparation method of a ZIF-67-based polyaryletherketone anion exchange membrane comprises the following specific steps:
the method comprises the following steps: weighing PAEKS polymer, dissolving in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide, stirring in 80 deg.C oil bath for 5 hr, and discharging in alcohol to obtain light yellow floccule (Br-PAEKS);
step two: putting the light yellow floccule obtained in the step one into a beaker, adding an NMP solvent, and stirring at room temperature to dissolve the polymer to obtain a uniform solution;
step three: weighing ZIF-67 powder, adding the ZIF-67 powder into the uniform solution obtained in the step two, carrying out ultrasonic dispersion on the obtained mixed solution for 4 hours, and then continuously stirring for 2-3 days to obtain film forming liquid; wherein, the mass fraction of ZIF-67 in the Br-PAEKS matrix in the film-forming solution is 2-10 wt%;
step four: casting the film-forming liquid obtained in the third step to clean glassOn a board at 80oDrying for 48 hours, naturally cooling to room temperature, and then demoulding in water to obtain the ZIF-67-based polyaryletherketone anion exchange membrane;
step five: soaking the ZIF-67-based polyaryletherketone anion-exchange membrane obtained in the third step in a sodium hydroxide solution for 24 hours, and then washing in deionized water to remove residual sodium hydroxide, so as to obtain the ZIF-67-based polyaryletherketone anion-exchange membrane.
In the above technical solution, the polyaryletherketone in the first step is prepared by the following steps:
(1) weighing 0.02 mol of 4, 4' -difluorobenzophenone, 0.02 mol of methylhydroquinone and a certain amount of salt forming agent in 40 partsoC, drying for 12 hours in a vacuum oven; the salt forming agent is anhydrous potassium carbonate;
(2) under the protection of nitrogen, adding a monomer, a salt forming agent, a water-carrying agent and a solvent into a three-mouth bottle, refluxing with water at 125-145 ℃ for 3-5 hours, then discharging the water-carrying agent, raising the temperature to 165-170 ℃, and continuing to react for 2-3 hours to obtain the polyaryletherketone. Wherein the water-carrying agent is toluene, and the solvent is NMP; the salt forming agent is anhydrous potassium carbonate, and the dosage of the salt forming agent is 1-2 mol.
Preferably, the solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO).
Preferably, the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dimethylsulfoxide.
Preferably, the water-carrying agent is toluene.
Preferably, the preparation method of the metal organic framework material ZIF-67 containing coordinated imidazole in the third step is as follows:
weighing 2-methylimidazole and cobalt nitrate hexahydrate, respectively adding into a beaker, adding a methanol solution, reacting the mixed solution at room temperature for 24 hours, and performing centrifugal separation. The resulting solid was washed 3 times with methanol. The sample was dried overnight at 80 ℃ and was designated ZIF-67.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly provides a ZIF-67-based polyaryletherketone anion exchange membrane, wherein the mass fraction of ZIF-67 in a Br-PAEKS matrix is 2-10 wt%. The metal ions in the ZIF-67 are cobalt ions, and the high molecular polymer is a polyaryletherketone polymer. Compared with the prior art, the alkali resistance of the ZIF-67-based anion exchange membrane is improved by using the alkali stability of the imidazole organic ligand in the ZIF-67, and meanwhile, the reaction of the imidazole group in the imidazole organic ligand and the polyaryletherketone bromide enables the long chain of a macromolecule to penetrate through the ZIF-67 structure, the framework is a hydrophobic structure, and the imidazole is a hydrophilic group, so that the conduction efficiency is improved. The experimental results show that: the ZIF-67-based polyaryletherketone anion exchange membrane has the ionic conductivity of 0.048-0.087S/cm at 80 ℃, and the thickness of the ZIF-67-based polyaryletherketone anion exchange membrane is 18-22 mu m.
The invention also provides a preparation method of the ZIF-67-based polyaryletherketone anion exchange membrane. The ZIF-67-based polyaryletherketone anion exchange membrane has the advantages of simple preparation process, short production period, low cost and wide commercial prospect, and can be applied to the field of fuel cells.
Drawings
FIG. 1 is an XRD spectrum of ZIF-67 of the present invention.
FIG. 2 is a nuclear magnetic spectrum of PAEKS and Br-PAEKS in example 1.
FIG. 3 is a SEM photograph of the ZIF-67 based polyaryletherketone anion exchange membrane of example 1.
Detailed description of the invention
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a ZIF-67-based polyaryletherketone anion exchange membrane comprises the following specific steps:
(1) weighing PAEKS polymer, dissolving in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinimido into 80 ℃ oil bath, stirring for 5 hours, discharging in alcohol to obtain light yellow floccule (Br-PAEKS).
