CN112142989A - Preparation method of mesoporous MOFs material - Google Patents
Preparation method of mesoporous MOFs material Download PDFInfo
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Abstract
The application belongs to the field of new materials and synthetic chemistry, and provides a preparation method of mesoporous MOFs materials. The maximum pore diameter of the obtained MOFs material can exceed 30 nm.
Description
Technical Field
The application relates to the field of new materials and synthetic chemistry, in particular to a preparation method of a novel mesoporous MOFs material.
Background
The porous material has a regular and uniform pore structure, and can be divided into micropores (smaller than 2nm), mesopores (2-50nm) and macropores (larger than 50nm) according to the pore size. With the continuous development of porous materials, Metal-Organic Frameworks (MOFs) are rapidly becoming one of the hot areas of research and application. MOFs are materials with supermolecular microporous network structure formed by complexing metal ions or metal clusters as centers and organic ligands for self-assembly. MOFs have the characteristics of uniform and adjustable pore size, easy functionalization, high specific surface area (up to 10000m2/g), high porosity (more than 50%) and the like, so that the MOFs are widely applied to the fields of gas storage, separation, optics, sensors, catalysis and the like.
The organic ligands for the synthesis of MOFs are often selected from the class of carboxylic acids and polyazaheterocycles: the carboxylic acid organic ligand is easy to modify, has multiple coordination modes, and can form various MOFs materials; the multi-nitrogen heterocyclic organic ligand has fixed coordination orientation, MOFs materials with expected stable structures can be obtained more easily, and the coordination bond energy between nitrogen atoms and metal ions is larger, so that the stability of the materials can be improved. At present, the common synthetic methods of the MOFs materials include: a water (solvent) thermal synthesis method, an electrochemical synthesis method, a microwave-assisted heating method, an ultrasonic synthesis method, an ionothermal synthesis method, and the like, wherein the water (solvent) thermal synthesis method is one of the most commonly used simple synthesis methods. However, the MOFs material synthesized by the method has a small pore size of only about 1nm at most. Therefore, in order to obtain mesoporous MOFs, other methods have to be used to enlarge the pore size of the MOFs material.
There are three common methods of reaming: surfactant templating, extended organic ligands and modifier induced defect formation. The surfactant template method is to form a porous skeleton with certain structure and morphology by using a multi-molecule aggregate (micelle, capsule and other forms) formed by mutually aggregating a plurality of surfactant molecules as a template and utilizing the interface action of organic molecules and inorganic substances, and then remove the template agent by chemical treatment to obtain a mesoporous structure. Along with the gradual increase of the addition amount of the template agent, the total pore volume and the specific surface area of the sample gradually increase, but the growth of crystals is influenced by the excessively fast crystallization speed, so that the appearance of the crystals is irregular, and the size of internal mesopores is not uniform. The extended organic ligand method is a method for constructing a metal organic framework material containing mesoporous cages by using organic ligands with longer sizes and the centers of metal clusters. As the MOFs constructed by the long-chain ligands are prone to collapse in the guest migration process and are often accompanied with skeleton interpenetration, the sizes of pores can be greatly reduced, and therefore macromolecules are limited from entering the MOFs. The regulator-induced defect formation method is a simple and universal MOFs (metal-organic frameworks) hole expanding method, and can prepare large-pore MOFs in the presence of monocarboxylic acid as a regulator through an insufficient reaction between a metal precursor and a ligand, but the MOFs prepared by the method has poor stability.
Disclosure of Invention
The technical problem that this application will solve lies in: provides a preparation method of mesoporous MOFs materials, and solves the problem that the mesoporous MOFs materials are difficult to prepare.
In order to solve the above problems, in a first aspect of the present application, a pyridine organic ligand for preparing mesoporous MOFs materials is provided, which has a structural formula as follows:
wherein X, Y, Z is selected from hydrogen, cyano, amino, carboxyl, dimethylamino;
R1、R2、R3、R4、R5、R6selected from hydrogen, methyl, ethyl, n-propyl, isopropyl.
