CN109894086B - Metal organic framework and ionic liquid composite material as well as preparation method and application thereof - Google Patents
Metal organic framework and ionic liquid composite material as well as preparation method and application thereof Download PDFInfo
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- CN109894086B CN109894086B CN201910246696.9A CN201910246696A CN109894086B CN 109894086 B CN109894086 B CN 109894086B CN 201910246696 A CN201910246696 A CN 201910246696A CN 109894086 B CN109894086 B CN 109894086B
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Abstract
The invention relates to a metal organic framework and ionic liquid composite material as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) preparation of ionic liquid: dissolving 1, 2-dibromoethane and N- (3-aminopropyl) imidazole in acetone, stirring and reacting for 18-24 h at normal temperature to obtain dark brown viscous liquid, and performing centrifugal separation and washing to obtain ionic liquid; 2) preparing a metal organic framework and ionic liquid composite material: dissolving ionic liquid in methanol, adding 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, then pouring the obtained ionic liquid solution into a methanol solution of cobalt nitrate, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, washing and drying to obtain the metal organic framework and ionic liquid composite material. The metal organic framework and ionic liquid composite material provided by the invention has a high carbon dioxide adsorption value, is nontoxic and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a metal organic framework and ionic liquid composite material as well as a preparation method and application thereof.
Background
With the development of society, the use of fossil fuels is greatly promoted, and a large amount of carbon dioxide is inevitably generated, and is one of the main gases causing the greenhouse effect. In 12 months of 2015, the paris agreement passes through the paris climate change meeting, the aim is to reduce the emission of greenhouse gases, the emission of the greenhouse gases is an international problem, and currently, scientists in various countries actively try to overcome the problem of the emission of the greenhouse gases. At present, the mature method for carbon dioxide adsorption is an alcohol amine adsorption method, and alcohol amine is used as a liquid phase adsorbent to adsorb carbon dioxide. However, this method also has its obvious disadvantages, such as the volatile adsorbent, the serious corrosion of the equipment, etc. Therefore, the green environment-friendly absorbent is developed, and the green environment-friendly absorbent is greatly helpful for solving the greenhouse effect.
The metal organic framework material is firstly proposed by the Yaghi subject group, is mainly formed by coordination of metal and organic ligand, has higher specific surface area and lower density, belongs to a microporous structure, and has natural advantages on selective adsorption of gas. The ionic liquid is salt which is composed of organic cation and inorganic or organic anion and is in a molten state at room temperature, and as a green solvent, the ionic liquid has strong selectivity and adsorbability on the adsorption of carbon dioxide. Particularly, the amino-functionalized ionic liquid provides a chemical adsorption site of carbon dioxide, and greatly improves the adsorption performance of the carbon dioxide. The ionic liquid and the metal organic framework are compounded, so that the carbon dioxide adsorbent with high adsorption efficiency is prepared.
The metal organic framework and ionic liquid composite material provided by the invention is used for carbon dioxide adsorption, and the adsorption value can reach 18.78cm under the conditions of 1bar and 298K3G (adsorption number of simple metal organic framework is 17.25 cm)3/g)。
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a metal organic framework and ionic liquid composite material, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the preparation method of the metal organic framework and ionic liquid composite material comprises the following steps:
1) preparation of ionic liquid: dissolving 1, 2-dibromoethane and N- (3-aminopropyl) imidazole in acetone, stirring and reacting for 18-24 h at normal temperature to obtain a dark brown viscous liquid, and performing centrifugal separation and washing to obtain an ionic liquid (brominated 1- (3-aminopropyl) -3- (2-bromoethyl) imidazole);
2) preparing a metal organic framework and ionic liquid composite material: dissolving the ionic liquid obtained in the step 1) in methanol, adding 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, then pouring the obtained ionic liquid solution into a methanol solution of cobalt nitrate, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, washing and drying to obtain the metal organic framework and ionic liquid composite material.
According to the scheme, the molar ratio of the 1, 2-dibromoethane to the N- (3-aminopropyl) imidazole in the step 1) is 1.01-1.30: 1, the volume ratio of the 1, 2-dibromoethane to acetone is 3-5: 10.
according to the scheme, the concentration of the ionic liquid in the ionic liquid solution in the step 2) is 2-5 mg/mL; the mass ratio of the ionic liquid to the 2-methylimidazole is 1: 10 to 15.
