CN113801334A - Preparation method of small-size MOF-801 material - Google Patents
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Abstract
The invention discloses a preparation method of a small-size MOF-801 material, which comprises the following steps: fumaric acid and a zirconium source are used as reaction precursors, the reaction precursors are prepared into a uniform solution by using a mixed solution consisting of an organic solvent and organic acid, and a hydro-thermal reaction is carried out to grow the MOF-801 material; and after the reaction is finished, cooling the reaction liquid to room temperature, then soaking and cleaning the obtained reaction precipitate with absolute ethyl alcohol, removing impurities, and finally drying and activating the precipitate in vacuum to obtain white MOF-801 powder. The invention can prepare the small-sized MOF-801 material with uniform size, has simple preparation process, short preparation period and high synthesis efficiency, and is suitable for practical application.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of a small-size MOF-801 material.
Background
Since the first synthesis of Metal Organic Frameworks (MOFs) by Robson, Moore, Yaghi, Kitagawa, and frerey et al in the 90 s, MOF materials have attracted attention from a number of researchers due to the abundant diversity of structural motifs, structural diversity and designability, and high porosity and specific surface area. Researchers are widely applied to the fields of adsorption, catalysis, ion exchange and the like according to the physical and chemical characteristics of different MOF materials. Due to the unique structure and characteristics of the MOF material, the MOF material is not limited to the application of manufacturing nano materials, catalysis, separation and the like, and in the future, the MOF material relates to various fields such as materials, chemistry, physics, biology and the like, and becomes a research hotspot crossing multiple disciplines.
The MOF-801 is a microporous MOF material composed of zirconium and fumaric acid, and the specific surface area can reach 950m2·g-1The composite material has good stability, can keep stable under aqueous solution and acidic conditions, is a good gas storage material of acidic gas, has good water absorption, and can also be used as a drying agent. Usually, the synthesis of MOF-801 materials in laboratories is performed by a hydrothermal/solvothermal method, which is a simple method for obtaining high-quality MOF materials, but the traditional hydrothermal method has long reaction time, low yield, harsh experimental conditions and the like, so that further application and commercialization are hindered. Although many methods of synthesis of MOF materials have been developed today, including electrochemical, microwave, spray drying, mechanochemical, atomic layer deposition, sol-gel, etc., the hydrothermal/solvothermal methods produce relatively the best quality products. Therefore, the method has very important practical significance for improving the synthesis efficiency of the hydrothermal method/solvothermal method and shortening the synthesis time by a simple method.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a method for preparing a small-sized MOF-801 material, which is used to solve the problems of long reaction time, low yield, low synthesis efficiency and the like of the MOF-801 material synthesis method-hydrothermal method/solvothermal method in the prior art.
To achieve the above and other related objects, the present invention provides a method for preparing a small-sized MOF-801 material, comprising the steps of: fumaric acid and a zirconium source are used as reaction precursors, the reaction precursors are prepared into a uniform solution by using a mixed solution consisting of an organic solvent and organic acid, and the uniform solution is subjected to hydrothermal reaction to grow into MOF-801; and after the reaction is finished, cooling the reaction liquid to room temperature, then soaking and cleaning the obtained reaction precipitate by using absolute ethyl alcohol, removing impurities, and finally drying and activating the precipitate in vacuum to obtain white MOF-801 powder, namely the MOF-801 material. Wherein, fumaric acid and zirconium source are solute, and the mixed solution composed of organic solvent and organic acid is solvent.
Alternatively, the molar ratio of fumaric acid to the zirconium source is 1: (0.5-2.0), preferably 1: (0.5-1.5), preferably 1: 1.
optionally, the concentration of the fumaric acid and the concentration of the zirconium source in the homogeneous solution are respectively 0.01-0.03 g/mL and 0.05-0.30 g/mL, preferably 0.01-0.02 g/mL and 0.05-0.20 g/mL, and more preferably 0.02g/mL and 0.06 g/mL.
