CN110698710B - Method for preparing covalent organic framework material film by quantitative layer-by-layer self-assembly - Google Patents
Method for preparing covalent organic framework material film by quantitative layer-by-layer self-assembly Download PDFInfo
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Abstract
The invention belongs to the technical field of functional materials, and particularly relates to a method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly. The method realizes the nucleation growth of the monomer on the surface of the substrate by quantitative layer-by-layer spraying, further realizes the quantitative controllable preparation of the covalent organic framework material film, has simple operation and high preparation efficiency, and is easy to realize the large-scale preparation and the industrialized popularization of the covalent organic framework material film.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly.
Background
The film material can be used in the fields of separation, photoelectricity, sensing, energy storage and the like, and has important application value. However, conventional membrane materials, which are mostly polymers or ceramics, generally have a broad pore size distribution, have a problem of inaccurate separation. The film of the novel porous material represented by covalent organic framework materials (COFs) has the advantages of narrow pore size distribution, large specific surface area, tailorable structure and the like, and can be used in the fields of precise separation, adsorption, sensing, photoelectric conversion, storage, catalysis and the like. The research on the preparation method, particularly the preparation method suitable for industrial popularization, becomes a research hotspot in the field.
However, the COFs are usually insoluble and refractory powder, and have poor processability, on one hand, a pure porous material film without defects is difficult to obtain by using the traditional methods such as spin coating, dip coating and the like; on the other hand, although the hybrid membrane can be prepared by utilizing the macromolecular connecting agent or the additive, the processability is improved, but the pore channels of the porous material are easily blocked by the connecting agent or the additive, the performance of the porous material is deteriorated, and the application of the porous material is limited.
At present, the solvent thermal synthesis method of the COFs membrane is the most common preparation method and the best researched preparation method. Adding a substrate, reactants, a dispersing solvent and reaction additives such as a catalyst into a reaction container, uniformly dispersing, sealing, reacting at a high temperature for a period of time, and separating, washing and vacuum drying after the reaction is finished to obtain a final product. And, due to the reactant pair O2And water and other environmental factors are sensitive, and auxiliary steps such as liquid nitrogen freezing, vacuumizing, vacuum tube sealing and the like are required to be arranged in the solvent thermosynthesis method so as to avoid defects in the aspects of film appearance and performance. However, the solvothermal synthesis method is not suitable for large-scale synthesis of COFs films and industrial popularization of the preparation method due to the problems of complicated steps, limited kinds of dispersing solvents, poor flexibility, harsh reaction conditions, long preparation time and the like.
In particular, the solvothermal synthesis method needs to immerse a substrate in a monomer solution, and the substrate is sealed and then reacts at high temperature and high pressure, so that a plurality of monomers directly react in the solution to generate a product, the monomer nucleated and grown on the substrate is difficult to measure, the utilization rate of raw materials is low, and the steps of seed crystal coating and secondary growth are generally needed. Therefore, it is not easy to control the amount of the industrial product and to prepare an ultrathin film.
Therefore, the development of a method for preparing the COFs membrane, which is controllable in quantification and convenient for large-scale preparation and industrial popularization, is an urgent problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a covalent organic framework material thin film, which is controllable in quantification and convenient for large-scale preparation and industrial popularization, aiming at the problems in the prior art, the method introduces an anchoring group on the surface of a substrate, then quantitatively sprays a monomer solution for synthesizing the covalent organic framework material thin film material on the substrate, reacts and bonds with the anchoring group on the surface of the substrate under a certain condition, sprays another monomer solution according to a metering ratio, reacts under a certain condition, repeats the spraying reaction process, and obtains the covalent organic framework material thin film with uniform pore diameter.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly comprises the following steps:
(1) pretreating a substrate, chemically modifying the substrate, and introducing an anchoring group on the surface of the substrate;
(2) preparing one or more monomer solutions;
(3) respectively spraying one or more monomer solutions obtained in the step (2) on the modified substrate obtained in the step (1) through spraying equipment according to a stoichiometric ratio, and carrying out reaction bonding to obtain a layer of grown film;
(4) and (3) continuously spraying one or more monomer solutions on the substrate on which the growing film is formed in the step (3) until the growing film is the required number of layers or thickness, and obtaining the covalent organic framework material film.
It is worth to be noted that, the preparation method of the covalent organic framework material film in the prior art needs to be carried out under extreme conditions, has long reaction period and is difficult to be used for large-scale synthesis preparation. The covalent organic framework material film is controllably prepared by a quantitative spray coating layer self-assembly method, and the method utilizes the covalent bond bonding capability of COFs materials and introduces anchoring groups through substrate chemical modification, thereby realizing the layer-by-layer self-assembly preparation of the covalent organic framework material film on the surface of the substrate.
