CN115651240B - Anion exchange membrane based on MOFs framework and preparation method and application thereof - Google Patents
Anion exchange membrane based on MOFs framework and preparation method and application thereof Download PDFInfo
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Abstract
The application provides an anion exchange membrane based on MOFs frames, a preparation method and application thereof, which comprises a polymer main body, and an MOFs frame structure composed of 2,3,6,7,10, 11-hexaaminotrityl salt and metal ions, wherein the metal ions are connected with the MOFs frame structure and the polymer main body, the metal ions are constructed to serve as intermediate connection media between the MOFs frame and the polymer, and the MOFs frame structure is fully dispersed in the anion membrane in an in-situ growth method mode, so that the anion exchange membrane has good ion conductivity.
Description
Technical Field
The application relates to the field of ion exchange membranes, in particular to an anion exchange membrane based on MOFs frames, and a preparation method and application thereof.
Background
The anion exchange membrane is a high molecular polymer membrane containing alkaline active groups and having selective permeability to anions, also called an ion selective permeability membrane, and the application of the anion exchange membrane in new energy electrochemical devices is also receiving more and more attention from researchers, and the anion exchange membrane can be applied to the fields of alkaline fuel cells, electrolyzed water, carbon dioxide reduction, flow batteries and the like, has good development prospect, plays a role in the conventional industries of chlor-alkali industry, heavy metal recovery, water treatment, hydrometallurgy and the like, and is very widely concerned, and the ion conductivity of the anion exchange membrane directly influences the application performance of the anion exchange membrane.
MOFs refer to a class of crystalline porous materials with periodic network structures formed by self-assembled interconnection of inorganic metal centers (metal ions or metal clusters) and bridged organic ligands, which can give the final product both the rigidity of the inorganic material and the flexibility characteristics of the organic material. The prior art CN106711483B provides an oriented MOFs-based anion exchange membrane and a preparation method thereof, the scheme is that the oriented MOFs-based anion exchange membrane is prepared by reacting oriented ZIF nanowires with a high polymer, wherein the oriented ZIFs are arranged in a one-dimensional linear orientation mode, and the conduction efficiency is improved by guiding hydroxyl ions to transfer along a consistent direction, but the scheme has the problems that the preparation method is complicated and the mechanical property of the prepared ion exchange membrane is limited by the preparation method; in the composite alkaline anion exchange membrane provided by CN114292425A, porous MOF with high alkali resistance is used as a container to introduce hydroxyl conductive carriers into holes of the porous MOF, but the MOF material cannot be perfectly and uniformly distributed.
In view of the foregoing, there is a need for a new in situ growth-preparable MOF framework-based anion exchange membrane with excellent mechanical properties and ionic conductivity.
Disclosure of Invention
The application aims to provide an anion exchange membrane based on MOFs frames, a preparation method and application thereof, wherein metal ions are used as intermediate connection media for the MOFs frames and polymers, and the MOFs frame structures are fully dispersed in the anion membrane by utilizing an in-situ growth method, so that the anion exchange membrane has good ionic conductivity.
To achieve the above object, in a first aspect, the present technical solution provides an anion exchange membrane based on MOFs framework, which is characterized in that a polymer body and a MOFs framework structure composed of molecules with six-functional aromatic hydrocarbon structures and metal ions are formed, and the metal ions connect the MOFs framework structure and the polymer body.
Preferably, the functional group of the molecule with the six-functional aromatic hydrocarbon structure is selected from one of amino, hydroxyl and mercapto, and the functional group is disposed in six orientations of the aromatic hydrocarbon structure.
Preferably, the aromatic hydrocarbon structure with six functional groups includes one of the aromatic hydrocarbon structures shown in structural formula (1), formula (2), formula (3), formula (4), formula (5) and formula (6):
preferably, the MOFs framework structure is a ring-shaped porous structure.
Preferably, the functional group of the aromatic hydrocarbon structure with six functional groups coordinates with metal ions to form MOFs framework structures.
Preferably, at least two hexafunctional aromatic hydrocarbon structures are linked by a functional group, the functional groups in the remaining positions being coordinated to the metal ion.
Preferably, the metal ion is selected from one or a combination of at least two or more of copper ion, gold ion, iron ion, cobalt ion, aluminum ion, calcium ion, nickel ion, zinc ion, and zirconium ion plasma.
