CN108822301B - Method for preparing functional covalent organic framework material by monomer exchange - Google Patents
Method for preparing functional covalent organic framework material by monomer exchange Download PDFInfo
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Abstract
The invention discloses a method for preparing a functionalized covalent organic framework material by monomer exchange, belonging to the technical field of preparation of covalent organic frameworks. Since the amino aldehyde group and the like are reactive groups for preparing the imine covalent organic framework, the imine covalent organic framework with functionalized reactive groups cannot be obtained by the conventional direct synthesis method. The method utilizes a monomer exchange mode to prepare the imine covalent organic framework with functionalized reaction groups, and the synthesized covalent organic framework with functionalized reaction groups has a specific crystal structure, a pore passage, a particle size and good thermal stability.
Description
Technical Field
The invention relates to a method for preparing a functionalized covalent organic framework material by monomer exchange, belonging to the technical field of preparation of covalent organic frameworks.
Background
The covalent organic framework is a highly ordered porous crystal polymer constructed by organic monomers consisting of light elements through covalent bonds, and has excellent properties of structural rigidity (2D or 3D), low density, good thermal stability and chemical stability, large specific surface area, highly ordered pore channels and the like, so that the covalent organic framework material has good application prospects in various fields of gas storage, catalysis, sensing, separation and the like. However, since the common amino, aldehyde and boronic acid groups are reactive groups for preparing covalent organic frameworks, these functionalized covalent organic frameworks cannot be prepared by direct synthesis (de novo), and thus few functionalized covalent organic frameworks have been reported. Although the post-modification method may obtain such functionalized covalent organic frameworks, the post-modification method has complicated preparation steps and is not uniform enough in functionalization, so it is important to develop a method for preparing such functionalized covalent organic frameworks rapidly and simply. Based on this, the present invention has developed a simple ligand exchange method to prepare these functionalized covalent organic framework materials that are not available by direct synthesis.
Disclosure of Invention
The invention aims to provide a preparation method of a monomer-exchanged functionalized covalent organic framework material aiming at the defects. The method uses covalent organic framework material prepared by direct synthesis as a matrix, and uses monomers with reaction groups (such as imine covalent organic framework, namely amino or aldehyde, and boron covalent organic framework, namely boric acid) to replace constituent units in the covalent organic framework of the matrix to prepare the functionalized covalent organic framework, thereby providing an effective way for preparing the functionalized covalent organic framework which is difficult to prepare by direct synthesis.
It is a first object of the present invention to provide a process for the preparation of functionalized covalent organic framework materials which is not possible by a simple direct synthesis.
In one embodiment, the covalent organic framework is an imine-based covalent organic framework.
In one embodiment, the covalent organic framework is a boron-based covalent organic framework.
In one embodiment, the aldehyde or amino functionalized covalent organic frameworks are prepared by replacing the parent covalent organic framework building block with an aldehyde or amino ligand.
In one embodiment, the boronic acid functionalized covalent organic frameworks are prepared by replacing parent covalent organic framework building blocks with boronic acid group ligands.
In one embodiment, the method comprises: mixing an amine compound or an aldehyde compound with a solvent, and then reacting for a period of time under certain conditions to obtain a matrix; and adding an amino ligand or an aldehyde ligand to continue reacting for a period of time, centrifuging, collecting solids, and cleaning to obtain the functionalized covalent organic framework.
In one embodiment, the aldehyde compound may be 2,4, 6-tris (4-formyl-phenyl) -1,3, 5-triazine, 1,3, 5-tris (4-formyl-phenyl) benzene, terephthalaldehyde, biphenyldicarboxaldehyde, 1,3, 5-benzenetrialdehyde.
In one embodiment, the amine compound may be 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, p-phenylenediamine, benzidine.
In one embodiment, the amino ligand may be 3,3' -diaminobenzidine, 1,2, 4-benzenetriamine dihydrochloride.
