CN113072728B - Preparation method for converting amorphous polymer film into crystalline covalent organic framework film - Google Patents
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Abstract
The invention relates to the technical field of film preparation, and discloses a preparation method for converting an amorphous polymer film into a crystalline covalent organic framework film, which mainly adopts a solution processing method to prepare micromolecular ammonia and aldehyde monomers into an amorphous polyimide film; and then the exchange monomer and the amorphous polyimide film are treated under the solvothermal condition to realize the conversion from the amorphous polyimide film to the crystalline covalent organic framework film, wherein the amorphous polyimide film and the crystalline covalent organic framework film are formed by accumulating nanoparticles, the film appearance is basically kept unchanged before and after the monomer exchange, and the crystallinity of the covalent organic framework film after the monomer exchange is good. The operation process of the invention is simple and controllable, the self-supporting covalent organic framework film prepared by the method has an intrinsic channel with high crystallinity, high specific surface area and regular order, and the film displays excellent proton conductivity after loading a proton carrier.
Description
Technical Field
The invention relates to the technical field of membrane preparation, in particular to a preparation method for converting an amorphous polymer membrane into a crystalline covalent organic framework membrane.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high efficiency, high energy density, no pollution and the like, and are promising energy conversion devices. The Proton Exchange Membrane (PEM), one of the core components of a fuel cell, has a crucial influence on the performance of the fuel cell. Most of the currently widely used PEMs are amorphous polymers, which are typically represented by perfluorosulfonic acid materials, which are composed of a hydrophobic polytetrafluoroethylene main chain and a hydrophilic side chain with sulfonic acid groups, such as Nafion series membranes developed by dupont. Due to the difference of hydrophilicity and hydrophobicity of the main chain and the side chain, the Nafion membrane can form an ion channel through microphase separation in a water absorption state, so that the Nafion membrane has good proton conductivity under high humidity. It is worth noting that the amorphous polymer material has a disordered structure, and the construction of a continuous and regular ion channel can hardly be realized. A large number of research results show that the construction of the ion transfer channel plays an important role in proton transfer of the PEM, the optimization of the membrane channel structure becomes one of the research hotspots in the field of PEM, and the improvement of the continuity of the channel becomes the consensus of strengthening the proton transfer process.
Recently, COFs (crystalline porous covalent organic frameworks) formed by organic building blocks through strong covalent bond connection become a new research hotspot. Compared with other porous materials, the COFs material is constructed by organic molecular units, so that the functionalization is easier; the connection mode is a covalent bond, and the hydrothermal and chemical stability is higher. The COFs have various outstanding advantages, so that the COFs become a new generation membrane material construction element, and a brand new possibility is provided for constructing the PEM with long-range ordered and regular channels. However, the traditionally synthesized COFs are all powder materials and cannot be processed into a large-area uniform film shape. The current methods for fabricating COFs films can be summarized in two categories, top-down and bottom-up. The top-down method mainly comprises the steps of firstly synthesizing the COFs powder material, and then stripping the COFs powder material through methods such as chemical post-treatment and mechanical grinding to prepare the COFs nanosheet. The method has the main defects that the yield of the COFs nano-sheets is extremely low, and the size and the thickness of the nano-sheets are not controllable. The bottom-up method mainly comprises the methods of solvent thermal synthesis, interfacial polymerization and the like. The solvent thermal synthesis method is to put the substrate under the solvent thermal condition and polymerize monomers on the substrate to obtain the COFs film. Because the COFs tend to nucleate and grow in the host solution, the method is not easy to control the thickness of the COFs film, and the yield is low. The interfacial polymerization method is to dissolve the monomers in the two-phase solution respectively to obtain the COFs film at the phase interface. The method needs a large number of trial and error experiments to match monomer diffusion, reaction and crystallization processes to obtain the COFs film with high crystallinity, and film defects are easily caused in the film transfer process. In view of this, preparing a complete, defect-free, orderly-oriented and stable COFs pure film is still a scientific research difficulty and hot spot. The simple and efficient preparation method of the COFs pure membrane has great significance for promoting scientific research and industrial application of the COFs membrane.
Disclosure of Invention
In view of the above prior art, the present invention aims to overcome the drawbacks of the above background art, and provides a method for preparing a covalent organic framework film by converting an amorphous polymer film into a crystalline covalent organic framework film, wherein a solution processing method is adopted to prepare an amorphous polyimide film from small molecular ammonia and aldehyde monomers; and then the exchange monomer and the amorphous polyimide film are treated under the solvothermal condition to realize the conversion from the amorphous polyimide film to the crystalline covalent organic framework film.