Preferably, X in the molecule of the aromatic hydrocarbon structure with six functional groups - Is Cl - ,Br - ,F - ,I - ,OH － ，HNO 3 - ,HCO 3 - ,HSO 4 - One or a combination of at least two or more plasmas.
In a second aspect, the present technical solution provides an anion exchange membrane based on MOFs framework, comprising: consists of a polymer main body, and MOFs framework structure composed of 2,3,6,7,10, 11-hexaaminotrityl salt shown in a formula (6) and metal ions, wherein the metal ions are connected with the MOFs framework structure and the polymer main body.
It is worth mentioning that the three benzene rings of the 2,3,6,7,10, 11-hexaaminotrityl salt are connected with each other through a six-membered ring compared with the benzene ring structure with six functional groups provided in the first aspect, so that the coordination capability of two amino groups and metal ions on the benzene ring structure is stronger.
Preferably, 2,3,6,7,10, 11-hexaaminotriaben in the MOFs framework is linked by metal ions.
Preferably, the MOFs framework structure is a ring-shaped porous structure.
Preferably, all amino groups of 2,3,6,7,10, 11-hexaaminotritene in the MOFs framework structure are connected with the metal ions, and the metal ions at the 2,3 positions are connected with a polymer main body.
The number of the 2,3,6,7,10, 11-hexaaminotrityl salts in the MOFs framework structure is more than or equal to 2.
Preferably, the anion X in the structure of the 2,3,6,7,10, 11-hexaaminotrityl salt - Is Cl - ,Br - ,F - ,I - ,OH － ，HNO 3 - ,HCO 3 - ,HSO 4 - One or a combination of at least two or more plasmas.
Preferably, the metal ion is selected from one or a combination of at least two or more of copper ion, gold ion, iron ion, cobalt ion, aluminum ion, calcium ion, nickel ion, zinc ion, and zirconium ion plasma.
Preferably, the metal ion is copper ion, and the MOFs framework structure has a porous structure as shown in formula (7):
in a third aspect, the present disclosure provides a method for preparing an anion exchange membrane based on MOFs framework, comprising the steps of:
mixing a polymer main body and 2,3,6,7,10, 11-hexaaminotrityl salt, and dissolving the mixture in DMSO to prepare a membrane;
soaking the membrane in an aqueous solution with metal ions for a set period of time to perform in-situ growth, taking out the membrane and soaking the membrane in a sodium hydroxide solution to obtain the anion exchange membrane,
the structure of the 2,3,6,7,10, 11-hexaaminotrityl salt is shown as a formula (6):
x in the chemical formula is an ion with monovalent negative electricity, and can be halogen or other negative ions.
Preferably, the metal ion in the aqueous solution of metal ion is one or more than two of copper ion, gold ion, iron ion, cobalt ion, aluminum ion, calcium ion, nickel ion, zinc ion and zirconium ion.
Preferably, the aqueous solution of metal ions is an aqueous solution of copper sulfate. And preferably, the film is immersed in a 0.5M aqueous solution of copper sulfate for 48 hours.
When the metal ion is copper ion, the chemical equation for in-situ growth of the film in the metal ion is as follows:
preferably, the polymer body is a polymer with a high molecular structure of an anion exchange polymer membrane.
Preferably, the polymeric body includes, but is not limited to: polystyrene, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polyethylene glycol, polysulfone, polyethylene, polypropylene, polynorbornene, chitosan.
In a fourth aspect, the application of an anion exchange membrane based on MOFs framework prepared above can be applied to electrolyzed water, carbon dioxide reduction, fuel cell.
Compared with the prior art, the technical scheme provides an anion exchange membrane based on MOFs frames, a preparation method and application thereof, and the MOFs frame structure composed of salt with six-functional benzene ring structure and metal ions is constructed, and can provide good ion conductivity performance when applied to the field of anion exchange membranes.
Preferably, the MOFs framework structure taking 2,3,6,7,10, 11-hexaaminotrityl salt as a raw material is constructed, the 2,3,6,7,10, 11-hexaaminotrityl salt in the MOFs framework structure is connected through metal ions, and the metal ions are connected with the MOFs framework structure and the polymer main body. According to the scheme, ions are conducted through metal ions with valence, the MOFs framework structure is of a porous structure, the specific surface area is large, and the formed pore canal can better transfer hydroxyl ions. And the two amino groups in the 2,3,6,7,10, 11-hexaaminotrityl salt have stronger coordination capability with metal ions, so the stability of the structure is stronger.
