CN111875808B - Nano zeolite imidazole framework material and CO2Auxiliary preparation method and application - Google Patents
Nano zeolite imidazole framework material and CO2Auxiliary preparation method and application Download PDFInfo
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Abstract
The invention discloses a nanometer zeolite imidazole framework material and CO2An auxiliary preparation method and application. By introducing CO during the synthesis of ZIFs2Using gas as conditioning medium, using CO2And (3) introducing and removing the gas to reversibly destroy the coordination bond between the metal ions and the organic ligand, so that the structure of the ZIFs is rapidly changed in the dissolving and recrystallization processes, and finally the nano ZIFs are prepared. The preparation method has the advantages of short time consumption, simple and convenient operation, good repeatability and economic and environment-friendly synthesis process, and the prepared nano ZIFs have the advantages of small particle size, large specific surface area, high crystallinity, good thermal stability, high purity and the like. Besides, nano ZIFs also have good catalytic activity for photodegradation of organic dyes.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a nano zeolite imidazole framework material and CO2An auxiliary preparation method and application.
Background
Zeolitic Imidazolate Frameworks (ZIFs) are built up of four-coordinated metal ions (e.g. Zn)2+Or Co2+) And an organic imidazole compound to form a metal-organic framework having a zeolite-like topology. Compared with most Metal Organic Frameworks (MOFs), ZIFs have higher physicochemical stability and higher specific surface area. Therefore, ZIFs have become promising materials in various industries, including gas storage, membrane separation, catalysis, and biomedicine.
Similar to inorganic nanomaterials, the particle size and morphology of ZIFs play a key role in physicochemical properties and application performance. Therefore, many methods such as changing the concentration of the precursor solution, the type of solvent, the synthesis temperature, adding capping agents or lye additives, etc., have been used to adjust the particle size and morphology of the ZIFs particles. For example, Cravilon et al (Chemistry of Materials,2011,23(8), 2130-. In addition, various surfactants and polymers have been used as structure directing agents to adjust the particle size and morphology of ZIFs. For example, Hu et al (ChemCatchem,2019,11(14),3212-3219) prepared ZIFs with different morphologies, such as solid spheres, hollow spheres, etc., using different surfactants as templates. However, optimizing various synthesis parameters during experimentation tends to be time consuming, expensive, and inefficient. In addition, in some cases, the addition of auxiliary chemicals to adjust the morphology and particle size of ZIFs particles may cause problems such as low purity or poor crystallinity, and therefore, it is important to develop a simpler and more direct method to precisely control the size and morphology of ZIFs crystals.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano zeolite imidazole framework material and CO2The auxiliary preparation method and the application solve the problems in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: providing a CO2The method for preparing nanometer zeolite imidazole framework material in an auxiliary way introduces CO in the synthesis process of ZIFs2Gas, using CO2Introducing and removing gas to make ZIFs generate structural transformation in the process of dissolving and recrystallizing, and preparing to obtain nano zeolite imidazole framework materials, which are marked as nano ZIFs;
the CO is2The gas introducing and removing treatment comprises the following steps:
after the metal salt and the organic ligand are mixed to generate precipitation, introducing CO with the pressure of 1-50 bar2Gas is discharged for 10-120 min, and then CO is removed2Gas stirringStirring and reacting for 10-120 min.
In a preferred embodiment of the present invention, the method comprises the following steps:
(1) dissolving metal salt in an alcohol solvent, and stirring until the metal salt is completely dissolved to obtain a solution A; dissolving an organic ligand in an alcohol solvent, adding an alkali liquor, and stirring until the organic ligand is completely dissolved to obtain a solution B; mixing the solution A and the solution B to obtain turbid liquid generating white solid precipitate;
(2) introducing CO into the turbid liquid2Gas, when the turbid liquid is converted into a clear solution; then CO is removed2Stirring the gas to ensure that the clear solution gradually generates a milky solid product; and centrifuging to recover a solid product, and cleaning and drying to obtain nano ZIFs.