Preferably, the substrate in the step (1) comprises a base film or matrix, and the material of the base film or matrix comprises metal, ceramic, metal oxide, sulfide, glass or polymer.
The base film or matrix is typically polysulfone, polyacrylonitrile, polyvinylidene fluoride, cellulose, glass, alumina, or silicate.
Further preferably, the anchor group in step (1) comprises a carboxyl group, an amino group, a hydroxyl group, an alkoxy group or a cyano group.
Preferably, the monomer in step (2) includes boric acid compounds, amine compounds, aldehyde compounds, acid chloride compounds and acid anhydride compounds.
Exemplarily, one monomer solution prepared in the step (2) is a 1, 4-p-phenylboronic acid solution.
Exemplarily, the two monomer solutions prepared in the step (2) are a 1, 4-p-phenylenediamine solution and a trimesic aldehyde solution.
Exemplarily, the two monomer solutions prepared in the step (2) are a 1, 4-dicyanobenzene solution and a zinc chloride solution.
Illustratively, the plurality of monomer solutions prepared in the step (2) are pyromellitic dianhydride solution, tris (4-aminophenyl) amine solution, 1,3, 5-tris (4-aminophenyl) aniline solution, and 1,3, 5-tris [ 4-amino (1, 1-biphenyl-4-yl) ] amine solution.
Preferably, the reaction bonding conditions in step (3) are: the reaction temperature is 25-120 ℃, and the reaction time is 1-6 hours.
Further preferably, the reaction bonding environment in the step (3) is vacuum, nitrogen or inert atmosphere.
Preferably, the monomer solution in step (4) is one or more groups of monomer solutions.
Further preferably, the step (4) of continuing spraying with the group of monomer solutions comprises: and (4) continuously spraying a group of monomer solutions which are the same as the monomer solutions sprayed in the step (3) on the substrate on which the growing film is formed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
Further preferably, the step (4) of continuing spraying by using multiple groups of monomer solutions comprises the following steps: continuously spraying a group of monomer solutions which are the same as the monomer solutions sprayed in the step (3) on the substrate on which the growing film is formed in the step (3) until the film grows to the required layer number or thickness; and (4) continuously spraying one or more groups of monomer solutions different from the monomer solution sprayed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
It is worth explaining that the step (3) and the step (4) of the invention realize the respective sequential spraying of the monomer reaction solutions according to the stoichiometric ratio through the spraying equipment, compared with the prior art, the quantitative spraying layer self-assembly method effectively avoids the defect that the quantity of the monomers nucleated and grown on the substrate cannot be measured due to the direct reaction of the monomers in the solution to generate the COFs material in the solvothermal synthesis of various monomer solutions, and realizes the quantitative and controllable preparation of the covalent organic framework material film through the accurate regulation and control of the temperature, the reactant concentration and the reaction time.
Compared with the prior art, the invention has the following beneficial effects:
1) the method is simple to operate, does not need the steps of seed crystal coating and secondary growth, has high preparation efficiency and high raw material utilization rate, can greatly reduce the cost, and is easy to realize large-scale preparation;
2) the preparation time is short, compared with a solvent thermal synthesis method, the single-layer preparation time is 1-6 h, the preparation time is greatly shortened, and the preparation efficiency of the covalent organic framework material film is improved;
3) the controllable quantitative preparation of the covalent organic framework material film can be realized by alternately and quantitatively spraying the monomer solution on the substrate according to the reaction metering ratio;
4) by changing the kind of the monomer solution, a double-layer or multi-layer heterostructure film can be prepared;
5) the spraying equipment realizes industrial production, and the covalent organic framework material film is prepared by using the spraying equipment, so that the preparation difficulty of the covalent organic framework material film is reduced, and the method is suitable for industrial popularization;
6) the porous material film prepared by the spray layer-by-layer self-assembly is expanded to the field of covalent organic framework materials, and a foundation is laid for device research and industrial application of COFs materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic diagram of a method for preparing a covalent organic framework material thin film by quantitative layer-by-layer self-assembly according to embodiment 1 of the present invention.
Fig. 2 is a scanning electron micrograph of a surface of a covalent organic framework material thin film provided in example 1 of the present invention.
Fig. 3 shows the nanofiltration effect of a covalent organic framework material film on different dyes provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention particularly discloses a preparation method of a COFs membrane which is controllable in quantification and convenient for large-scale preparation and industrial popularization, and has great market application and popularization values.