Drawings
FIG. 1 is a chart showing the Fourier transform infrared spectrum of the anion exchange membrane obtained in example 1 of the present application.
FIG. 2 is a graph showing the nuclear magnetic resonance characteristics of the anion exchange membrane obtained in example 2 of the present application.
FIG. 3 is a cross-sectional scanning electron micrograph of the anion exchange membrane obtained in example 2 of this embodiment.
Fig. 4 is a scanning electron microscope spectrogram of a cross section of the anion exchange membrane obtained in example 2 of the present embodiment.
Fig. 5 is a graph comparing the results of ion conductivity tests for the anion exchange polymer membranes of inventive examples 1, 2 and comparative example 1.
Fig. 6 is a stability test of example 2.
FIG. 7 is a block diagram of an MEA cell.
FIG. 8 is a graph comparing the performance of example 2 and comparative example 1 in MEA cells.
Fig. 9 is a schematic representation of the transport mechanism of MOFs grown in situ within a polymer film.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
Embodiment one:
providing a MOFs framework-based chitosan anion exchange membrane prepared by an in-situ growth method, wherein the MOFs framework structure is as follows:
the preparation method of the MOFs framework structure comprises the following steps:
80mg of chitosan and 5mg of 2,3,6,7,10, 11-hexaaminotrityl salt were mixed, then dissolved in 10mL of an aqueous solution containing 4wt% of acetic acid to prepare a membrane, and then the obtained membrane was immersed in a mixed solution containing 0.5M of copper sulfate and ammonia water for 48 hours, taken out and immersed in a potassium hydroxide solution to form an anion exchange membrane based on MOFs frame.
Chemical structure characterization:
the resulting anion exchange polymer was characterized using a nuclear magnetic resonance spectrometer model JASCO FTIR-6000, the infrared spectrum of which is shown in FIG. 1. As can be seen from FIG. 1, the biomolecular polymer film has absorption peaks of N-H bond and C-N bond, and the stretching vibration of N-H bond is 3300-3500 cm -1 The C-N bond has a stretching vibration of 1190cm -1 Left and right.
Embodiment two:
provided is an anion exchange membrane based on MOFs framework prepared by an in-situ growth method, wherein the structure of the MOFs framework is as follows:
the anionic polymer body is:
the preparation method of the anion exchange polymer main body comprises the following steps:
1) 2.00g (8.68 mmo1) of terphenyl was weighed into a 100mL flask, 1.17g (10.32 mmol) of N-methyl-4-piperidone was added, tetraphenyl methane (0.26 mmol) was added, 9' -spirobifluorene (0.09 mmol) was added, and then 8.8mL of methylene chloride was added to dissolve and disperse the reaction. 1.5mL of trifluoroacetic acid and 8.8mL of trifluoromethanesulfonic acid were added at 0deg.C and reacted for 6 hours. Pouring the viscous purple product into 1M (mol/L) K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a target product.
2) Quaternization reaction. 1.0g of the above intermediate polymer was weighed, 20mL of dimethyl sulfoxide was added, followed by 1.0mL of methyl iodide, and the mixture was reacted at room temperature for 12 hours, followed by raising the temperature to 60℃for 12 hours. Pouring the reaction product into ethyl ether (volume ratio of ethyl ether to ethanol is 6:1) solvent containing ethanol, precipitating to obtain yellow precipitate, washing with ethyl acetate three times, washing with water, and oven drying to obtain anion I - Is an anion exchange polymer of (a).
3) Film formation and ion exchange. 120mg of the above anion exchange polymer was weighed, 5mL of dimethyl sulfoxide was added, 5mg 2,3,6,7,10,11-hexaaminotrityl salt was added to the mixture to be mixed, and after the mixture was sufficiently dissolved, the mixture was poured into a glass petri dish having a diameter of 6cm, and the film was dried at 120℃to form a film, and the film was peeled from the glass. The resulting membrane was then immersed in a mixed solution containing 0.5M copper sulfate and aqueous ammonia for 48 hours, taken out and immersed in a potassium hydroxide solution to form an anion exchange membrane based on MOFs frames.