In a preferred embodiment of the present invention, the metal salt is one or more of anhydrous zinc acetate, zinc acetate dihydrate, anhydrous zinc nitrate, zinc nitrate hexahydrate, anhydrous zinc sulfate, zinc sulfate heptahydrate, anhydrous cobalt acetate, cobalt acetate tetrahydrate, anhydrous cobalt nitrate, cobalt nitrate hexahydrate, anhydrous cobalt sulfate, and cobalt sulfate heptahydrate.
In a preferred embodiment of the present invention, the alcohol solvent is one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, and propylene glycol.
In a preferred embodiment of the present invention, the organic ligand is one or more of 1-methylimidazole, 2-methylimidazole, 1, 2-methylimidazole, 2, 4-methylimidazole, 2-formylimidazole, 1-ethylimidazole and 2-ethylimidazole.
In a preferred embodiment of the present invention, the alkali solution is one or more of ethylenediamine, triethylamine, propylamine, n-butylamine, tert-butylamine, ammonia water, sodium hydroxide and potassium hydroxide.
In a preferred embodiment of the present invention, the molar ratio of the metal salt to the organic ligand is 1: 1-8, and the molar ratio of the alkali solution to the organic ligand is 1: 1-5.
In a preferred embodiment of the invention, the centrifugally recovered solid product is washed with ethanol for 3-5 times, and dried in an oven at 55-65 ℃ for 12-14 hours to obtain nano ZIFs.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the nanometer zeolite imidazole framework material prepared by the method is nanometer ZIFs particles, and the BET specific surface area of the nanometer zeolite imidazole framework material is 1180-1190 m2G, pore diameter is not more than 2 nm.
The third technical scheme adopted by the invention for solving the technical problems is as follows: provides the application of the nano zeolite imidazole framework material in catalyzing the photodegradation of organic dyes.
Compared with the background technology, the technical scheme has the following advantages:
1. the invention utilizes CO2The nucleation and growth of gas-mediated crystals reversibly destroy coordination bonds between metal ions and organic ligands, so that the ZIFs are rapidly subjected to structural transformation in the process of dissolution and recrystallization, and nano ZIFs are finally prepared;
2. the preparation method has the advantages of short time consumption, simple and convenient operation, good repeatability and economic and environment-friendly synthesis process;
3. the nano ZIFs prepared by the method has the advantages of small particle size, large specific surface area, high crystallinity, good thermal stability, high purity and the like;
4. the nano ZIFs prepared by the method has good catalytic activity for photodegradation of organic dyes.
Drawings
FIG. 1 is a scanning electron micrograph of nano ZIFs prepared in example 1, with a scale of 200 nm.
FIG. 2 is a scanning electron micrograph of nano ZIFs prepared in example 3, with a 2 μm scale in the middle.
FIG. 3 is a plot of the nitrogen physisorption and desorption isotherms of the nano ZIFs prepared in example 4 (the inset is the pore size distribution plot).
Detailed Description
Example 1
This example is a CO2The method for preparing the nano zeolite imidazole framework material in an auxiliary manner has the advantages of short time consumption, simple and convenient operation, good repeatability, economy, practicability and green and environment-friendly synthesis process. The method specifically comprises the following steps:
(1) 0.66g of zinc acetate dihydrate was dissolved in 8mL of methanol solution and stirred until completely dissolved. 1.0g of 1-methylimidazole was dissolved in 20mL of methanol solution, and 0.5mL of propylamine was added and stirred until completely dissolved. The two solutions were mixed to yield a white solid precipitate.
(2) Introducing the solution into 10bar CO for 20min2The gas, the reaction solution, changed from a milky turbid solution to a clear solution. CO removal2After gassing, stirring was again carried out for 40min and the solution gradually gave a milky white solid product. The solid product is recovered by centrifugation, washed 3 times by ethanol and dried in an oven at 60 ℃ for 12 h.
As shown in fig. 1, the nano zeolite imidazole framework materials nano ZIFs prepared in this embodiment have regular shapes, uniform particle sizes, narrow particle size distribution, and good dispersibility. In contrast, under the same conditions but without CO addition2During the preparation of gas-mediated nucleation and growth of crystals, we only obtained micron ZIFs particles. Visible, CO2Reversibly destroying the coordination bond between the metal ion and the organic ligand during the period of introducing and removing, so that the ZIFs can rapidly generate structural transformation in the process of dissolving and recrystallizing.
