CN110540654B - Amino functional modification method of metal organic framework MIL-101 - Google Patents
Amino functional modification method of metal organic framework MIL-101 Download PDFInfo
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- CN110540654B CN110540654B CN201910733398.2A CN201910733398A CN110540654B CN 110540654 B CN110540654 B CN 110540654B CN 201910733398 A CN201910733398 A CN 201910733398A CN 110540654 B CN110540654 B CN 110540654B
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Abstract
The invention belongs to the technical field of modification of metal organic frameworks, and discloses an amino functional modification method of a metal organic framework MIL-101, which specifically comprises the following steps: s1) preparing MIL-101; s2) grinding MIL-101; s3) weighingMIL-101 grinding powder and ultrapure water are put into a beaker for mixing; s4) carrying out ultrasonic dispersion on the mixed solution, adding an amino coupling agent after dispersion, and uniformly stirring; s5) putting the mixed solution formed in the step S4) into a three-neck flask, and performing reflux treatment; s6) carrying out centrifugal treatment on the refluxed reaction liquid, and separating out a precipitate obtained by reaction in the reaction liquid; s7) drying and precipitating to obtain NH 2 -a synthetic of MIL-101; according to the method, grafting between amino and the framework MIL-101 can be effectively realized, and functional modification on the metal organic framework MIL-101 is completed on the basis of keeping the original framework structure; meanwhile, the integral modification method also has the advantages of easy achievement of preparation conditions and simple and convenient preparation operation.
Description
Technical Field
The invention belongs to the technical field of modification of metal organic frameworks, and particularly relates to an amino functional modification method of a metal organic framework MIL-101.
Background
The metal-organic framework is a novel crystalline porous material which is formed by metal ions or metal clusters and organic ligands through coordination bonds and has a periodic infinite topological structure, and has the advantages of high porosity, large specific surface area, various structures and the like;
according to the prior art, functional groups are introduced into a metal organic framework in a certain way, and the functional metal organic framework is constructed, so that the service performance of the metal organic framework can be improved;
however, most of the functional modification methods used in the prior art have problems of complicated steps and difficulty in modification conditions, and thus it is necessary to provide a modification method that is simple in both operation and modification conditions.
Disclosure of Invention
The invention aims to provide an amino functional modification method of a metal organic framework MIL-101, so as to meet the requirement of preparing a functional metal organic framework more simply and conveniently in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: an amino functional modification method of a metal organic framework MIL-101 specifically comprises the following steps:
s1) dissolving 4-nitroimidazole, terephthalic acid and chromium nitrate nonahydrate in deionized water according to the concentration ratio of 1: 2, stirring until the mixture is completely dissolved, placing the mixture into a reaction kettle, crystallizing the mixture for 5 days in a drying box at 150 ℃, naturally cooling the crystallized mixture to room temperature, centrifuging the crystallized mixture for 10 minutes at the rotation speed of 10000 r/min to obtain a precipitate, and drying the precipitate in the drying box at 50 ℃ to obtain MIL-101;
s2) grinding the prepared MIL-101 into powder;
s3) weighing MIL-101 grinding powder and ultrapure water according to the mass ratio of 1: 50-60, and putting the MIL-101 grinding powder and the ultrapure water into a beaker for mixing; for example: when the dosage of MIL-101 is 0.30g, the dosage of ultrapure water is 15ml; in the following examples: when the dosage of MIL-101 is 0.50g, the dosage of ultrapure water is 30ml;
s4) carrying out ultrasonic dispersion on the mixed solution until the mixed solution is dispersed, adding an amino trimethoxy silane coupling agent, and uniformly stirring;
s5) putting the mixed solution formed in the step S4) into a three-neck flask, and performing reflux treatment at 100 ℃, wherein covalent bonding between amino groups in the amino trimethoxy silane coupling agent and hydroxyl groups in MIL-101 is realized in the reflux treatment;
s6) carrying out centrifugal treatment on the refluxed reaction liquid, and separating out a precipitate obtained by reaction in the reaction liquid;
s7) drying and precipitating at the temperature of 80 ℃ to obtain NH 2 -a synthetic of MIL-101.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method provided by the invention, grafting between amino and the framework MIL-101 can be effectively realized, and functional modification on the metal organic framework MIL-101 is completed on the basis of keeping the original framework structure; meanwhile, the integral modification method also has the advantages of easy achievement of preparation conditions and simple and convenient preparation operation.