In order to solve the technical problems, the invention provides a preparation method for converting an amorphous polymer film into a crystalline covalent organic framework film, which comprises the following steps:
step 1, preparing an amorphous polymer film: dissolving a small molecular ammonia monomer in N, N-dimethylacetamide, performing ultrasonic treatment to obtain a clear amine monomer solution with the mass volume concentration of 10mg/ml, dissolving aldehyde monomer aldehyde in N, N-dimethylacetamide, performing ultrasonic treatment to obtain a clear aldehyde monomer solution with the mass volume concentration of 5.65mg/ml, mixing and shaking the amine monomer solution and the aldehyde monomer solution according to a volume ratio of 1; placing a glass sheet with indium tin oxide coating as a substrate in a 60 ℃ oven, and mixing the solution A according to the proportion of 0.039-0.181ml/cm 2 Dropwise adding the solution to the surface of a glass substrate, and heating until the solvent is completely volatilized to obtain an amorphous polyimide film attached to the glass substrate;
step 2, preparation of a crystalline covalent organic framework film: taking a polybasic aldehyde monomer as an exchange monomer, adding the mixture into a reactor, wherein the volume ratio of the polybasic aldehyde monomer to the exchange monomer is 5.06:5.06:1, performing ultrasonic treatment for 15min to obtain a mixed solution C, adding the mixed solution C into a hydrothermal kettle with a polytetrafluoroethylene gasket, putting the amorphous polyimide film attached to the glass substrate prepared in the step 1 into the hydrothermal kettle with the surface facing downwards, heating the hydrothermal kettle in a 120 ℃ oven for 72h, taking out the hydrothermal kettle, cooling the hydrothermal kettle to room temperature with water, and washing the hydrothermal kettle for multiple times by adopting N, N-dimethylacetamide and acetone solvents to obtain a crystalline covalent organic framework film attached to the glass substrate;
and 3, soaking the crystalline covalent organic framework film attached to the glass substrate prepared in the step 2 in a dilute hydrochloric acid solution, peeling the film from the glass substrate, and washing the film to be neutral by adopting a large amount of water to obtain the self-supporting crystalline covalent organic framework film.
Further, the preparation method of the invention comprises the following steps:
in step 1, it is preferable to use the amount of the surfactant in terms of 0.157ml/cm 2 The mixed solution a was dropped to the surface of the glass substrate.
In step 1, the small molecule ammonia monomer is preferably 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, and the aldehyde monomer is preferably terephthalaldehyde.
In the step 2, the multi-aldehyde monomer is any one of 2, 5-dihydroxy terephthalaldehyde, 2, 6-dialdehyde-1, 5-dihydroxy naphthalene, trialdehyde phloroglucinol, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, 2-hydroxy-1, 3, 5-benzene triformal, 2, 3-dihydroxy naphthalene-1, 4-dicarboxaldehyde, 2, 3-dihydroxy terephthalaldehyde and 2,4, 6-tris (4-aldehyde phenyl) -1,3, 5-triazine.
Compared with the prior art, the invention has the beneficial effects that:
the method adopts a solution processing method to prepare the micromolecular ammonia and aldehyde monomers into the amorphous polyimide film, the film preparation method is convenient, simple, convenient and controllable, the operation is convenient, then the amorphous polyimide film is converted into the crystalline covalent organic framework film by adopting a monomer exchange method, and the prepared covalent organic framework film has high crystallinity, high specific surface area and pore volume, regular and ordered intrinsic channels, excellent stability and extremely high proton conductivity after loading a proton carrier.
Drawings
Fig. 1 is a scanning electron microscope cross-sectional view (a) of the amorphous polyimide film 1 and a scanning electron microscope cross-sectional view (b) of the crystalline covalent organic framework film 1 in example 1, a powder XRD diffraction curve (c) of the amorphous polyimide film 1 and a powder XRD diffraction curve (d) of the crystalline covalent organic framework film 1, a nitrogen desorption curve (e) of the amorphous polyimide film 1 and a nitrogen desorption curve (f) of the crystalline covalent organic framework film 1.
Fig. 2 is a proton conductivity diagram of the covalent organic framework membrane at different temperatures after phosphotungstic acid is loaded on the crystalline covalent organic framework membrane 1 in example 1.
Fig. 3 is a scanning electron micrograph of the amorphous polyimide film 2 (a) and the crystalline covalent organic framework film 2 (b) in example 1, and a powder XRD diffraction curve of the crystalline covalent organic framework film 2 (c).