50mg of the nano ZIFs prepared in this example were weighed into 30mL of methylene blue aqueous solution (20 mg/L). After 10min of ultrasonic treatment, a uniform mixed solution is obtained. In order to eliminate the influence of adsorption, the mixture was stirred in the dark for 30min before carrying out the photodegradation experiment. In the photodegradation reaction (wavelength: 365nm), 500. mu.L of the sample solution was periodically taken out, diluted and centrifuged to take out the supernatant, and the dye concentration was analyzed and determined using an ultraviolet-visible spectrophotometer. The result shows that the degradation rate of nano ZIFs on methylene blue is 75%, and the nano ZIFs have good catalytic activity for organic dye photodegradation.
Example 2
Example 2 differs from example 1 in that:
(1) 0.44g of anhydrous zinc acetate was dissolved in 10mL of isopropanol solution and stirred until completely dissolved. 0.77g of 1, 2-methylimidazole was dissolved in 20mL of an isopropanol solution, and 0.2mL of n-butylamine was added thereto and stirred until completely dissolved. The two solutions were mixed to yield a white solid precipitate.
(2) Introducing the solution into 20bar CO for 40min2Gas, reaction solution from opalescenceThe cloudy solution turned into a clear solution. CO removal2After gassing, stirring was again carried out for 60min, and the solution gradually gave a milky white solid product. Centrifuging to recover solid product, washing with ethanol for 3 times, and oven drying at 60 deg.C for 12 hr.
50mg of the nano ZIFs prepared in this example were weighed into 30mL of methylene blue aqueous solution (20 mg/L). After 10min of ultrasonic treatment, a uniform mixed solution is obtained. In order to eliminate the influence of adsorption, the mixture was stirred in the dark for 30min before carrying out the photodegradation experiment. In the photodegradation reaction (wavelength: 365nm), 500. mu.L of the sample solution was periodically taken out, diluted and centrifuged to take out the supernatant, and the dye concentration was analyzed and determined using an ultraviolet-visible spectrophotometer. The result shows that the degradation rate of nano ZIFs on methylene blue is 80%.
Example 3
Example 3 differs from example 1 in that:
(1) 0.71g of anhydrous cobalt acetate was dissolved in 15mL of ethanol solution, and stirred until completely dissolved. 1.64g of 2-methylimidazole was dissolved in 30mL of ethanol solution, and 0.42mL of tert-butylamine was added thereto and stirred until completely dissolved. The two solutions were mixed to yield a white solid precipitate.
(2) Introducing the solution into 20bar CO for 60min2The gas, the reaction solution, changed from a milky turbid solution to a clear solution. CO removal2After gassing, stirring was again carried out for 90min, and the solution gradually yielded a milky white solid product. Centrifuging to recover solid product, washing with ethanol for 3 times, and oven drying at 60 deg.C for 12 hr. Scanning electron micrographs (as shown in FIG. 2, with a scale of 2 μm) demonstrate that the nano ZIFs have uniform particle sizes and narrow particle size distributions. On the contrary, if CO is not introduced2Gas-mediated nucleation and growth of crystals, we obtained only micron ZIFs particles.
50mg of the nano ZIFs prepared in this example were weighed into 30mL of methylene blue aqueous solution (20 mg/L). After 10min of ultrasonic treatment, a uniform mixed solution is obtained. In order to eliminate the influence of adsorption, the mixture was stirred in the dark for 30min before carrying out the photodegradation experiment. In the photodegradation reaction (wavelength: 365nm), 500. mu.L of the sample solution was periodically taken out, diluted and centrifuged to take out the supernatant, and the dye concentration was analyzed and determined using an ultraviolet-visible spectrophotometer. The result shows that the degradation rate of nano ZIFs on methylene blue is 78%.
Example 4
Example 4 differs from example 1 in that:
(1) 0.62g of zinc nitrate hexahydrate was dissolved in 10mL of methanol solution and stirred until completely dissolved. 1.24g of 2-methylimidazole was dissolved in 25mL of methanol solution, and 1.0mL of triethylamine was added thereto and stirred until completely dissolved. The two solutions were mixed to yield a white solid precipitate.