Chemical structure characterization:
the resulting anion exchange polymer was characterized using a nuclear magnetic resonance spectrometer model Bruker AVANCE III HD (400 MHz) and the hydrogen profile nuclear magnetic pattern is shown in FIG. 2. Deuterated dimethyl sulfoxide (d 6-DMS 0) was used to solubilize the samples in the test.
The MOFs framework of the present scheme is grown in situ in an anion exchange polymeric membrane, and the transport mechanism of the in situ grown MOFs within the polymeric membrane is shown in fig. 9.
Characterization of porosity:
the cross-sectional morphology of the anion exchange membrane obtained in example 2 was obtained by scanning electron microscopy, as shown in fig. 3. From the cross-sectional morphology, the ion exchange membrane has a certain porous structure.
The energy spectrum of the cross section of the anion exchange membrane obtained in example 2 was obtained by scanning electron microscope energy spectrum test, as shown in fig. 4. From the test results, the ion exchange membrane contained a certain amount of Cu element.
Embodiment III:
the present solution provides an anion exchange polymer37-50-grade T, manufactured by Dioxide materials company.
Performance test:
1) Ion conductivity test
Measuring OH of all-wet anion exchange membrane in pure water by four-electrode alternating current impedance method - The ionic conductivity, specific test parameters, are as follows: taking an area of 2X2cm 2 Film material with a thickness of 25 μm, using an Autolab302N electrochemical workstation, at a frequency of 0.1HzAnd (3) carrying out alternating current impedance test within 1000KHz, and carrying out fitting on a curve to calculate the ion conductivity. The ionic conductivities of example 1, example 2, example 3 at 80℃are shown in FIG. 5. It can be seen that the ion conductivity of the anion exchange membranes obtained in examples 1 and 2 is as high as 170.2 and 198.3mS/cm。
2) Stability test
The stability test results of example 2 are shown in fig. 6, by immersing the anion exchange membrane in a 1M NaOH solution at 80 ℃ to test the ionic conductivity for various periods of time. It can be seen that the anion exchange membrane shows good ionic conductivity within 500 h.
3) Electrolytic water performance test
The specific structure of the MEA electrolytic cell is shown in figure 7: the assembly (1) is a stainless steel backing plate; a component (2) copper electrode; the component (3) is a graphite catholyte flow chamber; a component (4) cathode catalyst; an ion transport membrane of the assembly (5); the component (6) anode catalyst; the component (7) is a graphite anode electrolyte flow chamber.
The test uses NiFeOOH/nickel mesh as the anode gas diffusion electrode (1.0 cm 2 ) Platinum carbon/carbon cloth is used as a cathode gas diffusion electrode (1.0 cm) 2 ) The above Membrane Electrode Assembly (MEA) was assembled into a device using the anion exchange membrane prepared in example 1 as a membrane material. Continuously introducing anode and cathode for 100mL min -1 The cell operating temperatures were room temperature, 40 ℃, 60 ℃, 80 ℃, respectively, and using an Autolab30 equipped with a 10A current amplifier 2 Before the test of the polarization curve, the polarization curve is activated for 1h by Cyclic Voltammetry (CV), the voltage range is 1.0-2.6V, the sweeping speed is 200mV s-1, and the voltage range used for the test of the polarization curve is 1.0-2.6V, and the sweeping speed is 10mV s-1.
The catalyst preparation process is as follows:
firstly, the nickel screen is pretreated, and the specific operation is as follows: firstly, putting a nickel screen into a 3mol/L oxalic acid aqueous solution, etching for 1 hour at 100 ℃, respectively washing for a plurality of times by deionized water and absolute ethyl alcohol, and drying for later use.
Preparation of FeNiOOH catalyst: 360mg Fe (NO) 3 Dissolving in 12mL of aqueous solution, placing the etched nickel screen in the solution, and adding 70mg of Na 2 S 2 O 3 After 10 minutes of reaction, deionized water and absolute ethyl alcohol are used for washing for a plurality of times, and the mixture is dried for standby.