In one embodiment, the aldehyde-based ligand may be 3,3' -dialdehyde biphenyl aldehyde, 2, 5-dialdehyde terephthalaldehyde.
In one embodiment, the method is specifically:
1) mixing an amine compound or an aldehyde compound, acetic acid, Tetrahydrofuran (THF) and N, N-dimethylacetamide, and performing ultrasonic treatment for 5 minutes to obtain a uniform reaction solution;
2) transferring the reaction tube to the condition of 70-140 ℃ for reaction for 2-4 days to obtain a yellow parent body covalent organic framework material;
3) and cooling to room temperature, directly adding an amino ligand or an aldehyde ligand into the preparation reaction tube, continuously reacting for 2-4 days at the temperature of 30-80 ℃, centrifugally collecting the finally generated red solid, and cleaning to obtain the required amino functionalized covalent organic framework.
In one embodiment, the molar ratio of the amine compound to the triazine compound is (0.1-0.4) mmol: 0.1 mmol. The addition amount of the amino ligand or the aldehyde ligand is 8-12 times of equivalent.
In one embodiment, the method comprises the steps of:
1) mixing 1,3, 5-tri (4-formyl-phenyl) triazine, p-phenylenediamine, acetic acid, Tetrahydrofuran (THF) and N, N-dimethylacetamide in a Schlenk tube, and performing ultrasonic treatment for 5 minutes to obtain a uniform reaction solution;
2) the reaction tube was transferred to 120 ℃ and reacted for 3 days to obtain a yellow precursor covalent organic framework material PTPA.
3) And after cooling to room temperature, directly and continuously adding 3,3' -diaminobenzidine into the reaction tube, continuously reacting for 3 days at 40 ℃, centrifuging at 10000rpm to collect the finally generated red solid, and alternately washing the separated solid with THF and DCM for 3 times, and centrifuging and washing to obtain the required amino functionalized covalent organic skeleton.
The molar ratio of p-phenylenediamine to 1,3, 5-tris (4-formyl-phenyl) triazine was 0.15 mmol: 0.1mmol, and the total amount of the final reaction solution was 2m L.3, 3' -diaminobenzidine added in an amount of 10-fold equivalents.
It is a second object of the present invention to provide a functionalized covalent organic framework material prepared according to the above method.
The third purpose of the invention is to provide the application of the functionalized covalent organic framework material, such as the removal of carbon dioxide and energy storage (methane or hydrogen), and after the amino group is further functionalized, the obtained material can also be used as a liquid phase, a gas phase stationary phase, a solid phase extraction adsorbent and the like.
Advantageous effects
The method firstly prepares a parent covalent organic framework material with high crystallinity, and then utilizes a monomer with a reaction group for preparing the covalent organic framework to exchange a constituent monomer of the parent covalent organic framework material, thereby preparing the functional covalent organic framework material which can not be prepared by a direct synthesis method and has high crystallinity. The invention can prepare functional covalent organic frameworks which can not be prepared by the conventional direct method, such as amino, aldehyde or phenylboronic acid functional covalent organic framework materials. The prepared covalent organic framework material has high crystallinity, good thermal stability and chemical stability.
Drawings
FIG. 1 shows the parent covalent organic framework material PTPA and the amino-functionalized covalent organic framework PTBD-NH obtained in example 12Powder X-ray diffraction pattern of (1).
FIG. 2 shows the parent covalent organic framework material PTPA and the amino-functionalized covalent organic framework PTBD-NH obtained in example 12An infrared spectrum of (1).
FIG. 3 is the amino-functionalized covalent organic backbone PTBD-NH prepared in example 12Thermogram of (c).
FIG. 4 is the amino-functionalized covalent organic backbone PTBD-NH prepared in example 12Transmission electron micrograph (D).
Detailed Description
Example 1
A method for preparing a functional covalent organic framework material by monomer exchange comprises the following steps:
1) 16.3mg of p-phenylenediamine, 39.3mg of 1,3, 5-tris (4-formyl-phenyl) triazine, 0.3M of L6M of acetic acid, 2M of L of tetrahydrofuran and 1M of L N, N-diethylacetamide were mixed in a Schlenk tube and subjected to sonication for 5min to obtain a uniform reaction solution.
