CN111234253A - Preparation method of nano metal organic framework material - Google Patents
Preparation method of nano metal organic framework material Download PDFInfo
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- CN111234253A CN111234253A CN202010123487.8A CN202010123487A CN111234253A CN 111234253 A CN111234253 A CN 111234253A CN 202010123487 A CN202010123487 A CN 202010123487A CN 111234253 A CN111234253 A CN 111234253A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention relates to the technical field of material preparation, in particular to a preparation method of a nano metal organic framework material. The method has mild reaction conditions, does not need high temperature and high pressure, has low requirements on equipment technology, has good system uniformity, and can control the microstructure of the nano material by changing the parameter cutting of the sol-gel process. In the sol-gel process, the sol is prepared from solution, so that the chemical components in colloidal particles and among colloidal particles are completely consistent, and the method enables reactants to react and mix at the molecular level, and enables the product to achieve high uniformity and high refinement. The invention has controllable component proportion, easy modification and wide doping range.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a preparation method of a nano metal organic framework material.
Background
The rational design and synthesis of Metal-organic frameworks (MOFs) materials have been gaining attention because of their porosity, high specific surface area, and diversity of composition and structure, which make them of important application value in many fields. In addition to the design of the structure and composition thereof at the molecular scale, more and more researches have been focused in recent years on controlling the super structure constructed by the MOFs crystal at the nanometer scale, such as a hollow structure, a thin film, a multi-level structure and the like, and these efforts bring new directions to the application of the MOFs material. Another new development direction of the MOFs material is to compound the MOFs material and functional Nanoparticles (NPs) to form composite material MOFs-NPs, and the composite material has the porosity of the MOFs material and the functionality of the NPs, so that the MOFs material has great potential research value. However, the research on such materials is still in the laboratory stage, and the industrial mass production of the materials cannot be realized. Moreover, most of the materials are prepared on an inorganic plane substrate by adopting a secondary growth method containing an organic solvent at a higher temperature, and the thickness of the materials is thicker. If a production process of the nano metal organic framework material which has high production efficiency and is convenient for industrial production can be researched, the nano metal organic framework material can be prepared in a low-temperature nontoxic solvent, and considerable economic income is undoubtedly brought to inorganic material enterprises.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a preparation method of a nano metal organic framework material, which comprises the steps of adding a solvent into a metal alkoxide solution for decomposition at normal temperature or approximately normal temperature, simultaneously carrying out polycondensation reaction to prepare sol, further reacting to form gel and further solidifying, and then carrying out low-temperature heat treatment to obtain the nano metal organic framework material.
The technical scheme for solving the technical problems is as follows:
a preparation method of a nanometer metal organic framework material is characterized in that the nanometer metal organic framework material is a nanometer film, and a sol-gel method is adopted to carry out nanocrystallization on a metal organic framework to obtain the nanometer metal organic framework material.
The method comprises the following specific steps:
1) preparing a precursor of metal alkoxide with the concentration of 0.01-0.2Kg/L by using a metal organic framework material as a raw material and selecting a proper solvent, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and hydrolyzing, alcoholyzing or carrying out polymerization reaction on the salt until the mixture solution is clear to generate a uniform and stable sol system;
3) and aging the sol system obtained in the step 2) at room temperature to remove water or alcohol adsorbed on the surface of the gel, and drying at 60 +/-2 ℃ to obtain the nano metal organic framework material.
Further, the solvent in step 1) is selected from any one of water, absolute ethyl alcohol and ethylene glycol.
Further, the addition amount of the coagulant in the step 2) is 0.05-0.1g per liter of the solution.
Further, the coagulant in step 2) is any one of calcium sulfate, calcium chloride, magnesium chloride, propylene glycol and disodium ethylene diamine tetraacetate.
The invention has the beneficial effects that:
the invention provides a preparation method of a nano metal organic framework material, which adopts a sol-gel method to carry out nanocrystallization on the metal organic framework material, has mild reaction conditions, does not need high temperature and high pressure, has low requirements on equipment technology and good system uniformity, and can control the microstructure of the nano material by changing the parameter cutting of the sol-gel process. In the sol-gel process, the sol is prepared from solution, so that the chemical components in colloidal particles and among colloidal particles are completely consistent, and the method enables reactants to react and mix at the molecular level, and enables the product to achieve high uniformity and high refinement. The invention has controllable component proportion, easy modification and wide doping range.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1:
1) taking a metal organic framework material as a raw material, selecting water as a solvent, adding a small amount of a general dispersant to prepare a precursor of metal alkoxide with the concentration of 0.1Kg/L, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and hydrolyzing, alcoholyzing or carrying out polymerization reaction on the salt until the mixture solution is clear to generate a uniform and stable sol system; the addition amount of coagulant is 0.1g per liter of solution. The coagulant is calcium sulfate.
3) And aging the sol system obtained in the step 2) at room temperature until water adsorbed on the surface of the gel is removed, and drying at 60 ℃ to obtain the nano metal organic framework material.
Example 2:
1) preparing a precursor of metal alkoxide with the concentration of 0.01Kg/L by using a metal organic framework material as a raw material and selecting absolute ethyl alcohol as a solvent, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and carrying out salt alcoholysis or polymerization reaction until the mixture solution is clear to generate a uniform and stable sol system; the addition amount of coagulant is 0.05g per liter of solution. The coagulant is calcium chloride.
3) And aging the sol system obtained in the step 2) at room temperature to remove water or alcohol adsorbed on the surface of the gel, and drying at 58 ℃ to obtain the nano metal organic framework material.