Fig. 4 is a scanning electron micrograph of the amorphous polyimide film 3 (a) and the crystalline covalent organic framework film 3 (b) in example 1, and a powder XRD diffraction curve of the crystalline covalent organic framework film 3 (c).
Fig. 5 is a scanning electron micrograph of the amorphous polyimide film 4 (a) and the crystalline covalent organic framework film 4 (b) in example 1, and a powder XRD diffraction curve of the crystalline covalent organic framework film 4 (c).
Fig. 6 is a scanning electron micrograph of the amorphous polyimide film 5 (a) and the crystalline covalent organic framework film 5 (b) in example 1, and a powder XRD diffraction curve of the crystalline covalent organic framework film 5 (c).
FIG. 7 is a scanning electron micrograph cross-sectional view and a powder XRD diffraction profile of crystalline covalent organic framework films obtained in examples 2-8: (a-b) is example 2; (c-d) is example 3; (e-f) is example 4; (g-h) is example 5; (i-j) is example 6; (k-l) is example 7; (m-n) is example 8.
Detailed Description
The invention provides a design idea of a preparation method for converting an amorphous polymer film into a crystalline covalent organic framework film, which is to prepare micromolecular ammonia and aldehyde monomers into an amorphous polyimide film by adopting a solution processing method; and then the exchange monomer and the amorphous polyimide film are treated under the solvothermal condition to realize the conversion from the amorphous polyimide film to the crystalline covalent organic framework film.
The invention will be further described with reference to the following drawings and specific examples, which are not intended to limit the invention in any way.
Example 1, a crystalline covalent organic framework film was prepared from an amorphous polyimide film by the following steps:
step 1, preparing an amorphous polyimide film: dissolving 20mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in 2ml of N, N-dimethylacetamide, and subjecting to ultrasonic treatment to obtain a clear amine monomer solution; dissolving 11.3mg of terephthalaldehyde in 2ml of N, N-dimethylacetamide, and performing ultrasonic treatment to obtain a clear aldehyde monomer solution; mixing and shaking the amine monomer solution and the aldehyde monomer solution uniformly, adding 70 mu L of anhydrous acetic acid, and carrying out ultrasonic treatment for 5min to obtain a mixed solution A; a glass plate with an indium tin oxide coating and a diameter of 3.6cm was placed in an oven at 60 ℃ on a substrate, and 1.6ml of the mixed solution A was added dropwise to the surface of the glass substrate (0.157 ml/cm) 2 ) The amorphous polyimide film 1 was heated until the solvent was completely volatilized, and the cross section thereof was as shown in fig. 1 (a), the powder XRD diffraction curve thereof was as shown in fig. 1 (c), and the nitrogen desorption curve thereof was as shown in fig. 1 (e). Similarly, 1.2ml (0.118 ml/cm) was prepared by repeating the above procedure 2 )、0.8ml(0.079ml/cm 2 )、0.6ml(0.059ml/cm 2 ) And 0.4ml (0.039 ml/cm) 2 ) The mixed solution a is dropped on the surface of the glass substrate, and the obtained amorphous polyimide films are respectively referred to as amorphous polyimide films 2,3, 4, and 5 in order, and the corresponding cross sections are shown in fig. 3 to 6 (a).
Step 2, preparation of a crystalline covalent organic framework film: mixing 4.55mL of 1, 2-dichlorobenzene, 4.55mL of n-butanol and 0.9mL of 6M acetic acid aqueous solution to form a mixed solution, and marking as a mixed solution B; adding 13.6mg of 2, 5-dihydroxy terephthalaldehyde into the mixed solution B by taking 2, 5-dihydroxy terephthalaldehyde as an exchange monomer, performing ultrasonic treatment for 15min to obtain a mixed solution C, adding the mixed solution C into a hydrothermal kettle with a polytetrafluoroethylene gasket, putting the amorphous polyimide film 1 attached to the glass substrate prepared in the step 1 into the hydrothermal kettle with the film surface facing downwards, putting the hydrothermal kettle into an oven at 120 ℃ for heating for 72h, taking out the hydrothermal kettle, cooling the hydrothermal kettle to room temperature by using water, and washing the hydrothermal kettle for multiple times by using N, N-dimethylacetamide and acetone solvents to obtain a crystalline covalent organic framework film attached to the glass substrate, wherein the cross section of the crystalline covalent organic framework film 1 is shown as (B) in figure 1, the powder XRD diffraction curve of the crystalline covalent organic framework film is shown as (d) in figure 1, and the nitrogen absorption and desorption curve of the crystalline covalent organic framework film is shown as (f) in figure 1. Similarly, the above operations are repeated, and the amorphous polyimide films 2,3, 4, and 5 obtained in step 1 are processed as above, and the crystalline covalent organic framework films attached to the glass substrate are respectively and sequentially marked as crystalline covalent organic framework films 2,3, 4, and 5, and the corresponding cross-sections are shown in fig. 3 to 6 (b), and the corresponding powder XRD diffraction curves are shown in fig. 3 to 6 (c).