2) The reaction tube was transferred to 120 ℃ and reacted for 3 days to obtain a yellow precursor covalent organic framework material PTPA.
3) After cooling to room temperature, 3' -diaminobenzidine was added directly to the reaction tube for PTPA preparation, the reaction was continued for 3 days at 40 ℃, the red solid formed finally was collected by centrifugation at 10000rpm, and the separated solid was washed alternately with THF and DCM for 3 times with centrifugal washing to obtain the desired amino functionalized covalent organic backbone PTBD-NH2 with a yield of 71%.
FIG. 1 is a powder X-ray diffraction pattern of the prepared parent covalent organic framework material PTPA and amino functionalized covalent organic framework PTBD-NH 2. The figure shows that after ligand exchange, the main diffraction characteristic peak of the resulting amino functionalized covalent organic framework is significantly changed compared to the parent, wherein the position of the main peak is changed from 2.9 to 2.4, indicating the success of the amino ligand exchange.
FIG. 2 shows the resulting parent covalent organic frameworks PTPA and amino-functionalized covalent organic frameworks PTBD-NH2An infrared spectrum of (1). The prepared PTBD-NH is shown23197cm in the infrared image-1Obvious vibration peak of amino group appears, and the amino group functionalized covalent organic framework is successfully prepared.
FIG. 3 is a thermogram of the prepared amino-functionalized covalent organic framework. The prepared PTBD-NH is shown2The material has good thermal stability, and the thermal stability temperature can reach 400 ℃.
FIG. 4 is a transmission electron micrograph of the prepared amino-functionalized covalent organic frameworks, showing the prepared PTBD-NH2And (3) a bit sheet layer structure material.
Example 2
A method for preparing a functionalized covalent organic framework material by monomer exchange is basically the same as that in example 1, except that an amino ligand in step 3 is replaced by 1,2, 4-benzenetriamine dihydrochloride, and the prepared nano material is structurally characterized by adopting a method similar to that in example 1, and the result shows that the amino functionalized covalent organic framework is really obtained. The yield of amino-functionalized covalent organic frameworks was 80%.
Example 3
A method for preparing a functionalized covalent organic framework material by monomer exchange, which comprises the steps and the method which are basically the same as those in example 1, except that p-phenylenediamine is replaced by benzidine in the step 1, and the prepared nano material is structurally characterized by adopting the method which is similar to that in example 1, the result shows that the amino functionalized covalent organic framework is really obtained, and the yield of the obtained amino functionalized covalent organic framework is 73 percent.
Example 4
A method for preparing a functionalized covalent organic framework material by monomer exchange, which comprises the steps and the method which are basically the same as those in example 1, except that p-phenylenediamine in step 1 is replaced by benzidine, amino ligand in step 3 is replaced by 1,2, 4-benzenetriamine dihydrochloride, and the prepared nano material is structurally characterized by adopting the method which is similar to that in example 1, the result shows that the amino functionalized covalent organic framework is really obtained, and the yield of the obtained amino functionalized covalent organic framework is 75%.
Example 5
A method for preparing a functionalized covalent organic framework material by monomer exchange is basically the same as that in example 1, except that p-phenylenediamine and 1,3, 5-tri (4-formyl-phenyl) triazine in step 1 are replaced by p-phthalaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, and an amino ligand in step 3 is replaced by an aldehyde ligand 3,3' -dialdehyde biphenyl aldehyde, and the prepared nanomaterial is structurally characterized by adopting a method similar to that in example 1, and the result shows that the aldehyde functionalized covalent organic framework is really obtained, and the yield of the obtained aldehyde functionalized covalent organic framework is 82%.
