CN106076262B - Application of macrocyclic compound metal organic framework material and preparation method thereof - Google Patents
Application of macrocyclic compound metal organic framework material and preparation method thereof Download PDFInfo
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- CN106076262B CN106076262B CN201610447327.2A CN201610447327A CN106076262B CN 106076262 B CN106076262 B CN 106076262B CN 201610447327 A CN201610447327 A CN 201610447327A CN 106076262 B CN106076262 B CN 106076262B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The invention discloses application of a macrocyclic compound metal-organic framework material and a preparation method thereof, wherein the macrocyclic compound metal-organic framework material is applied to purifying harmful gases such as formaldehyde, benzopyrene, benzene and toluene, and is a hybrid material which is formed by chelating a macrocyclic compound and metal ions and has a crystal configuration and a porous structure. Mixing a macrocyclic compound aqueous solution with an aqueous solution containing metal ions, wherein the molar ratio of the macrocyclic compound to the metal ions is (1:0.05) - (1: 50), fully mixing, putting the whole mixed solution into steam of a poor solvent for assembly reaction, separating out a white precipitate, carrying out solid-liquid separation after full separation, repeatedly washing the obtained solid-phase white precipitate with an organic solvent, naturally volatilizing the solvent, and drying to obtain the macrocyclic compound metal organic framework material to be prepared. The preparation method has the advantages of simple process, small equipment investment, convenient operation and the like.
Description
Technical Field
The invention belongs to the field of functional polymer chemistry, and particularly relates to application and preparation of a metal organic framework material of a macrocyclic compound in the field of air purification.
Technical Field
The metal organic framework material is a crystalline porous material with a periodic and uniform network structure formed by connecting inorganic metal ions (metal ions or metal ion clusters) as centers and organic ligands in a self-assembly mode. The metal organic framework material, also called coordination polymer, is an organic-inorganic hybrid material, which is different from inorganic porous materials and common organic complexes. Combines the rigidity of inorganic materials with the flexibility of organic materials. It has great development potential and attractive development prospect in the aspect of modern material research.
At present, the application field of the metal organic framework material is mainly used for hydrogen storage, catalysis, drug carriers and the like. In recent years, as the demand for clean energy has become more stringent, the demand for hydrogen as a clean fuel has also increased. The metal organic framework material is applied to hydrogen storage, and is used as a material for adsorbing and storing hydrogen after the hydrogen is prepared, so that the problems of safe and efficient storage and utilization of the hydrogen are solved. Metal organic framework materials have also been used for the separation of the greenhouse gas carbon dioxide.
In recent years, the problem of air pollution has been receiving increasing attention. The emission of harmful gases in industrial waste gas and automobile exhaust not only pollutes the environment, but also threatens the health of people. In daily life, formaldehyde and benzene substances used in interior decoration or car interior decoration materials are recognized as harmful carcinogenic substances in the world, and long-term inhalation of the harmful gases greatly improves the probability of cancer of human bodies and easily causes malformation of newborns. The adsorbent is used for removing and purifying harmful components in the air, has the advantages of difficult secondary pollution, simple and convenient purification mode and the like, and is one of the most common modes for purifying the air at present. At present, although there are many kinds of materials as the adsorbent, the material uses micropores in the porous structure adsorbent to adsorb the harmful gas in the air, for example, the most widely used carbon-based adsorbent at present, that is, the carbon-based adsorbent uses micropores to adsorb the harmful gas in the air, but the adsorption efficiency is limited, and especially the adsorption and purification efficiency for the toxic and harmful substances such as formaldehyde, benzene and the like in the air is not high. Along with the deep understanding that people threaten the health of people to harmful substances such as formaldehyde, benzene and the like, people urgently need to provide a purifying agent which can more effectively adsorb and purify the harmful substances such as formaldehyde, benzene and the like in the air, create a clean living space environment and protect the health of people.
Disclosure of Invention
Aiming at the current situation and the defects of the purification technology of harmful substances such as formaldehyde, benzene and the like, the first purpose of the invention is to provide a new application of a macrocyclic compound metal-organic framework material; the second purpose of the invention is to provide a preparation method of the macrocyclic compound metal organic framework material.
Aiming at the first object of the invention, the novel application of the macrocyclic compound metal-organic framework material provided by the invention is the application of the macrocyclic compound metal-organic framework material in purifying harmful gases such as formaldehyde, benzopyrene, benzene and toluene, and the macrocyclic compound metal-organic framework material is a hybrid material which is formed by chelating a macrocyclic compound and metal ions and has a crystal configuration and a porous structure.
In the above uses, the macrocyclic compound metal-organic framework material can be used as an adsorbent for purifying air in a room, an automobile or an unspecified space. The macrocyclic compound metal organic framework material is used as an adsorbent, and can be directly placed in a room to be purified, an automobile or an unspecified space. The dosage of the macrocyclic compound metal organic framework material is related to the size of the space to be purified, the concentration of harmful substances in the air, the time for completing the purification and the like. The specific dosage depends on the size of the space to be purified, the concentration of harmful substances in the air and the time for completing the purification. The macrocyclic compound metal organic framework material is used as an air purification adsorbent, and the air atmosphere temperature is preferably in the range of-20-70 ℃.