The invention discloses a method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly, which comprises the following steps:
(1) pretreating a substrate, chemically modifying the substrate, and introducing an anchoring group on the surface of the substrate;
(2) preparing one or more monomer solutions;
(3) respectively spraying one or more monomer solutions obtained in the step (2) on the modified substrate obtained in the step (1) through spraying equipment according to a stoichiometric ratio, and carrying out reaction bonding to obtain a layer of grown film;
(4) and (4) continuously spraying one or more monomer solutions on the substrate on which the growing film is formed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
In order to further optimize the above technical solution, the substrate in step (1) includes a base film or a base body, and the material of the base film or the base body includes metal, ceramic, metal oxide, sulfide, glass or polymer.
In order to further optimize the above technical solution, the anchoring group in step (1) comprises carboxyl, amino, hydroxyl, alkoxy or cyano.
In order to further optimize the technical scheme, the monomers in the step (2) comprise boric acid compounds, amine compounds, aldehyde compounds, acyl chloride compounds and anhydride compounds.
In order to further optimize the technical scheme, the reaction bonding conditions in the step (3) are as follows: the reaction temperature is 25-120 ℃, and the reaction time is 1-6 hours.
In order to further optimize the above technical scheme, the reaction bonding environment in the step (3) is vacuum, nitrogen or inert atmosphere.
In order to further optimize the technical scheme, the monomer solution in the step (4) is one or more groups of monomer solutions.
In order to further optimize the technical scheme, the method for continuously spraying the group of monomer solutions in the step (4) comprises the following steps: and (4) continuously spraying a group of monomer solutions which are the same as the monomer solutions sprayed in the step (3) on the substrate on which the growing film is formed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
In order to further optimize the technical scheme, the method for continuously spraying the plurality of groups of monomer solutions in the step (4) comprises the following steps: continuously spraying a group of monomer solutions which are the same as the monomer solutions sprayed in the step (3) on the substrate on which the growing film is formed in the step (3) until the film grows to the required layer number or thickness; and (4) continuously spraying one or more groups of monomer solutions different from the monomer solution sprayed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
The technical solutions and advantages of the present invention are further illustrated below with reference to specific examples, but the present invention is not limited to the following examples.
Example 1: preparation of COF-LZU1/PAN film
A method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly is to place a PAN base film in 2mol/L NaOH aqueous solution at 30 ℃ to be soaked for 1 h. Then the membrane is taken out and washed by deionized water for a plurality of times until the washing liquid is neutral, and the-CN group is converted into the-COOH group. And finally, airing the modified PAN-based film at 25 ℃. Preparing dioxane solution of trimesic aldehyde and dioxane solution of p-phenylenediamine; spraying a certain volume of p-phenylenediamine solution on the modified PAN base film, and standing for 2h at 25 ℃ for reaction; and spraying a mesitylene formaldehyde solution according to the metering ratio, and reacting for 2h at 25 ℃ under vacuum to form a COF-LZU1 film. By repeating the steps alternately, a plurality of separation membranes can be formed on the surface of the PAN base membrane, and the preparation process is shown in figure 1.
SEM scanning is carried out on the surface of the prepared COF-LZU1/PAN composite film, and the obtained scanning electron micrograph is shown in figure 2. It can be seen that the present invention provides a continuous defect-free thin film of covalent organic framework material by a quantitative spray coating layer self-assembly process. The raw material utilization rate was 98% by weight calculation of the prepared COF-LZU1/PAN composite film (shown in Table 1).
Performing nanofiltration performance test on the prepared composite membrane, filtering a COF-LZU1 membrane by using a nanofiltration device under 0.1MPa to obtain 50mg/L water-soluble acidic orange red solution, water-soluble chrome black T solution, water-soluble acidic fuchsin solution, water-soluble Congo red solution, water-soluble aniline blue solution and water-soluble methyl blue solution, wherein the effective area of a membrane is 19.625cm2. The retention rate (green point) and the permeation flux (red point) were measured, and the results are shown in FIG. 3, in which the retention rate was slightly increased (92.4%, 90.20%, 94.24%, 96.50%, 99.43%, 98.34%) with the increase in molecular weight, and the permeation flux was slightly decreased (465.1, 462.5, 433.2, 415.4, 407.6, 398.3L m)-2h-1MPa-1) The retention rate of the film on each dye can reach more than 90 percent, which shows that the COF-LZU1 film has good retention effect on dye molecules with the molecular weight of 300-800.