(2) Introducing the solution into 1bar CO for 60min2The gas, the reaction solution, changed from a milky turbid solution to a clear solution. CO removal2After gassing, stirring was again carried out for 60min, and the solution gradually gave a milky white solid product. Centrifuging to recover solid product, washing with ethanol for 3 times, and oven drying at 60 deg.C for 12 hr. The BET specific surface area of the nitrogen physisorption isotherm graph and the pore size distribution graph (shown in FIG. 3) is 1185m2The pore size distribution is mostly below 2nm, indicating that it has a microporous structure.
50mg of the nano ZIFs prepared in this example were weighed into 30mL of methylene blue aqueous solution (20 mg/L). After 10min of ultrasonic treatment, a uniform mixed solution is obtained. In order to eliminate the influence of adsorption, the mixture was stirred in the dark for 30min before carrying out the photodegradation experiment. In the photodegradation reaction (wavelength: 365nm), 500. mu.L of the sample solution was periodically taken out, diluted and centrifuged to take out the supernatant, and the dye concentration was analyzed and determined using an ultraviolet-visible spectrophotometer. The result shows that the degradation rate of nano ZIFs on methylene blue is 83%.
Example 5
Example 5 differs from example 1 in that:
(1) 1.15g of zinc sulfate heptahydrate was dissolved in 20mL of ethanol solution, and stirred until completely dissolved. 1.92g of 2, 4-methylimidazole was dissolved in 40mL of an ethanol solution, and 2mL of a sodium hydroxide solution (2mol/L) was added thereto and stirred until completely dissolved. The two solutions were mixed to yield a white solid precipitate.
(2) Introducing the solution into 30bar CO for 60min2Gas, reaction solution from milky turbid liquidThe transition to a clear solution. CO removal2After gassing, stirring again for 90min, the solution gradually gave a milky white solid product. Centrifuging to recover solid product, washing with ethanol for 3 times, and oven drying at 60 deg.C for 12 hr.
50mg of the nano ZIFs prepared in this example were weighed into 30mL of methylene blue aqueous solution (20 mg/L). After 10min of ultrasonic treatment, a uniform mixed solution is obtained. In order to eliminate the influence of adsorption, the mixed solution was stirred in the dark for 30min before carrying out the photodegradation experiment. In the photodegradation reaction (wavelength: 365nm), 500. mu.L of the sample solution was periodically taken out, diluted and centrifuged to take out the supernatant, and the dye concentration was analyzed and determined using an ultraviolet-visible spectrophotometer. The result shows that the degradation rate of nano ZIFs on methylene blue is 75%.
Example 6
Example 6 differs from example 1 in that:
(1) 0.89g of cobalt nitrate hexahydrate was dissolved in 15mL of ethylene glycol solution and stirred until completely dissolved. 1.23g of 2-methylimidazole was dissolved in 30mL of ethylene glycol solution, and 1.2mL of triethylamine was added thereto and stirred until completely dissolved. The two solutions were mixed to yield a white solid precipitate.
(2) Introducing 30bar CO for 40min2The gas, the reaction solution, changed from a milky turbid solution to a clear solution. CO removal2After gassing, stirring was again carried out for 60min, and the solution gradually gave a milky white solid product. Centrifuging to recover solid product, washing with ethanol for 3 times, and oven drying at 60 deg.C for 12 hr.