(2) 0.2 g of Br-PAEKS was weighed into a beaker, 6 ml of NMP solvent was added and the mixture was stirred at room temperature to dissolve the polymer and obtain a homogeneous solution. Wherein Br-PAEKS represents polyaryletherketone bromide; NMP stands for N-methyl-2-pyrrolidone.
(3) 0.004 g of ZIF-67 powder was weighed and added to the homogeneous solution of step (1). And ultrasonically dispersing the obtained mixed solution for 4 hours, and then continuously stirring for 48 hours to obtain a film forming solution. Wherein ZIF-67 represents a metal organic framework material containing coordinated imidazole; the mass fraction of ZIF-67 in the Br-PAEKS matrix in the film-forming solution is 2 wt%.
(4) Casting the deposition solution obtained in step (3) onto a clean glass plate at 80 deg.CoAnd C, drying for 48 hours, naturally cooling to room temperature, and then demoulding in water to obtain the ZIF-67-based polyaryletherketone anion exchange membrane.
(5) And (3) soaking the ZIF-67-based polyaryletherketone anion-exchange membrane obtained in the step (4) in a 1M sodium hydroxide solution for 24 hours, and then repeatedly washing the membrane in deionized water to remove residual sodium hydroxide, so as to obtain the pretreated ZIF-67-based polyaryletherketone anion-exchange membrane.
The preparation method of the polyaryletherketone sulfone in the step (1) comprises the following steps:
under the protection of nitrogen, 0.02 mol of 4, 4' -difluorobenzophenone and 0.02 mol of methylhydroquinone are added into a three-necked bottle, after uniform mixing, a salt forming agent, a water carrying agent and a solvent are added, after refluxing with water at 125-145 ℃ for 3-5 hours, the water carrying agent is discharged, the temperature is raised to 165-170 ℃, and the reaction is continued for 2-3 hours, so that the polyaryletherketone polymer is obtained.
The preparation method of the metal organic framework material ZIF-67 containing coordination imidazole in the step (3) is as follows:
weighing 2-methylimidazole and cobalt nitrate hexahydrate, respectively adding into a beaker, adding a methanol solution, reacting the mixed solution at room temperature for 24 hours, and performing centrifugal separation. The resulting solid was washed 3 times with methanol. The sample was dried overnight at 80 ℃ and was designated ZIF-67.
The obtained pre-treated ZIF-67 based polyaryletherketone anion exchange membrane is placed at 80oThe conductivity of the anion exchange composite membrane is 0.048S cm when tested under C-1Film thickness 12 μm at 30oTested under C, the conductivity of the material is 0.015 Scm-1. SEM of ZIF-67-based polyaryletherketone anion exchange membrane obtained in example 1 is shown in FIG. 2, and as can be seen from FIG. 3, the ZIF-67-based polyaryletherketone anion exchange membrane was successfully synthesized in the example.
Example 2
A preparation method of a ZIF-67-based polyaryletherketone anion exchange membrane comprises the following specific steps:
(1) weighing PAEKS polymer, dissolving in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinimido into 80 ℃ oil bath, stirring for 5 hours, discharging in alcohol to obtain light yellow floccule (Br-PAEKS).
(2) 0.2 g of Br-PAEKS was weighed into a beaker, 6 ml of NMP solvent was added and the mixture was stirred at room temperature to dissolve the polymer and obtain a homogeneous solution. Wherein Br-PAEKS represents polyaryletherketone bromide; NMP stands for N-methyl-2-pyrrolidone.
(3) 0.01 g of ZIF-67 powder was weighed and added to the homogeneous solution of step (1). And ultrasonically dispersing the obtained mixed solution for 4 hours, and then continuously stirring for 48 hours to obtain a film forming solution. Wherein ZIF-67 represents a metal organic framework material containing coordinated imidazole; the mass fraction of ZIF-67 in the Br-PAEKS matrix in the film-forming solution is 5 wt%.
(4) Casting the deposition solution obtained in step (3) onto a clean glass plate at 80 deg.CoAnd C, drying for 48 hours, naturally cooling to room temperature, and then demoulding in water to obtain the ZIF-67-based polyaryletherketone anion exchange membrane.
(5) And (3) soaking the ZIF-67-based polyaryletherketone anion-exchange membrane obtained in the step (4) in a 1M sodium hydroxide solution for 24 hours, and then repeatedly washing the membrane in deionized water to remove residual sodium hydroxide, so as to obtain the pretreated ZIF-67-based polyaryletherketone anion-exchange membrane.