Platinum carbon/carbon cloth catalyst preparation: dispersing 60% platinum carbon powder in ethanol solutionAdding proper amount of Nafion solution, fully dissolving, spraying onto carbon cloth, and loading about 1.5-2 mg/cm 2 。
The results of the alkaline electrolyzed water MEA test are shown in fig. 8. The results showed that the anion exchange membrane of example 2 showed excellent current densities [ ] at 80℃at a cell pressure of 2.0V, respectively>5A) G is higher than the current density of comparative example 1. Furthermore, at 1A/cm 2 Example 2 only required a 1.57V cell pressure at current density, whereas comparative example 1 required a 1.66V cell pressure. It follows that anion exchange membranes containing in-situ grown MOFs framework exhibit superior performance compared to the currently commercial anion exchange membranes.
The present application is not limited to the above-mentioned preferred embodiments, and any person who can obtain other various products under the teaching of the present application can make any changes in shape or structure, and all the technical solutions that are the same or similar to the present application fall within the scope of the present application.
Claims (7)
1. An MOFs framework-based anion exchange membrane comprising: polymer body
The polymer comprises MOFs framework structure composed of molecules with six-functional aromatic hydrocarbon structures and metal ions, wherein the metal ions connect the MOFs framework structure and the polymer main body, and the molecules with six-functional aromatic hydrocarbon structures are 2,3,6,7,10, 11-hexaaminotrityl salts;
mixing a polymer main body and 2,3,6,7,10, 11-hexaaminotrityl salt, dissolving in DMSO to prepare a membrane, soaking the membrane in an aqueous solution with metal ions for a set period of time to perform in-situ growth, taking out the membrane, and soaking in a sodium hydroxide solution to obtain the anion exchange membrane.
2. The MOFs framework-based anion exchange membrane of claim 1, wherein the 2,3,6,7,10, 11-hexaaminotriaben in the MOFs framework is linked by metal ions.
3. The MOFs framework-based anion exchange membrane of claim 1, wherein the metal ions are copper ions and the MOFs framework structure is a porous structure having the formula (7):
4. a method for preparing an anion exchange membrane based on MOFs framework, comprising: mixing a polymer main body and 2,3,6,7,10, 11-hexaaminotrityl salt, and dissolving the mixture in DMSO to prepare a membrane;
and soaking the membrane in an aqueous solution with metal ions for a set period of time to perform in-situ growth, taking out the membrane, and soaking the membrane in a sodium hydroxide solution to obtain the anion exchange membrane.
5. The method according to claim 4, wherein the metal ions in the aqueous solution of metal ions are one or a combination of at least two selected from the group consisting of iron ions, cobalt ions, aluminum ions, calcium ions, nickel ions, zinc ions, and zirconium ions.
6. The method according to claim 4, wherein the polymer body is a polymer having a high molecular structure of an anion exchange polymer membrane.
7. Use of an anion exchange membrane based on MOFs framework according to any of claims 1 to 3, characterized in that it is applied to electrolysis of water, reduction of carbon dioxide, fuel cells.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106711483A (en) * | 2016-12-08 | 2017-05-24 | 中国科学技术大学 | Oriented MOFs-based anion exchange membrane as well as preparation method and application thereof |
| CN111537577A (en) * | 2020-03-13 | 2020-08-14 | 郑州轻工业大学 | Metal-organic framework graphene analogue and preparation method thereof, aptamer sensor and preparation method thereof |
| CN115109236A (en) * | 2022-07-29 | 2022-09-27 | 西湖大学 | Sp-containing polymer 3 Piperidine tertiary amine group polymer with carbon-based skeleton structure and application thereof |
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| CN111554936B (en) * | 2020-05-18 | 2021-03-26 | 齐鲁工业大学 | Conductive MOF modified carbon fiber paper insertion layer material for lithium-sulfur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106711483A (en) * | 2016-12-08 | 2017-05-24 | 中国科学技术大学 | Oriented MOFs-based anion exchange membrane as well as preparation method and application thereof |
| CN111537577A (en) * | 2020-03-13 | 2020-08-14 | 郑州轻工业大学 | Metal-organic framework graphene analogue and preparation method thereof, aptamer sensor and preparation method thereof |
| CN115109236A (en) * | 2022-07-29 | 2022-09-27 | 西湖大学 | Sp-containing polymer 3 Piperidine tertiary amine group polymer with carbon-based skeleton structure and application thereof |
Non-Patent Citations (1)
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| Chen, Tianyang et al.Continuous Electrical Conductivity Variation in M-3(Hexaiminotriphenylene)(2) (M = Co, Ni, Cu) MOF Alloys.Journal of the American Chemical Society.2020,12367-12373. * |
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