Step 3, preparation of the crystal covalent organic framework film loaded with phosphotungstic acid: and (3) soaking the crystalline covalent organic framework membrane 1 with the glass substrate prepared in the step (2) in 20ml of phosphotungstic acid aqueous solution (20 wt.%) for 48h, stripping the membrane from the glass substrate, and washing the membrane to be neutral by adopting a large amount of water, wherein the proton conductivity of the prepared phosphotungstic acid loaded crystalline covalent organic framework membrane is 0.53S/cm under the conditions of 80 ℃ and 100% humidity, and the proton conductivity at different temperatures is shown in figure 2.
From the SEM cross-sectional views of fig. 1 and 3-6, it can be seen that the amorphous polyimide film and the crystalline covalent organic framework film are formed by nanoparticle stacking, and the film morphology remains substantially unchanged before and after monomer exchange. From the powder XRD diffraction graphs of fig. 1 and fig. 3 to 6, it can be confirmed that the covalent organic framework film after monomer exchange has good crystallinity.
Example 2, a crystalline covalent organic framework film was prepared in substantially the same manner as in example 1, using a 3.6cm diameter glass slide with an indium tin oxide coating as the substrate, and 1.6ml of the above mixed solution a was added dropwise to the surface of the glass substrate in step 1, except that:
in step 2, the exchange monomer was changed from 13.6mg of 2, 5-dihydroxy terephthalaldehyde to 17.2mg of trialdehyde phloroglucinol; preparing a crystalline covalent organic framework film attached to a glass substrate;
and 3, soaking the crystalline covalent organic framework film attached to the glass substrate prepared in the step 2 in a dilute hydrochloric acid solution, peeling the film from the glass substrate, washing the film to be neutral by adopting a large amount of water, and showing the scanning electron microscope section diagram and the powder XRD diffraction curve of the finally prepared crystalline covalent organic framework film as shown in a and b in figure 7.
Example 3 a crystalline covalent organic framework film was prepared, which was prepared substantially as in example 2, except that:
in step 2, the monomer exchange was changed from 17.2mg of trialdehyde phloroglucinol to 15.9mg of 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde. The cross-sectional view of the scanning electron microscope and the powder XRD diffraction curve of the finally prepared crystalline covalent organic framework film are shown as c and d in figure 7.
Example 4 a crystalline covalent organic framework film was prepared, which was prepared substantially identically to example 2, except that:
in step 2, the monomer exchange was changed from 17.2mg of trialdehyde phloroglucinol to 14.6mg of 2-hydroxy-1, 3, 5-benzenetricarboxylic acid. The cross-sectional view of the finally prepared crystalline covalent organic framework film by scanning electron microscope and the diffraction curve of powder XRD are shown as e and f in figure 7.
Example 5 a crystalline covalent organic framework film was prepared, which was prepared substantially as in example 2, except that:
in step 2, the exchange monomer was changed from 17.2mg of trialdehyde phloroglucinol to 32.2mg of 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine. The scanning electron microscope section view and the powder XRD diffraction curve of the finally prepared crystalline covalent organic framework film are shown as g and h in figure 7.
Example 6 a crystalline covalent organic framework film was prepared, which was prepared substantially identically to example 2, except that:
in step 2, the exchange monomer was changed from 17.2mg of trialdehyde phloroglucinol to 13.6mg of 2, 3-dihydroxy terephthalaldehyde. The scanning electron microscope section view and the powder XRD diffraction curve of the finally prepared crystalline covalent organic framework film are shown as i and j in figure 7.
Example 7 a crystalline covalent organic framework film was prepared, which was prepared substantially identically to example 2, except that:
in step 2, the monomer exchange was changed from 17.2mg of trialdehyde phloroglucinol to 17.7mg of 2, 6-dialdehyde-1, 5-dihydroxynaphthalene. The cross-sectional view of the finally prepared crystalline covalent organic framework film by scanning electron microscope and the diffraction curve of powder XRD are shown as k and l in figure 7.