The preparation method of the polyaryletherketone sulfone in the step (1) comprises the following steps:
under the protection of nitrogen, 0.02 mol of 4, 4' -difluorobenzophenone and 0.02 mol of methylhydroquinone are added into a three-necked bottle, after uniform mixing, a salt forming agent, a water carrying agent and a solvent are added, after refluxing with water at 125-145 ℃ for 3-5 hours, the water carrying agent is discharged, the temperature is raised to 165-170 ℃, and the reaction is continued for 2-3 hours, so that the polyaryletherketone polymer is obtained.
The preparation method of the metal organic framework material ZIF-67 containing coordination imidazole in the step (3) is as follows:
weighing 2-methylimidazole and cobalt nitrate hexahydrate, respectively adding into a beaker, adding a methanol solution, reacting the mixed solution at room temperature for 24 hours, and performing centrifugal separation. The resulting solid was washed 3 times with methanol. The sample was dried overnight at 80 ℃ and was designated ZIF-67.
The obtained pre-treated ZIF-67 based polyaryletherketone anion exchange membrane is placed at 80oThe conductivity of the anion exchange composite membrane is 0.060S cm when tested under C-1Film thickness 11 μm at 30oTested under C, the conductivity of the material is 0.019 Scm-1。
Example 3
A preparation method of a ZIF-67-based polyaryletherketone anion exchange membrane comprises the following specific steps:
(1) weighing PAEKS polymer, dissolving in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinimido into 80 ℃ oil bath, stirring for 5 hours, discharging in alcohol to obtain light yellow floccule (Br-PAEKS).
(2) 0.2 g of Br-PAEKS was weighed into a beaker, 6 ml of NMP solvent was added and the mixture was stirred at room temperature to dissolve the polymer and obtain a homogeneous solution. Wherein Br-PAEKS represents polyaryletherketone bromide; NMP stands for N-methyl-2-pyrrolidone.
(3) 0.016 g of ZIF-67 powder was weighed and added to the homogeneous solution of step (1). And ultrasonically dispersing the obtained mixed solution for 4 hours, and then continuously stirring for 48 hours to obtain a film forming solution. Wherein ZIF-67 represents a metal organic framework material containing coordinated imidazole; the mass fraction of ZIF-67 in the Br-PAEKS matrix in the film-forming solution is 8 wt%.
(4) Casting the deposition solution obtained in step (3) onto a clean glass plate at 80 deg.CoAnd C, drying for 48 hours, naturally cooling to room temperature, and then demoulding in water to obtain the ZIF-67-based polyaryletherketone anion exchange membrane.
(5) And (3) soaking the ZIF-67-based polyaryletherketone anion-exchange membrane obtained in the step (4) in a 1M sodium hydroxide solution for 24 hours, and then repeatedly washing the membrane in deionized water to remove residual sodium hydroxide, so as to obtain the pretreated ZIF-67-based polyaryletherketone anion-exchange membrane.
The preparation method of the polyaryletherketone sulfone in the step (1) comprises the following steps:
under the protection of nitrogen, 0.02 mol of 4, 4' -difluorobenzophenone and 0.02 mol of methylhydroquinone are added into a three-necked bottle, after uniform mixing, a salt forming agent, a water carrying agent and a solvent are added, after refluxing with water at 125-145 ℃ for 3-5 hours, the water carrying agent is discharged, the temperature is raised to 165-170 ℃, and the reaction is continued for 2-3 hours, so that the polyaryletherketone polymer is obtained.
The preparation method of the metal organic framework material ZIF-67 containing coordination imidazole in the step (3) is as follows:
weighing 2-methylimidazole and cobalt nitrate hexahydrate, respectively adding into a beaker, adding a methanol solution, reacting the mixed solution at room temperature for 24 hours, and performing centrifugal separation. The resulting solid was washed 3 times with methanol. The sample was dried overnight at 80 ℃ and was designated ZIF-67.
The obtained pre-treated ZIF-67 based polyaryletherketone anion exchange membrane is placed at 80oThe conductivity of the anion exchange composite membrane is 0.073S cm when tested under C-1The film thickness is 10 μm at 30oTested under C, the conductivity of the material is 0.020 Scm-1。
The above description of the embodiments is only for the purpose of assisting understanding of the method of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (6)
1. The ZIF-67-based polyaryletherketone anion exchange membrane is characterized by being obtained by reacting polyaryletherketone bromide (Br-PAEKS) with a metal organic framework material (ZIF-67) containing coordination imidazole, wherein the metal organic framework material (ZIF-67) containing coordination imidazole accounts for 2-10% of the polyaryletherketone bromide (Br-PAEKS) in percentage by mass, and the polyaryletherketone bromide (Br-PAEKS) has a structural formula shown as a formula I:
formula I.