In the above uses, the macrocyclic compound metal-organic framework material can be used as an adsorption filtration component in gas masks, air purification equipment or automobile exhaust gas purifiers.
In the above uses, the macrocyclic compound is preferably selected from one of crown ethers, cucurbiturils, cyclodextrins and derivatives thereof.
In the above applications, the particle size of the macrocyclic compound metal-organic framework material is generally controlled in the range of 2-20 um.
Aiming at the second purpose of the invention, the preparation method of the macrocyclic compound metal-organic framework material provided by the invention comprises the following steps: mixing a macrocyclic compound aqueous solution with an aqueous solution containing metal ions, wherein the molar ratio of the macrocyclic compound to the metal ions is (1:0.05) - (1: 50), fully mixing, putting the whole mixed solution into steam of a poor solvent for assembly reaction, separating out a white precipitate, carrying out solid-liquid separation after full separation, repeatedly washing the obtained solid-phase white precipitate with an organic solvent, naturally volatilizing the solvent, and drying to obtain the macrocyclic compound metal organic framework material to be prepared.
In the above method, the time for the assembly reaction is generally controlled to 4 to 240 hours by allowing the entire mixed solution to stand in the vapor of the poor solvent. The length of time is related to the molar ratio of macrocyclic compound to metal ion, and a larger concentration of metal ion will result in a shorter assembly reaction time, whereas the opposite will result in a longer assembly reaction time. The preferential molar ratio of macrocyclic compound to metal ion is (1:0.5) - (1: 5).
In the above process, the poor solvent is preferably selected from the group consisting of acetone, tetrahydrofuran, dioxane, methanol, ethanol and glycerol.
The inventor of the present invention has unconsciously found that the macrocyclic compound metal organic framework material has the adsorption and purification effect on formaldehyde gas in the research of the macrocyclic compound metal organic framework material. Based on the above accidental findings, the inventor further researches the formaldehyde gas adsorption and purification performance of the macrocyclic compound metal organic framework material, and finds that the macrocyclic compound metal organic framework material has very good formaldehyde gas adsorption and purification performance, and also has very good adsorption and purification performance on benzene harmful gases such as benzopyrene, benzene, toluene and the like.
The research of the inventor further finds that the adsorption purification performance of the macrocyclic compound metal organic framework material is far better than that of a carbon-based adsorption material, and one reason is that the macrocyclic compound metal organic framework material used in the invention not only has a large number of structural micropores, but also is more interesting: the macrocyclic substance in the frame itself also has an annular internal pore. The annular inner holes can generate host-guest supramolecular acting force with gas, and the gas is included in the inner holes to form supramolecular chemisorption. The double adsorption mode of micropore physical adsorption and large ring inner hole supermolecule adsorption of the structure ensures that the large ring compound metal organic framework material has super strong adsorption and purification performance on formaldehyde, benzene and other harmful gases. The second reason is that the carbon-based adsorbing material is a non-polar substance, a large amount of harmful gas in the air has stronger polarity, and the carbon-based adsorbing material is used for adsorbing and purifying the harmful gas by utilizing the single physical adsorption principle of micropores in the porous structure of the carbon-based adsorbing material, so that the adsorption efficiency is not high and is limited to a certain extent; and the macrocyclic compound metal organic framework material has pores with two sizes and polarities of a macrocyclic pore and a framework pore, so that the adsorption capacity of the macrocyclic compound metal organic framework material is far superior to that of a carbon-based material. The macrocyclic compound metal organic framework material has super strong adsorption and purification performance on formaldehyde, benzene and other harmful gases, and the inventor of the invention finds that the macrocyclic compound metal organic framework material is the first creation of the invention to be used as an adsorbent for adsorbing and purifying formaldehyde, benzene and other harmful gases and used for filtering and purifying formaldehyde, benzene and other harmful gas components.
Drawings
FIG. 1 is a schematic diagram of the structure of a macrocyclic compound metal-organic framework material.
FIG. 2 is a scanning electron microscope image of a macrocyclic compound metal-organic framework material.
Detailed Description
The use of the macrocyclic metal-organic framework materials disclosed in the present invention and their preparation are further illustrated below by way of examples:
example 1
Weighing 1.3g of alpha-cyclodextrin and 0.45g of potassium hydroxide, adding the alpha-cyclodextrin and the potassium hydroxide into deionized water with the volume of about 20mL, placing the whole body in an air atmosphere containing methanol steam after the alpha-cyclodextrin and the potassium hydroxide are completely dissolved, standing for 2-7 days, enabling white precipitate to appear at the bottom of a container, centrifuging at a rotating speed of 12000r/min after the white precipitate is completely separated out, pouring out methanol solution of supernatant to obtain white precipitate, repeatedly washing the white precipitate for 5 times by using methanol solvent, naturally volatilizing the solvent under the normal temperature condition, naturally volatilizing the white precipitate, drying and activating at the temperature of 40 ℃, and finally obtaining white crystals, namely the metal organic framework material.