Example 6
A method for preparing a functionalized covalent organic framework material by monomer exchange, which comprises the steps and the method which are basically the same as those in example 1, except that p-phenylenediamine and 1,3, 5-tri (4-formyl-phenyl) triazine in the step 1 are replaced by terephthalaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, an amino ligand in the step 3 is replaced by an aldehyde ligand 2, 5-dialdehyde terephthalaldehyde, and the prepared nano material is structurally characterized by adopting a method which is similar to that in example 1, and the result shows that the aldehyde functionalized covalent organic framework is really obtained, and the yield of the obtained aldehyde functionalized covalent organic framework is 77%.
Example 7
A method for preparing a functionalized covalent organic framework material by monomer exchange is basically the same as that in example 1, except that p-phenylenediamine and 1,3, 5-tri (4-formyl-phenyl) triazine in step 1 are replaced by biphenyl dicarboxaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, and an amino ligand in step 3 is replaced by an aldehyde ligand 3,3' -dialdehyde biphenyl aldehyde, and the prepared nanomaterial is structurally characterized by adopting a method similar to that in example 1, and the result shows that the aldehyde functionalized covalent organic framework is really obtained and the yield of the obtained aldehyde functionalized covalent organic framework is 74%.
Example 8
A method for preparing a functionalized covalent organic framework material by monomer exchange, which comprises the steps and the method which are basically the same as those in example 1, except that p-phenylenediamine and 1,3, 5-tri (4-formyl-phenyl) triazine in the step 1 are replaced by biphenyl dicarboxaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, and amino ligand in the step 3 is replaced by aldehyde ligand 2, 5-dialdehyde terephthalaldehyde, and the prepared nano material is structurally characterized by adopting a method which is similar to that in example 1, and the result shows that the aldehyde functionalized covalent organic framework is really obtained, and the yield of the obtained aldehyde functionalized covalent organic framework is 77%.
Claims (6)
1. A method for preparing a functionalized covalent organic framework material is characterized in that the functionalized covalent organic framework material is a covalent organic framework material which cannot be prepared by a direct synthesis method (de novo); the method is characterized in that a covalent organic framework material prepared by a direct synthesis method is used as a matrix, and a monomer with a reaction group used in the preparation of the matrix is used for replacing a constitutional unit in the covalent organic framework of the matrix to prepare a functionalized covalent organic framework;
the functional group of the functional covalent organic framework material is any one or more of amino, aldehyde group and boric acid group;
the monomers for preparing the parent covalent organic frameworks are aldehyde compounds, amine compounds and boric acid compounds.
2. The method according to claim 1, characterized in that it comprises: dissolving or dispersing a reaction monomer capable of being used for preparing a covalent organic framework in a solvent, reacting for a period of time under certain conditions to obtain a parent covalent organic framework, adding a ligand with a reaction group for preparing the covalent organic framework for continuous reaction, centrifuging, collecting solids, and cleaning to obtain the functionalized covalent organic framework.
3. The method according to claim 1, characterized in that it is in particular:
1) mixing an amine compound and an aldehyde compound or a boric acid compound, acetic acid, Tetrahydrofuran (THF) and N, N-dimethylacetamide, and carrying out ultrasonic treatment for 5 minutes to obtain a uniform reaction solution;
2) transferring the reaction solution to the condition of 70-140 ℃ for reaction for 2-4 days to obtain a parent body covalent organic framework material;
3) cooling to room temperature, directly adding amino ligand, aldehyde group or boric acid group ligand into the reaction tube, continuing to react for 2-4 days at 30-80 ℃, centrifugally collecting the finally generated solid, and cleaning to obtain the required functionalized covalent organic framework.
4. The method according to claim 3, wherein the molar ratio for preparing the covalent organic framework monomers is (0.1-0.4) mmol: 0.1 mmol; the addition amount of the functionalized ligand is 1-12 times equivalent
5. A functionalized covalent organic framework material prepared according to the method of any one of claims 1 to 4.
6. Use of the functionalized covalent organic framework material according to claim 5.
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