(2) The invention takes the amino trimethoxy silane coupling agent as the basis of amino grafting, and has the advantage of shortening the reaction time while ensuring the effective grafting.
(3) The skeleton crystal particles prepared based on the method are in an octahedral structure, so that the modified crystal structure is more uniform.
Drawings
FIG. 1 is a table comparing synthetic products prepared according to different APS contents of the present invention;
FIG. 2 is an XRD spectrum of a synthetic product prepared according to different APS contents in the present invention;
FIG. 3 is a FT-IR spectrum of synthetic products of the present invention prepared according to different APS contents;
FIG. 4 is a scanning electron micrograph of a composite of the present invention prepared according to different APS contents;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
1. The reagents used in the present invention: the catalyst comprises 4-nitroimidazole, terephthalic acid and chromium nitrate nonahydrate, wherein the concentration of the 4-nitroimidazole is 0.1mol/L, the concentration of the terephthalic acid is 0.2mol/L, and the concentration of the chromium nitrate nonahydrate is 0.2mol/L;
2. MIL-101 preparation and skeleton MIL-101 functional modification are carried out based on the reagent:
example 1:
1.1 MIL-101 preparation:
weighing 2g of 4-nitroimidazole, 4g of terephthalic acid and 4g of chromium nitrate nonahydrate, and dissolving the weighed materials in a certain amount of deionized water in sequence, wherein 70ml of deionized water is taken as an example in the embodiment and stirring is carried out at room temperature until the materials are completely dissolved; then the prepared mixed solution is transferred into a stainless steel reaction kettle with a lining and crystallized for 5 days in a drying box at the temperature of 150 ℃; closing the drying box after crystallization, and naturally cooling to room temperature; centrifuging the mixed solution in the reaction kettle at 10000 r/min for 10 min; after centrifugation, collecting separated solid, and drying the solid in a drying box at 50 ℃ to obtain MIL-101;
1.2 Amino functionalization of MIL-101:
grinding the prepared MIL-101 into powder; then weighing 0.3g of MIL-101, putting the MIL-101 into a beaker, adding 15ml of ultrapure water into the beaker, putting the beaker into an ultrasonic cleaner, and performing ultrasonic dispersion until the MIL-101 is completely dispersed; adding 0.05ml of amino trimethoxy silane coupling agent into the mixed solution after dispersion, and uniformly stirring; then the mixed solution is transferred into a three-neck flask, and reflux reaction is carried out at the temperature of 100 ℃, the reaction time is 12 hours or 24 hours, in the embodiment, 24 hours is taken as an example; after the reaction, carrying out centrifugal separation on the reaction liquid, and collecting reaction precipitates; finally, the precipitate is dried in a drying box at the temperature of 80 ℃ to obtain NH 2 -a synthesis of MIL-101 and labeled NH 2 -MIL-101-APS-X-Y；
The specific APS means an amino trimethoxy silane coupling agent, X means the amount of addition, and Y means the reaction time, i.e., the above-mentioned symbol is NH 2 -MIL-101-APS-0.05-24；
Example 2:
the amination procedure was the same as in example 1, except that the amount of aminotrimethoxysilane coupling agent used in this example was 0.08ml, whereby NH was finally obtained 2 -MIL-101-APS-0.08-24；
Example 3:
the amination process is the same as the previous embodiment, but the amount of MIL-101 used in this embodiment is 0.5g, corresponding to 30ml of ultrapure water; the amount of the aminotrimethoxysilane coupling agent used was 0.1ml, whereby NH was finally obtained 2 -MIL-101-APS-0.1-24；
Example 4:
in this example, the amount of the aminotrimethoxysilane coupling agent was 0.2ml relative to example 3, whereby NH was finally obtained 2 -MIL-101-APS-0.2-24；
Combining the above examples to construct the comparison table shown in FIG. 1, deionized water shown in FIG. 1 is the ultrapure water selected in the above examples;