TABLE 1
Example 2: preparation of DAB-TFP COF film
A method for preparing covalent organic frame material film by quantitative layer-by-layer self-assembly comprises placing cleaned silicon wafer into clean culture dish, and using H2O2Concentrated H2SO4The mixed solution of 3/7(v/v) was soaked at 70 ℃ for 30min, cooled and washed three times with deionized water. 14. mu.l of 3-Aminopropyltriethoxysilane (APTES) was weighed into 20ml of acetone and sonicated for 1 min. The hydrophilically treated substrate was then immersed face down in an APTES solution for 2h at 25 ℃. Preparing a dioxane solution of 1,3, 5-triacyl phloroglucinol (10.5mg, 0.01mol/L), spraying the dioxane solution on the modified silicon chip, and placing the silicon chip at 100 ℃ for reaction for 2 hours; and spraying a p-phenylenediamine solution according to the metering ratio, continuously placing the solution at 100 ℃ for reacting for 2h to form the DAB-TFP COF film, and repeating the experiment in such an alternating way. The DAB-TFP COF/ITO electrode is subjected to performance test, and the aperture smaller than or larger than that of the DAB-TFP COF is selected
Having redox activity
The three ions of (a) are used as probe molecules, and then a cyclic voltammetry test (CV) is performed on each ion by using a three-electrode method. Experimental results show that the three probe molecules generate oxidation-reduction reaction on the surface of the ITO electrode to generate a strong current signal, and the three probe molecules have certain permeability to the three probe molecules with oxidation-reduction activity. The DAB-TFP COF film obtained by preparation is weighed, and the utilization rate of raw materials is 97%.
Example 3: preparation of COF-1/PVDF film
A method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly is characterized in that a PVDF (polyvinylidene fluoride) base film is placed in deionized water to be soaked for 12 hours, then a membrane is taken out, and the membrane is dried at 25 ℃. Preparing a dioxane solution of 1, 4-p-phenylboronic acid; spraying a certain volume of 1, 4-p-phenylboronic acid solution on a PVDF base film, placing the PVDF base film at 80 ℃ for 1h of reaction under vacuum, and reacting at 80 ℃ under vacuum for a period of time to form a COF-1 film. By repeating the steps alternately, a plurality of separation membranes can be formed on the surface of the PVDF base membrane. The prepared COF-1/PVDF composite membrane is weighed, and the utilization rate of raw materials is 98%. The membrane can be widely applied to the field of adsorption.
Example 4: preparation of COF-42/COF-43/PTFE film
A method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly comprises the steps of placing a PTFE (polytetrafluoroethylene) base film in deionized water to be soaked for 12 hours, taking out a film, and airing at 25 ℃. Preparing a dioxane solution of 2, 5-diethoxy-1, 4-benzenedicarboxhydrazide and a dioxane solution of 1,3, 5-tribenzaldehyde; spraying a certain volume of 2, 5-diethoxy-1, 4-phenyldicarboxhydrazide solution on a PTFE base film, and standing for 2 hours at 25 ℃ under vacuum for reaction; and spraying 1,3, 5-triphenylformaldehyde solution according to the metering ratio, and reacting for 3 hours at 25 ℃ in vacuum to form the COF-42 film. Preparing a dioxane solution of 2, 5-diethoxy-1, 4-benzenedicarboxhydrazide, a dioxane solution of 1,3, 5-tri (p-formylphenyl) benzene and 1,3, 5-tribenzaldehyde; spraying a certain volume of 2, 5-diethoxy-1, 4-phenyldicarboxhydrazide solution on a PTFE base film, and standing for 2 hours at 25 ℃ under vacuum for reaction; then respectively spraying 1,3, 5-triphenylformaldehyde solution and 1,3, 5-tri (p-formylphenyl) benzene solution according to the metering ratio, and reacting for 2h under vacuum at 25 ℃ to form a COF-43 film. The COF-42/COF-43/PTFE composite membrane can be prepared by the alternate repetition. The raw material utilization rate is 98 percent by weighing and calculating the prepared COF-42/COF-43/PTFE composite film.
EXAMPLE 5 preparation of PAF-56/PVDF film.
A method for preparing covalent organic framework material film by quantitative layer-by-layer self-assembly is characterized in that a polyvinylidene fluoride film is soaked in water in advance and dried at room temperature. At room temperature, 6 mol. L-1The NaOH solution is uniformly dripped on the surface of the modified PVDF membrane, reacts for 6 hours, is washed to be neutral by deionized water, and is dried at 105 ℃. Spraying 1, 4-dioxane solution (0.05 mol. L) of cyanuric chloride on the modified polyvinylidene fluoride membrane-1) And reacting at 50 ℃ for 1 h. In one beaker 1.5mmol of p-terphenyl was dissolved in 7ml of 1, 4-dioxane and in another beaker 0.5mmol of cyanuric chloride was dissolved in 1.5mmol of trifluoromethanesulfonic acid. And alternately spraying the two solutions on the modified polyvinylidene fluoride membrane, sealing and heating at 50 ℃ for 3h, cooling, washing with 1, 4-dioxane and ethanol, drying at room temperature to obtain the PAF-56/PVDF membrane, weighing, and calculating to obtain the material utilization rate of 96%.