In a preferred embodiment, the pyridine organic ligand is at least one of the following:
in a second aspect of the present application, a preparation method of mesoporous MOFs materials is provided, wherein a pyridine organic ligand is used to synthesize the mesoporous MOFs materials, and the structural general formula of the mesoporous MOFs materials is as follows:
wherein X, Y, Z is selected from hydrogen, cyano, amino, carboxyl, dimethylamino;
R1、R2、R3、R4、R5、R6selected from hydrogen, methyl, ethyl, n-propyl, isopropyl.
In a preferred embodiment, the pyridine organic ligand is at least one of the following:
in a preferred embodiment, the mesoporous MOFs material is synthesized by any one of hydrothermal synthesis, microwave-assisted heating and ultrasonic synthesis; and (3) reaming the mesoporous MOFs material by using a surfactant template method.
In a third aspect of the present application, a method for preparing a mesoporous MOFs material is provided, which comprises the following steps:
s1, dissolving a metal ion precursor in an aqueous solution;
s2, adding a solution in which a pyridine organic ligand is dissolved, uniformly mixing, and adding a template agent; the pyridine organic ligand has the following structural general formula:
wherein X, Y, Z is selected from hydrogen, cyano, amino, carboxyl, dimethylamino; r1、R2、R3、R4、R5、R6Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl;
s3, placing the mixed solution in a reaction kettle, and carrying out hydrothermal, microwave-assisted heating or ultrasonic reaction to obtain the mesoporous MOFs material.
In a preferred embodiment, in step S1, the metal ion precursor is at least one of copper nitrate, zinc nitrate, copper acetate, zinc acetate, copper chloride, zinc chloride, cobalt nitrate, ferric nitrate, aluminum nitrate, manganese nitrate, and zirconium nitrate; in the step S2, the solution is at least one of methanol, ethanol, isopropanol, n-butanol, pentanediol, dimethylformamide, dichloromethane, acetone, ethyl acetate, n-hexane, benzene, and toluene. The metal ion precursor and the solution have similar properties, and the MOFs material obtained by synthesis has small difference in surface appearance and pore size.
In a preferred embodiment, in step S2, the template is at least one of CTAB, TMB, n-decane and citric acid.
The application has the following beneficial effects: the obtained MOFs material has regular crystal morphology, uniform internal mesoporous size and good stability, and the maximum pore diameter can exceed 30 nm.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the mesoporous MOFs material obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the mesoporous MOFs material obtained in example 2;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the mesoporous MOFs material obtained in example 3;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the mesoporous MOFs material obtained in example 4.
Detailed Description
The technical solutions of the present application will be described in detail below with reference to the accompanying drawings and specific embodiments, but the description of the embodiments is only a part of the embodiments of the present application, and most of them are not limited thereto.
The starting materials used in the following examples are commercially available unless otherwise specified.
Example 1
4.5mmol of copper nitrate were dissolved in 15ml of deionized water and mixed with 2.5mmol of 4- (4-pyridine) benzonitrile dissolved in 15ml of ethanol. Then, 0.7mmol of cetyltrimethylammonium bromide (CTAB) and 0.7mmol of mesitylene (TMB) were added while stirring. The mixture was placed in a 60mL hydrothermal kettle and reacted at 120 ℃ for 12 h. After the reaction, the mixture was filtered, and the obtained powder was washed with water and ethanol. And finally, extracting for three times by using an ethanol solution to remove a template agent (CTAB/TMB), and drying to obtain the MOFs material. The obtained material is a micron-sized porous sheet structure, the average pore diameter is 8nm, and an SEM image is shown in figure 1.
Example 2
4.5mmol of copper nitrate were dissolved in 15ml of deionized water and mixed with 4.3mmol of 4- (4-pyridine) benzonitrile dissolved in 15ml of ethanol. Then, while stirring, the templates 2.7mmol of cetyltrimethylammonium bromide (CTAB) and 2.7mmol of mesitylene (TMB) were added. The mixture was placed in a 60mL hydrothermal kettle and reacted at 120 ℃ for 12 h. After the reaction, the mixture was filtered, and the obtained powder was washed with water and ethanol. And finally, extracting for three times by using an ethanol solution to remove a template agent (CTAB/TMB), and drying to obtain the MOFs material. The obtained material is a micron-sized porous sheet structure, the average pore diameter is 12nm, and an SEM image is shown in figure 2.