Example 8 a crystalline covalent organic framework film was prepared, which was prepared substantially as in example 2, except that: in step 2, the monomer exchange was changed from 17.2mg of trialdehyde phloroglucinol to 17.7mg of 2, 3-dihydroxynaphthalene-1, 4-dicarboxaldehyde. The cross-sectional view of the scanning electron microscope and the powder XRD diffraction curve of the finally prepared crystalline covalent organic framework film are shown as m and n in figure 7.
From the SEM cross-sectional view of fig. 7, it can be seen that both the amorphous polyimide film and the crystalline covalent organic framework film are formed by nanoparticle stacking, and the film morphology remains substantially unchanged before and after monomer exchange. From the powder XRD diffraction graph of fig. 7, it can be confirmed that the covalent organic framework film after monomer exchange has good crystallinity.
In summary, the preparation method for converting the amorphous polymer film into the crystalline covalent organic framework film provided by the invention mainly adopts a solution processing method to prepare the amorphous polyimide film from the small molecular ammonia and aldehyde monomers; and then the exchange monomer and the amorphous polyimide film are treated under the solvothermal condition to realize the conversion from the amorphous polyimide film to the crystalline covalent organic framework film. The self-supporting covalent organic framework membrane prepared by the method has an intrinsic channel with high crystallinity, high specific surface area and regular order, and the proton conductivity is 0.53S/cm under the conditions of 80 ℃ and 100% humidity after the phosphotungstic acid is loaded as a proton carrier.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (2)
1. A method for converting an amorphous polymer film to a crystalline covalent organic framework film, comprising the steps of:
step 1, preparing an amorphous polymer film: dissolving small molecular ammonia monomer in N, N-dimethyl acetylAmine, performing ultrasonic treatment to obtain a clarified amine monomer solution with the mass volume concentration of 10mg/ml, dissolving an aldehyde monomer in N, N-dimethylacetamide, performing ultrasonic treatment to obtain a clarified aldehyde monomer solution with the mass volume concentration of 5.65mg/ml, mixing and shaking the amine monomer solution and the aldehyde monomer solution according to a volume ratio of 1; placing the glass sheet with indium tin oxide coating as a substrate in an oven at 60 ℃, and enabling the mixed solution A to be 0.039-0.181ml/cm 2 Dropwise adding the solution to the surface of a glass substrate, and heating until the solvent is completely volatilized to obtain an amorphous polyimide film attached to the glass substrate;
step 2, preparation of a crystalline covalent organic framework film: taking a polybasic aldehyde monomer as an exchange monomer, adding the mixture into a reactor, wherein the volume ratio of the polybasic aldehyde monomer to the exchange monomer is 5.06:5.06:1, performing ultrasonic treatment for 15min to obtain a mixed solution C, adding the mixed solution C into a hydrothermal kettle with a polytetrafluoroethylene gasket, putting the amorphous polyimide film attached to the glass substrate prepared in the step 1 into the hydrothermal kettle with the surface facing downwards, heating the hydrothermal kettle in a 120 ℃ oven for 72h, taking out the hydrothermal kettle, cooling the hydrothermal kettle to room temperature with water, and washing the hydrothermal kettle for multiple times by adopting N, N-dimethylacetamide and acetone solvents to obtain a crystalline covalent organic framework film attached to the glass substrate;
step 3, soaking the crystalline covalent organic framework film attached to the glass substrate prepared in the step 2 in a dilute hydrochloric acid solution, peeling the film from the glass substrate, and washing the film to be neutral by adopting a large amount of water to obtain a self-supporting crystalline covalent organic framework film;
in the step 1, the small molecule ammonia monomer is 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, and the aldehyde monomer aldehyde is terephthalaldehyde;
in the step 2, the multi-aldehyde monomer is any one of 2, 5-dihydroxy terephthalaldehyde, 2, 6-dialdehyde-1, 5-dihydroxy naphthalene, trialdehyde phloroglucinol, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, 2-hydroxy-1, 3, 5-benzene triformal, 2, 3-dihydroxy naphthalene-1, 4-dicarboxaldehyde, 2, 3-dihydroxy terephthalaldehyde and 2,4, 6-tris (4-aldehyde phenyl) -1,3, 5-triazine.
2. The method according to claim 1, wherein the amount of the surfactant used in the step 1 is 0.157ml/cm 2 The mixed solution a was dropped to the surface of the glass substrate.
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| WO2016174468A1 (en) * | 2015-04-30 | 2016-11-03 | The University Of Liverpool | Porous materials |
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