2. The preparation method of the ZIF-67 based polyaryletherketone anion exchange membrane of claim 1, which is characterized by comprising the following specific steps:
the method comprises the following steps: weighing PAEKS polymer, dissolving in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide, stirring in 80 deg.C oil bath for 5 hr, and discharging in alcohol to obtain light yellow floccule (Br-PAEKS);
step two: putting the light yellow floccule obtained in the step one into a beaker, adding an NMP solvent, and stirring at room temperature to dissolve the polymer to obtain a uniform solution;
step three: weighing ZIF-67 powder, adding the ZIF-67 powder into the uniform solution obtained in the step two, carrying out ultrasonic dispersion on the obtained mixed solution for 4 hours, and then continuously stirring for 2-3 days to obtain film forming liquid; wherein, the mass fraction of ZIF-67 in the Br-PAEKS matrix in the film-forming solution is 2-10 wt%;
step four: casting the deposition solution obtained in step three onto a clean glass plate at 80 deg.CoDrying for 48 hours, naturally cooling to room temperature, and then demoulding in water to obtain the ZIF-67-based polyaryletherketone anion exchange membrane;
step five: soaking the ZIF-67-based polyaryletherketone anion-exchange membrane obtained in the third step in a sodium hydroxide solution for 24 hours, and then washing in deionized water to remove residual sodium hydroxide, so as to obtain the ZIF-67-based polyaryletherketone anion-exchange membrane.
3. The preparation method of the ZIF-67 based polyaryletherketone anion exchange membrane of claim 2, wherein the preparation method of polyaryletherketone comprises the following steps: under the protection of nitrogen, 0.02 mol of 4, 4' -difluorobenzophenone and 0.02 mol of methylhydroquinone are added into a three-necked bottle, after uniform mixing, a salt forming agent, a water carrying agent and a solvent are added, after refluxing with water at 125-145 ℃ for 3-5 hours, the water carrying agent is discharged, the temperature is raised to 165-170 ℃, and the reaction is continued for 2-3 hours, so that the polyaryletherketone polymer is obtained.
4. The method of claim 3, wherein the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, or dimethylsulfoxide.
5. The preparation method of the ZIF-67 based polyaryletherketone anion exchange membrane of claim 3, wherein the water-carrying agent is toluene.
6. The preparation method of the ZIF-67 based polyaryletherketone anion exchange membrane of claim 2, wherein the preparation method of the metal organic framework material ZIF-67 containing the coordinated imidazole in the third step is as follows:
weighing 2-methylimidazole and cobalt nitrate hexahydrate, respectively adding into a beaker, adding a methanol solution, reacting the mixed solution at room temperature for 24 hours, carrying out centrifugal separation, washing the obtained solid with methanol for 3 times, and drying at 80 ℃ overnight to obtain a sample as ZIF-67.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114471177A (en) * | 2022-01-30 | 2022-05-13 | 天津大学 | Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof |
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| CN113067022A (en) * | 2021-03-30 | 2021-07-02 | 长春工业大学 | Amino-containing sulfonated polyaryletherketone sulfone blended metal organic framework composite membrane and preparation method thereof |
| CN113178602A (en) * | 2021-04-25 | 2021-07-27 | 长春工业大学 | Preparation of ZIF-8/polyether-ether-ketone and ZIF-8@ GO/polyether-ether-ketone anion composite membrane |
| CN113185737A (en) * | 2021-04-25 | 2021-07-30 | 长春工业大学 | Side chain type sulfonated polyaryletherketone sulfone/ZIF-67 @ GO composite membrane and preparation method thereof |
| CN113185738A (en) * | 2021-04-25 | 2021-07-30 | 长春工业大学 | Amino-containing polyaryletherketone sulfone/cationic metal-organic framework anion exchange membrane and preparation method thereof |
| CN113185738B (en) * | 2021-04-25 | 2024-01-30 | 长春工业大学 | Amino-containing polyaryletherketone sulfone/cationic metal-organic framework anion exchange membrane and preparation method thereof |
| CN113921875A (en) * | 2021-09-16 | 2022-01-11 | 盐城工学院 | Method for preparing MOFs (metal-organic frameworks)/viscose/PVA (polyvinyl alcohol) proton exchange membrane |
| CN114471177A (en) * | 2022-01-30 | 2022-05-13 | 天津大学 | Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof |
| CN114471177B (en) * | 2022-01-30 | 2023-10-27 | 天津大学 | Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof |
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