1g of the metal-organic framework material is placed in air at 20 ℃ at 1m with excess formaldehyde3In a closed container, the ratio of the total carbon content to the total carbon content exceeds the national standard by 5 times within half an hourThe formaldehyde removal rate of (2) was 98%.
Example 2
Weighing 1.3g of beta-cyclodextrin and 0.9g of sodium hydroxide, adding the beta-cyclodextrin and the sodium hydroxide into deionized water with the volume of about 40mL, placing the mixture in an ethanol steam atmosphere after the beta-cyclodextrin and the sodium hydroxide are completely dissolved, standing the mixture for 1 to 3 days, washing the white precipitate at the bottom of a container for 3 times by using an ethanol solution, and obtaining white crystals, namely the metal organic framework structure.
1g of the metal organic framework material is placed in a closed container containing excessive toluene in the air at the temperature of 4 ℃, and the removal rate of the toluene which exceeds 5 times of the national standard is 90 percent within 1 hour.
Example 3
Weighing 1.3g of gamma-cyclodextrin and 0.45g of potassium hydroxide, adding the gamma-cyclodextrin and the potassium hydroxide into deionized water with the volume of about 20mL, placing the mixture in a methanol steam atmosphere after the gamma-cyclodextrin and the potassium hydroxide are completely dissolved, standing for 2-7 days, separating out white precipitate at the bottom of a container, and washing the container for several times by using a methanol solution to obtain white crystals, namely the metal organic framework material.
10g of the metal organic framework material is placed in a gas mask poison filtering piece, TVOC which is 5 times higher than the national standard can be continuously removed for 50 hours, and the removal rate is 100 percent.
Example 4
Weighing 1.5g of 12 crown-4 and 1g of Zn4O(CO2)6Adding the mixture into deionized water with the volume of about 40mL, placing the mixture in an air atmosphere containing acetone vapor after the mixture is completely dissolved, standing the mixture for 2 to 7 days, separating out white crystals at the bottom of a container, and washing the white crystals for a plurality of times by using ethanol solution to obtain the white crystals, namely the metal organic framework structure.
1g of this metal-organic framework material was placed at room temperature in a volume of 1m of air containing an excess of total volatile organic compounds TVOC3In a closed container, the TVOC removal rate exceeding 5 times of the national standard within 10 hours is 88 percent.
Claims (3)
1. The use of macrocyclic compound metal organic framework material is characterized in that the macrocyclic compound metal organic framework material is used in the purification of formaldehyde harmful gas, is used as an adsorbent for purifying air in a room, an automobile or an unspecified space, or is used as an adsorption filtration component in a gas mask, an air purification device or an automobile exhaust purifier, the macrocyclic compound metal organic framework material is a hybrid material which is formed by chelating macrocyclic compound with metal ions and has a crystal configuration and a porous structure, the porous structure has pores with two sizes and polarities of macrocyclic pores and framework pores, and the macrocyclic compound is selected from crown ether, cucurbituril, cyclodextrin and derivatives thereof.
2. Use of the macrocyclic metal organic framework material according to claim 1, wherein the macrocyclic metal organic framework material is placed in a room, an automobile and an unspecified space for purifying air at an air atmosphere temperature of-20-70 ℃.
3. Use of a macrocycle metal organic framework material according to claim 1 or 2, wherein the pore size of said macrocycle metal organic framework material is between 0.002 and 20 μm.
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| CN107362774A (en) * | 2017-07-11 | 2017-11-21 | 宁夏大学 | It is enriched with the preparation of sulfa antibiotics SPE material and its detection to being enriched with sulfa antibiotics |
| CN108671890A (en) * | 2018-06-01 | 2018-10-19 | 中国农业大学 | A kind of preparation of cyclodextrin metal organic frame carbon material and its application in water process |
| CN109411817B (en) * | 2018-10-30 | 2020-10-27 | 中南大学 | Lithium ion battery or lithium sulfur battery electrolyte |
| CN109916874B (en) * | 2019-04-16 | 2021-07-13 | 贵州大学 | Preparation method of fluorescent material for formaldehyde gas detection |
| CN111790209A (en) * | 2020-07-23 | 2020-10-20 | 张宗洲 | Automobile air conditioner filter screen and interlayer preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153328A (en) * | 2015-04-10 | 2015-12-16 | 佳木斯大学 | Cyclodextrin metal-organic framework compound and its preparation method and use |
| CN105199017A (en) * | 2015-04-10 | 2015-12-30 | 佳木斯大学 | Cs-CD-MOFs compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105153328A (en) * | 2015-04-10 | 2015-12-16 | 佳木斯大学 | Cyclodextrin metal-organic framework compound and its preparation method and use |
| CN105199017A (en) * | 2015-04-10 | 2015-12-30 | 佳木斯大学 | Cs-CD-MOFs compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Carbohydrate-Mediated Purication of Petrochemicals;James M.Holcroft et al;《J.Am.Chem.Soc.》;20150325;第137卷;第5706-5719页及其Supporting Information * |
| Metal-Organic Frameworks from Edible Natural Products;Ronald A. Smaldone et al;《Angew. Chem. Int. Ed.》;20100816;第49卷;第8630-8634页 * |
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