According to the scheme, the methanol solution of the cobalt nitrate in the step 2) is prepared by dissolving cobalt nitrate hexahydrate in methanol, and the concentration of the cobalt nitrate is 0.1-0.15 mol/L; the molar ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate is 4: 1.
the invention also comprises a preparation method of the metal organic framework and ionic liquid composite material, which comprises the following steps:
1) preparation of ionic liquid: dissolving 1, 2-dibromoethane and N- (3-aminopropyl) imidazole in acetone, stirring and reacting for 18-24 h at normal temperature to obtain dark brown viscous liquid, and performing centrifugal separation and washing to obtain ionic liquid;
2) preparing a metal organic framework and ionic liquid composite material: dissolving the ionic liquid obtained in the step 1) in methanol, adding 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, then pouring the obtained ionic liquid solution into a methanol solution of cobalt nitrate, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, washing and drying to obtain the metal organic framework and ionic liquid composite material.
And the application of the metal organic framework and ionic liquid composite material as a carbon dioxide adsorbent.
The invention firstly synthesizes an amino functionalized ionic liquid, and then utilizes the coordination between nitrogen on the amino and metal cobalt to load the ionic liquid on a metal organic framework.
The invention has the beneficial effects that: 1. the adsorption value of the metal organic framework and ionic liquid composite material on carbon dioxide is high (up to 18.78 cm) under the conditions of 1bar and 298K3The material is non-toxic and environment-friendly. 2. The preparation method provided by the invention has the advantages of simple process, low preparation energy consumption, no pollution, good repeatability and easy realization.
Drawings
FIG. 1 is an infrared image of an ionic liquid prepared in example 1 of the present invention;
FIG. 2 is an infrared image of the metal organic framework and ionic liquid composite prepared in example 1;
FIG. 3 is a BET plot of the metal organic framework material prepared in example 1;
FIG. 4 is a BET plot of the metal organic framework and ionic liquid composite prepared in example 1;
FIG. 5 is a thermogram of an ionic liquid prepared in example 1;
FIG. 6 is a thermogram of the metal organic framework material prepared in example 1;
FIG. 7 is a thermogram of the metal organic framework and ionic liquid composite prepared in example 1;
FIG. 8 is a carbon dioxide adsorption curve of the metal organic framework material prepared in example 1;
fig. 9 is a carbon dioxide adsorption curve of the metal organic framework and ionic liquid composite prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
A metal organic framework and ionic liquid composite material for carbon dioxide adsorption is prepared by the following steps:
preparation of ionic liquid: in a 50mL two-necked flask under N2Dissolving 3mL of 1, 2-dibromoethane and 4mL of N- (3-aminopropyl) imidazole in 10mL of acetone under protection, stirring at normal temperature to obtain a dark brown viscous liquid, centrifuging, and washing with acetone to obtain an ionic liquid (brominated 1- (3-aminopropyl) -3- (2-bromoethyl) imidazole);
dissolving 120mg of the prepared ionic liquid in 30mL of methanol, adding 1.232g of 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, dissolving 1.096g of cobalt nitrate hexahydrate in 30mL of methanol to obtain a cobalt nitrate solution, pouring the ionic liquid solution into the cobalt nitrate solution, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, repeatedly washing with methanol, and finally vacuum-drying at 80 ℃ for 24 hours to obtain the metal organic framework and ionic liquid composite material.
Preparation of metal organic framework materials for comparison: dissolving 1.232g of 2-methylimidazole in 30mL of methanol to obtain a 2-methylimidazole solution, dissolving 1.096g of cobalt nitrate hexahydrate in 30mL of methanol to obtain a cobalt nitrate solution, pouring the obtained 2-methylimidazole solution into the cobalt nitrate solution, stirring for 10min, standing for 24h to obtain a purple precipitate, centrifuging, repeatedly washing with methanol, and finally vacuum-drying at 80 ℃ for 24h to obtain the metal-organic framework material.
As shown in fig. 1, which is an infrared diagram of the ionic liquid prepared in this example, and fig. 2 is an infrared diagram of the metal organic framework and the ionic liquid composite material prepared in this example, it can be seen from a comparison between the infrared diagrams of fig. 1 and fig. 2 that the stretching vibration peak at 1164 is C ═ C-N-, which proves that the ionic liquid is introduced into the metal organic framework.
Fig. 3 is a BET diagram of the metal organic framework material prepared as described above, and fig. 4 is a BET diagram of the metal organic framework and ionic liquid composite material prepared in this example, comparing that the addition of the ionic liquid does not have a great influence on the specific surface area, which indicates that the ionic liquid does not enter into the pores of the metal organic framework.