50mg of the nano ZIFs prepared in this example were weighed into 30mL of methylene blue aqueous solution (20 mg/L). After 10min of ultrasonic treatment, a uniform mixed solution is obtained. In order to eliminate the influence of adsorption, the mixture was stirred in the dark for 30min before carrying out the photodegradation experiment. In the photodegradation reaction (wavelength: 365nm), 500. mu.L of the sample solution was periodically taken out, diluted and centrifuged to take out the supernatant, and the dye concentration was analyzed and determined using an ultraviolet-visible spectrophotometer. The result shows that the degradation rate of nano ZIFs on methylene blue is 79%.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The application of the nanometer zeolite imidazole framework material in catalyzing the blue light degradation of organic dye methylene is characterized in that: the preparation method of the nanometer zeolite imidazole framework material comprises the following steps: introduction of CO during synthesis of ZIFs2Gas, using CO2Introducing and removing gas to make ZIFs generate structural transformation in the process of dissolving and recrystallizing, and preparing to obtain nano zeolite imidazole framework materials, which are marked as nano ZIFs;
the CO is2The gas introducing and removing treatment comprises the following steps:
(1) dissolving metal salt in an alcohol solvent, and stirring until the metal salt is completely dissolved to obtain a solution A; dissolving an organic ligand in an alcohol solvent, adding an alkali liquor, and stirring until the organic ligand is completely dissolved to obtain a solution B; mixing the solution A and the solution B to obtain turbid liquid generating white solid precipitate;
the molar ratio of the metal salt to the organic ligand is 1: 1-8, and the molar ratio of the alkali liquor to the organic ligand is 1: 1-5;
(2) after the metal salt and the organic ligand are mixed to generate precipitation, introducing CO with the pressure of 1-50 bar into the turbid liquid2The gas is used for 10-120 min, and the turbid liquid is converted into a clear solution; then CO is removed2Stirring and reacting for 10-120 min to enable the clear solution to gradually generate a milky solid product; and centrifuging to recover a solid product, and cleaning and drying to obtain nano ZIFs.
2. Use according to claim 1, characterized in that: the metal salt is one or more of anhydrous zinc acetate, zinc acetate dihydrate, anhydrous zinc nitrate, zinc nitrate hexahydrate, anhydrous zinc sulfate, zinc sulfate heptahydrate, anhydrous cobalt acetate, cobalt acetate tetrahydrate, anhydrous cobalt nitrate, cobalt nitrate hexahydrate, anhydrous cobalt sulfate and cobalt sulfate heptahydrate.
3. Use according to claim 1, characterized in that: the alcohol solvent is one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol and propylene glycol.
4. Use according to claim 1, characterized in that: the organic ligand is one or more of 1-methylimidazole, 2-methylimidazole, 1, 2-methylimidazole, 2, 4-methylimidazole, 2-formylimidazole, 1-ethylimidazole and 2-ethylimidazole.
5. Use according to claim 1, characterized in that: the alkali liquor is one or more of ethylenediamine, triethylamine, propylamine, n-butylamine, tert-butylamine, ammonia water, sodium hydroxide and potassium hydroxide.
6. Use according to claim 1, characterized in that: and washing the centrifugally recovered solid product with ethanol for 3-5 times, and drying in an oven at 55-65 ℃ for 12-14 hours to obtain nano ZIFs.
7. Use according to claim 1, characterized in that: the nanometer zeolite imidazole framework material is nanometer ZIFs particles, and the BET specific surface area of the nanometer zeolite imidazole framework material is 1180-1190 m2(ii)/g, pore diameter is not more than 2 nm.
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| CN102335626A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing micro/nano zeolitic imidazolate frameworks (ZIFs) |
| CN102731538A (en) * | 2012-06-07 | 2012-10-17 | 中国石油大学(华东) | Preparation method of nanometer-to-micrometer scale zeolitic imidazolate frameworks (ZIFs) |
| CN110483787A (en) * | 2019-03-12 | 2019-11-22 | 中国石油大学(北京) | A kind of zeolitic imidazolate framework material and preparation method thereof |
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| CN102335626A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing micro/nano zeolitic imidazolate frameworks (ZIFs) |
| CN102731538A (en) * | 2012-06-07 | 2012-10-17 | 中国石油大学(华东) | Preparation method of nanometer-to-micrometer scale zeolitic imidazolate frameworks (ZIFs) |
| CN110483787A (en) * | 2019-03-12 | 2019-11-22 | 中国石油大学(北京) | A kind of zeolitic imidazolate framework material and preparation method thereof |
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| "Synthesis and Characterization of Imidazole Topological Structure ZIF-67 in Supercritical CO2";Wenqing Han et al.;《中国化学会·第一届全国西部资源化利用学术会议摘要集》;20191108;第81页 * |
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