3. according to the state of the art on NH 2 The usual assay for-MIL-101, for the aboveNH formed by four examples 2 -X-ray diffraction and infrared diffraction of the MIL-101-APS-X-Y synthetic product to form an XRD spectrum as shown in figure 2 and an FT-IR spectrum as shown in figure 3, respectively:
by combining the three main characteristic peaks formed by the four synthetic products under X-ray diffraction, the peak shapes and peak positions in the infrared short wave direction are not changed, so that the combination of amino groups does not influence the original MIL-101 framework, and the integrity of the original framework is effectively ensured;
further, it is shown at 3000cm in FIG. 3 -1 -3500cm -1 The absorption peak and the stretching vibration peak formed by N-H in the amino group appear in the range of (1), thereby showing that the operation of the above embodiment can effectively graft the amino group on the MIL-101;
in addition, fig. 2 shows that as the content of APS increases, the peak intensity thereof is significantly decreased; the method specifically comprises the following steps: after amino is introduced by the MIL-101 framework, the original pore or surface structure in the framework is occupied; when the amino group introduction amount is more, namely the APS content is more, the occupied pore channel or surface structure is also larger, so that the combination of the amino group effectively reduces the crystallization degree of the MIL-101 framework.
4. Scanning and imaging the composite product formed by the four embodiments according to an imaging method commonly used in the art to form an electron microscope image shown in fig. 4:
specifically, a is a crystal diagram of the framework formed in example 1; b is a diagram of the framework crystal formed in example 2; c is a diagram of the framework crystal formed in example 3; d is a diagram of the framework crystal formed in example 4;
according to the crystal structure shown in the figure, the NH formed in the above embodiment 2 The shape of the MIL-101 crystal particles is a uniform octahedral structure.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. An amino functional modification method of a metal organic framework MIL-101 is characterized in that an amino on an amino coupling agent is grafted on the framework MIL-101, and specifically comprises the following steps:
s1) dissolving 4-nitroimidazole, terephthalic acid and chromium nitrate nonahydrate in deionized water according to the concentration ratio of 1: 2, stirring until the mixture is completely dissolved, putting the mixture into a reaction kettle, crystallizing the mixture for 5 days in a drying box at 150 ℃, naturally cooling the crystallized mixture to room temperature, centrifugally collecting the crystallized mixture, and drying the crystallized mixture at 50 ℃ to obtain MIL-101;
s2) grinding the prepared MIL-101 into powder;
s3) weighing MIL-101 grinding powder and ultrapure water according to the mass ratio of 1: 50-60, and putting the MIL-101 grinding powder and the ultrapure water into a beaker for mixing;
s4) carrying out ultrasonic dispersion on the mixed solution until the mixed solution is dispersed, adding an amino coupling agent, and uniformly stirring, wherein the amino coupling agent is an amino trimethoxy silane coupling agent;
s5) putting the mixed solution formed in the step S4) into a three-neck flask, and performing reflux treatment at 100 ℃;
s6) carrying out centrifugal treatment on the refluxed reaction liquid, and separating out a precipitate obtained by reaction in the reaction liquid;
s7) drying and precipitating to obtain NH 2 -a synthetic of MIL-101.
2. The method for amino-functional modification of metal-organic framework MIL-101 as claimed in claim 1, wherein: the centrifugal collection in the step S1) is to finish the collection by centrifuging for 10 minutes under the condition that the rotating speed is 10000 r/min.
3. The method for amino-functional modification of metal-organic framework MIL-101 as claimed in claim 1, wherein: the drying temperature in step S7) is 80 ℃.
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