Fig. 5-7 are thermogravimetric graphs of the ionic liquid, the metal-organic framework material, and the metal-organic framework and ionic liquid composite material prepared in this example, respectively, where the pure ionic liquid is rapidly lost at about 230 ℃, the pure metal-organic framework material is rapidly lost at about 550 ℃, and the composite material (the metal-organic framework and the ionic liquid composite material) is rapidly lost at 400 ℃, and the heat loss temperature of the composite material is significantly higher than that of the pure ionic liquid, which indicates that the ionic liquid is compounded in the metal-organic framework in a certain bonding manner, rather than simply physically mixed.
Fig. 8 is a carbon dioxide adsorption curve of the metal organic framework material prepared as described above, fig. 9 is a carbon dioxide adsorption curve of the metal organic framework and ionic liquid composite material prepared in this example, and it can be seen from the graph,at 800mmHg (1bar, 298K), the carbon dioxide adsorption value of the pure metal-organic framework material is 17.25cm3The carbon dioxide adsorption value of the metal organic framework and ionic liquid composite material reaches 18.78cm3/g。
Example 2
A metal organic framework and ionic liquid composite material for carbon dioxide adsorption is prepared by the following steps:
preparation of ionic liquid: in a 50mL two-necked flask under N2Under protection, dissolving 3mL of 1, 2-dibromoethane and 4mL of N- (3-aminopropyl) imidazole in 10mL of acetone, stirring at normal temperature to obtain a dark brown viscous liquid, performing centrifugal separation, and washing with acetone to obtain an ionic liquid;
dissolving 90mg of the prepared ionic liquid in 30mL of methanol, adding 1.232g of 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, dissolving 1.096g of cobalt nitrate hexahydrate in 30mL of methanol to obtain a cobalt nitrate solution, pouring the ionic liquid solution into the cobalt nitrate solution, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, repeatedly washing with methanol, and finally vacuum-drying at 80 ℃ for 24 hours to obtain the metal organic framework and ionic liquid composite material.
The performance of the metal organic framework and ionic liquid composite material prepared in the embodiment is close to that of the metal organic framework and ionic liquid composite material prepared in the embodiment 1.
Claims (6)
1. The metal organic framework and ionic liquid composite material is characterized by comprising the following preparation method steps:
1) preparation of ionic liquid: dissolving 1, 2-dibromoethane and N- (3-aminopropyl) imidazole in acetone, stirring and reacting for 18-24 h at normal temperature to obtain dark brown viscous liquid, and performing centrifugal separation and washing to obtain ionic liquid;
2) preparing a metal organic framework and ionic liquid composite material: dissolving the ionic liquid obtained in the step 1) in methanol, adding 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, then pouring the obtained ionic liquid solution into a methanol solution of cobalt nitrate, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, washing and drying to obtain the metal organic framework and ionic liquid composite material.
2. The metal-organic framework and ionic liquid composite material as claimed in claim 1, wherein the molar ratio of the 1, 2-dibromoethane to the N- (3-aminopropyl) imidazole in the step 1) is 1.01-1.30: 1, the volume ratio of the 1, 2-dibromoethane to acetone is 3-5: 10.
3. the metal organic framework and ionic liquid composite material as claimed in claim 1, wherein the ionic liquid concentration in the ionic liquid solution in the step 2) is 2-5 mg/mL; the mass ratio of the ionic liquid to the 2-methylimidazole is 1: 10 to 15.
4. The metal organic framework and ionic liquid composite material as claimed in claim 1, wherein the methanol solution of cobalt nitrate in step 2) is prepared by dissolving cobalt nitrate hexahydrate in methanol, and the concentration of cobalt nitrate is 0.1-0.15 mol/L; the molar ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate is 4: 1.
5. a preparation method of the metal organic framework and ionic liquid composite material according to any one of claims 1 to 4, which is characterized by comprising the following specific steps:
1) preparation of ionic liquid: dissolving 1, 2-dibromoethane and N- (3-aminopropyl) imidazole in acetone, stirring and reacting for 18-24 h at normal temperature to obtain dark brown viscous liquid, and performing centrifugal separation and washing to obtain ionic liquid;
2) preparing a metal organic framework and ionic liquid composite material: dissolving the ionic liquid obtained in the step 1) in methanol, adding 2-methylimidazole, stirring at normal temperature for 12 hours to obtain an ionic liquid solution, then pouring the obtained ionic liquid solution into a methanol solution of cobalt nitrate, stirring for 10 minutes, standing for 24 hours to obtain a purple precipitate, centrifuging, washing and drying to obtain the metal organic framework and ionic liquid composite material.
6. Use of a metal organic framework according to any one of claims 1 to 4 in combination with an ionic liquid as a carbon dioxide adsorbent.
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