Example 3
4.5mmol of copper nitrate were dissolved in 15ml of deionized water and mixed with 4.3mmol of 4- (4-pyridine) benzonitrile dissolved in 15ml of ethanol. Then, 1.4mmol of cetyltrimethylammonium bromide (CTAB) and 0.7mmol of mesitylene (TMB) were added while stirring. The mixture was placed in a 60mL hydrothermal kettle and reacted at 120 ℃ for 12 h. After the reaction, the mixture was filtered, and the obtained powder was washed with water and ethanol. And finally, extracting for three times by using an ethanol solution to remove a template agent (CTAB/TMB), and drying to obtain the MOFs material. The obtained material is a micron-sized porous sheet structure, the average pore diameter is 32nm, and an SEM image is shown in figure 3.
Example 4
The difference from example 3 is that 4.3mmol of 4- (4-pyridine) benzonitrile was changed to 4.3mmol of 4- (4-pyridine) aniline. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 33 nm.
Example 5
The difference from example 3 is that 4.3mmol of 4- (4-pyridine) benzonitrile was changed to 4.3mmol of 4- (4-pyridine) benzoic acid. The obtained material is a micron-sized porous sheet structure, the average pore diameter is 35nm, and an SEM image is shown in figure 4.
Example 6
The difference from example 3 is that 4.5mmol of copper nitrate was changed to 4.5mmol of zinc nitrate. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 26 nm.
Example 7
The difference from example 4 was that 4.5mmol of copper nitrate was changed to 4.5mmol of zinc nitrate. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 28 nm.
Example 8
The difference from example 5 is that 4.5mmol of copper nitrate was changed to 4.5mmol of zinc nitrate. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 30 nm.
Example 9
4.5mmol of copper nitrate were dissolved in 15ml of deionized water and mixed with 4.3mmol of 4- (4-pyridine) benzonitrile dissolved in 15ml of ethanol. Then, 1.4mmol of cetyltrimethylammonium bromide (CTAB) and 0.7mmol of mesitylene (TMB) were added while stirring. The mixture was placed in a 100mL microwave reactor and reacted for 3h at 500W microwave power and 2500MHz frequency. After the reaction, the mixture was filtered, and the obtained powder was washed with water and ethanol. And finally, extracting for three times by using an ethanol solution to remove a template agent (CTAB/TMB), and drying to obtain the MOFs material. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 29 nm.
Example 10
4.5mmol of copper nitrate were dissolved in 15ml of deionized water and mixed with 4.3mmol of 4- (4-pyridine) benzonitrile dissolved in 15ml of ethanol. Then, 1.4mmol of cetyltrimethylammonium bromide (CTAB) and 0.7mmol of mesitylene (TMB) were added while stirring. The mixture was placed in a 100mL ultrasonic reactor and reacted for 3h at 600W ultrasonic power, 22kHz operating frequency, 50 ℃. After the reaction, the mixture was filtered, and the obtained powder was washed with water and ethanol. And finally, extracting for three times by using an ethanol solution to remove a template agent (CTAB/TMB), and drying to obtain the MOFs material. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 28 nm.
Example 11
Except for using 1.4mmol of cetyltrimethylammonium bromide (CTAB) and 0.7mmol of mesitylene (TMB) as templates, and changing them to 1.4mmol of n-decane and 0.7mmol of citric acid as in example 3. The obtained material is a micron-sized porous sheet structure, and the average pore diameter is 30 nm.
The MOFs materials prepared in examples 1-11 above were subjected to BET nitrogen adsorption testing and SEM characterization testing, respectively.
The results of the tests for examples 1-11 above are shown in the following table.
Aiming at the problems that the crystal growth is influenced by the too fast crystallization speed along with the increase of the addition amount of the template agent, the crystal appearance is irregular, and the size of an internal mesoporous is not uniform, the novel pyridine organic ligand is used for inhibiting the crystallization speed, and the MOFs material with regular crystal appearance, uniform size of the internal mesoporous and good stability is successfully obtained. The maximum pore diameter of the obtained MOFs material can exceed 30 nm.