Example 3:
1) preparing a precursor of metal alkoxide with the concentration of 0.2Kg/L by using a metal organic framework material as a raw material and ethylene glycol as a solvent, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and carrying out salt alcoholysis or polymerization reaction until the mixture solution is clear to generate a uniform and stable sol system; the addition amount of coagulant is 0.08g per liter of solution. The coagulant is magnesium chloride.
3) And aging the sol system obtained in the step 2) at room temperature to remove water or alcohol adsorbed on the surface of the gel, and drying at 62 ℃ to obtain the nano metal organic framework material.
Example 4:
1) preparing a precursor of metal alkoxide with the concentration of 0.08Kg/L by using a metal organic framework material as a raw material and selecting absolute ethyl alcohol as a solvent, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and carrying out salt alcoholysis or polymerization reaction until the mixture solution is clear to generate a uniform and stable sol system; the coagulant is added in an amount of 0.09g per liter of the solution. The coagulant is propylene glycol.
3) And aging the sol system obtained in the step 2) at room temperature to remove water or alcohol adsorbed on the surface of the gel, and drying at 60 ℃ to obtain the nano metal organic framework material.
Example 5:
1) preparing a precursor of metal alkoxide with the concentration of 0.15Kg/L by using a metal organic framework material as a raw material and ethylene glycol as a solvent, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and hydrolyzing, alcoholyzing or carrying out polymerization reaction on the salt until the mixture solution is clear to generate a uniform and stable sol system; the coagulant is added in an amount of 0.075g per liter of the solution. The coagulant is disodium edetate.
3) And aging the sol system obtained in the step 2) at room temperature to remove water or alcohol adsorbed on the surface of the gel, and drying at 61 ℃ to obtain the nano metal organic framework material.
The principle of the invention is as follows: preparing a precursor of metal inorganic salt or metal alkoxide by using a liquid chemical reagent, dissolving the precursor in a solvent to form a uniform solution (sometimes adding a small amount of a dispersing agent), adding a proper amount of a coagulant to hydrolyze and alcoholyze the salt or perform a polymerization reaction to generate a uniform and stable sol system, standing (aging) or drying for a long time to polymerize and gelatinize the solute, drying the gel, and roasting to remove organic components to obtain the nano metal organic framework material.
The invention provides a preparation method of a nano metal organic framework material, which adopts a sol-gel method to carry out nanocrystallization on the metal organic framework material, has mild reaction conditions, does not need high temperature and high pressure, has low requirements on equipment technology and good system uniformity, and can control the microstructure of the nano material by changing the parameter cutting of the sol-gel process. In the sol-gel process, the sol is prepared from the solution, so that the chemical components in colloidal particles and among colloidal particles are completely consistent, and the method enables reactants to react and mix at the molecular level, and enables the product to achieve high uniformity and high refinement. The invention has controllable component proportion, easy modification and wide doping range.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.
Claims (5)
1. The preparation method of the nanometer metal organic framework material is characterized in that the nanometer metal organic framework material is a nanometer film, and the nanometer metal organic framework material is obtained by performing nanocrystallization on a metal organic framework by adopting a sol-gel method.
2. The method for preparing a nanometal organic framework material according to claim 1, which comprises the following steps:
1) preparing a precursor of metal alkoxide with the concentration of 0.01-0.2Kg/L by using a metal organic framework material as a raw material and selecting a proper solvent, and stirring until the mixture is transparent and clear, so that the metal organic framework material is dissolved in the solvent to form a uniform solution;
2) adding a proper amount of coagulant into the solution obtained in the step 1), and hydrolyzing, alcoholyzing or carrying out polymerization reaction on the salt until the mixture solution is clear to generate a uniform and stable sol system;
3) and aging the sol system obtained in the step 2) at room temperature to remove water or alcohol adsorbed on the surface of the gel, and drying at 60 +/-2 ℃ to obtain the nano metal organic framework material.
3. The method for preparing nano metal organic framework material according to claim 2, wherein the solvent in step 1) is selected from any one of water, absolute ethyl alcohol and ethylene glycol.
4. The method for preparing nano metal organic framework material according to claim 2, wherein the coagulant is added in the amount of 0.05-0.1g per liter of the solution in step 2).
5. The method for preparing a nanometal organic framework material according to claim 2, wherein the coagulant in step 2) is any one of calcium sulfate, calcium chloride, magnesium chloride, propylene glycol and disodium ethylene diamine tetraacetate.
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| CN202010123487.8A CN111234253A (en) | 2020-02-27 | 2020-02-27 | Preparation method of nano metal organic framework material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892713A (en) * | 2020-07-30 | 2020-11-06 | 太原理工大学 | Method for synthesizing MIL-100Cr integral material by sol-gel method |
| CN116425992A (en) * | 2023-04-28 | 2023-07-14 | 华中科技大学 | Method for converting waste polylactic acid into metal-organic framework material by utilizing solvothermal method |
| CN116425992B (en) * | 2023-04-28 | 2024-04-19 | 华中科技大学 | Method for converting waste polylactic acid into metal-organic framework material by utilizing solvothermal method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892713A (en) * | 2020-07-30 | 2020-11-06 | 太原理工大学 | Method for synthesizing MIL-100Cr integral material by sol-gel method |
| CN111892713B (en) * | 2020-07-30 | 2022-02-18 | 太原理工大学 | Method for synthesizing MIL-100Cr integral material by sol-gel method |
| CN116425992A (en) * | 2023-04-28 | 2023-07-14 | 华中科技大学 | Method for converting waste polylactic acid into metal-organic framework material by utilizing solvothermal method |
| CN116425992B (en) * | 2023-04-28 | 2024-04-19 | 华中科技大学 | Method for converting waste polylactic acid into metal-organic framework material by utilizing solvothermal method |
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Application publication date: 20200605 |