To further verify the excellent effects of the present invention, the inventors also conducted the following comparative experiments:
comparative example 1
The same COF-LZU1/PAN film as in example 1 was prepared by solvothermal synthesis, and the PAN-based film was immersed in 2mol/L NaOH aqueous solution at 30 ℃ for 1 hour. Then the membrane is taken out and washed by deionized water for a plurality of times until the washing liquid is neutral, and the-CN group is converted into the-COOH group. And finally, airing the modified PAN-based film at 25 ℃. Preparing dioxane solution of trimesic aldehyde and dioxane solution of p-phenylenediamine; and adding the modified PAN base film into a p-phenylenediamine solution and a trimesic aldehyde solution for in-situ solvothermal reaction, and reacting at 60 ℃ for 3 days to form a COF-LZU1 film. The raw material utilization rate is only 80 percent by weighing and calculating the prepared COF-LZU1/PAN composite film.
As can be seen from the raw material utilization rates of example 1 and comparative example 1, compared with the conventional method for preparing a covalent organic framework material thin film by means of solvothermal synthesis and quantitative layer-by-layer self-assembly, the method for preparing a covalent organic framework material thin film by means of spray coating and quantitative layer-by-layer self-assembly according to the present invention is simple to operate, does not require the steps of seed crystal coating and secondary growth, has short preparation time and high raw material utilization rate (the preparation time and the raw material utilization rate of the COFs films having the same number of layers are shown in table 2), can greatly reduce the cost, and is easy to implement.
TABLE 2
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A method for preparing a covalent organic framework material film by quantitative layer-by-layer self-assembly is characterized by comprising the following steps:
(1) pretreating a substrate, chemically modifying the substrate, and introducing an anchoring group on the surface of the substrate;
(2) preparing one or more monomer solutions;
(3) respectively spraying one or more monomer solutions obtained in the step (2) on the modified substrate obtained in the step (1) through spraying equipment according to a stoichiometric ratio, and carrying out reaction bonding to obtain a layer of grown film;
(4) and (4) continuously spraying one or more monomer solutions on the substrate on which the growing film is formed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
2. The method for preparing the covalent organic framework material film according to claim 1, wherein the substrate in step (1) comprises a base film or a matrix, and the material of the base film or the matrix comprises metal, ceramic, metal oxide, sulfide, glass or macromolecule.
3. The method for preparing a covalent organic framework material film according to claim 2, wherein the anchor group in step (1) comprises carboxyl, amino, hydroxyl, alkoxy or cyano.
4. The method for preparing the covalent organic framework material film according to claim 1, wherein the monomers in the step (2) comprise boric acid compounds, amine compounds, aldehyde compounds, acyl chloride compounds and anhydride compounds.
5. The method for preparing the covalent organic framework material film by quantitative layer-by-layer self-assembly according to claim 1, wherein the reaction bonding conditions in the step (3) are as follows: the reaction temperature is 25-120 ℃, and the reaction time is 1-6 hours.
6. The method for preparing the covalent organic framework material film according to claim 5, wherein the reaction bonding environment in the step (3) is vacuum, nitrogen or inert atmosphere.
7. The method for preparing the covalent organic framework material film according to claim 1, wherein the monomer solution in step (4) is one or more groups of monomer solutions.
8. The method for preparing the covalent organic framework material film by quantitative layer-by-layer self-assembly according to claim 7, wherein the step (4) of continuously spraying the group of monomer solutions comprises: and (4) continuously spraying a group of monomer solutions which are the same as the monomer solutions sprayed in the step (3) on the substrate on which the growing film is formed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
9. The method for preparing the covalent organic framework material film by quantitative layer-by-layer self-assembly according to claim 7, wherein the step (4) of continuously spraying the plurality of groups of monomer solutions comprises: continuously spraying a group of monomer solutions which are the same as the monomer solutions sprayed in the step (3) on the substrate on which the growing film is formed in the step (3) until the film grows to the required layer number or thickness; and (4) continuously spraying one or more groups of monomer solutions different from the monomer solution sprayed in the step (3) until the film grows to the required number of layers or thickness, and obtaining the covalent organic framework material film.
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