The foregoing examples further illustrate the content of the present application but are not to be construed as limiting the present application. Modifications and substitutions to methods, steps or conditions of the present application are intended to be within the scope of the present application without departing from the spirit and substance of the present application. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Claims (8)
1. The pyridine organic ligand for preparing the mesoporous MOFs material is characterized by having the following structural general formula:
wherein X, Y, Z is selected from hydrogen, cyano, amino, carboxyl, dimethylamino;
R1、R2、R3、R4、R5、R6selected from hydrogen, methyl, ethyl, n-propyl, isopropyl.
2. The pyridine organic ligand according to claim 1, wherein the pyridine organic ligand is at least one of:
3. a preparation method of mesoporous MOFs materials is characterized in that pyridine organic ligands are used for synthesizing the mesoporous MOFs materials, and the structural general formula of the mesoporous MOFs materials is as follows:
wherein X, Y, Z is selected from hydrogen, cyano, amino, carboxyl, dimethylamino;
R1、R2、R3、R4、R5、R6selected from hydrogen, methyl, ethyl, n-propyl, isopropyl.
4. The method according to claim 3, wherein the pyridine organic ligand is at least one of:
5. the method according to claim 3, wherein the mesoporous MOFs material is synthesized by any one of hydrothermal synthesis, microwave-assisted heating and ultrasonic synthesis; and (3) reaming the mesoporous MOFs material by using a surfactant template method.
6. A preparation method of mesoporous MOFs materials is characterized by comprising the following steps:
s1, dissolving a metal ion precursor in an aqueous solution;
s2, adding a solution in which a pyridine organic ligand is dissolved, uniformly mixing, and adding a template agent; the pyridine organic ligand has the following structural general formula:
wherein X, Y, Z is selected from hydrogen, cyano, amino, carboxyl, dimethylamino; r1、R2、R3、R4、R5、R6Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl;
s3, placing the mixed solution in a reaction kettle, and carrying out hydrothermal, microwave-assisted heating or ultrasonic reaction to obtain the mesoporous MOFs material.
7. The preparation method according to claim 6, wherein in the step S1, the metal ion precursor is at least one of copper nitrate, zinc nitrate, copper acetate, zinc acetate, copper chloride, zinc chloride, cobalt nitrate, ferric nitrate, aluminum nitrate, manganese nitrate, and zirconium nitrate; in the step S2, the solution is at least one of methanol, ethanol, isopropanol, n-butanol, pentanediol, dimethylformamide, dichloromethane, acetone, ethyl acetate, n-hexane, benzene, and toluene.
8. The method according to claim 6, wherein in step S2, the template is at least one of CTAB, TMB, n-decane and citric acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538241A (en) * | 2009-04-30 | 2009-09-23 | 广西师范大学 | 4-(4-pyridyl) phenylformic acid complex material and preparation method and application thereof |
| CN103920462A (en) * | 2013-01-15 | 2014-07-16 | 中国科学院大连化学物理研究所 | Preparation method for metal-organic framework nanoparticle material with mesoporous structure |
| CN107245136A (en) * | 2017-05-13 | 2017-10-13 | 淮阴师范学院 | A kind of ordered mesoporous polymer material and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538241A (en) * | 2009-04-30 | 2009-09-23 | 广西师范大学 | 4-(4-pyridyl) phenylformic acid complex material and preparation method and application thereof |
| CN103920462A (en) * | 2013-01-15 | 2014-07-16 | 中国科学院大连化学物理研究所 | Preparation method for metal-organic framework nanoparticle material with mesoporous structure |
| CN107245136A (en) * | 2017-05-13 | 2017-10-13 | 淮阴师范学院 | A kind of ordered mesoporous polymer material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| ROC MATHEU等: "Behavior of Ru–bda Water-Oxidation Catalysts in Low Oxidation States", 《CHEM. EUR. J.》 * |
| 苗东亮: "吡啶苯甲酸系列金属配合物的合成及生物活性研究", 《中国优秀硕士学位论文全文数据库》 * |
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Application publication date: 20201229 |