Alternatively, the zirconium source is selected from a zirconium element-containing compound dissolved in an organic solvent and an organic acid, the zirconium source being selected from at least one of zirconium oxychloride, zirconium tetrachloride, zirconium tetraiodide.
Optionally, the organic solvent is at least one selected from Dimethylformamide (DMF), absolute ethanol, methanol, and diethyl ether, preferably Dimethylformamide (DMF).
Optionally, the organic acid is selected from at least one of formic acid, acetic acid, propionic acid and trifluoroacetic acid, and is preferably formic acid.
Optionally, in the mixed solution, the volume ratio of the organic solvent to the organic acid is (20-30): (5-10), preferably 20 (6-8), more preferably 20: 7.
Optionally, the organic solvent is Dimethylformamide (DMF), the organic acid is formic acid, and the volume ratio of the Dimethylformamide (DMF) to the formic acid in the mixed solution is 20 (6-8), preferably 20: 7.
Optionally, the homogeneous solution is put into a hydrothermal reaction kettle for hydrothermal reaction.
Optionally, the hydrothermal reaction process is as follows: the homogeneous solution is firstly reacted for 0.5 to 1.5 hours at the preheating temperature, then heated to 110 to 140 ℃ for reaction for 3 to 5 hours, and finally cooled to 90 to 100 ℃ for reaction for 0.5 to 1.5 hours. In the hydrothermal reaction, the reaction is carried out by adjusting the reaction temperature and controlling the temperature in sections, which is beneficial to shortening the reaction time.
Optionally, the hydrothermal reaction process is as follows: the homogeneous solution is firstly reacted for 0.5-1.5 hours at the preheating temperature, then heated to 120-130 ℃ for reaction for 3-5 hours, and finally cooled to 90-100 ℃ for reaction for 0.5-1.5 hours.
Optionally, the preheating temperature is 90-100 ℃.
Optionally, after the growth is finished, slowly cooling the reaction solution to room temperature, which is favorable for forming high-quality MOF-801 crystals.
Optionally, the reaction precipitate is soaked in absolute ethyl alcohol for 2-4 days. Optionally, in the soaking process of the reaction precipitate, washing with absolute ethyl alcohol for 3-5 times every day.
Optionally, the vacuum drying temperature is 120-180 ℃, and preferably 140-160 ℃.
Optionally, the size of the white MOF-801 powder is 100-400 nm, preferably 150-310 nm.
The invention also provides the MOF-801 material prepared by the method.
As mentioned above, the preparation method of the small-size MOF-801 material has the following beneficial effects:
in the process of preparing the MOF-801 material, the hydrothermal reaction of the precursor can be effectively promoted by regulating and controlling the concentration of the precursor, the reaction environment of uniform solution and the growth temperature; the temperature reduction and cooling in the step 4) are beneficial to the formation of high-quality MOF-801; and 5) and 6) can effectively remove impurities in the pores of the material.
The invention can prepare the small-sized MOF-801 material with uniform size, has simple preparation process, short preparation period, high synthesis efficiency and high yield, is suitable for practical application and has very important practical significance.
Drawings
FIG. 1 is a schematic diagram of the basic principle of the invention for preparing MOF-801 material, wherein a precursor A is a zirconium source and a precursor B is fumaric acid;
FIG. 2 is a graph of temperature control for the preparation of MOF-801 powder in example 1 of the present invention;
FIG. 3 is an XRD pattern of a MOF-801 powder produced in example 1 of the present invention, with the inset being a molecular structure diagram of a MOF-801 secondary building unit;
FIG. 4 is an SEM image of MOF-801 powder prepared in example 1 of the present invention at different sizes.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a preparation method of a small-size MOF-801 material, which comprises the following steps: fumaric acid and a zirconium source are used as reaction precursors, the reaction precursors are prepared into a uniform solution by using a mixed solution consisting of an organic solvent and organic acid, and the uniform solution is subjected to hydrothermal reaction to grow into MOF-801; and after the reaction is finished, cooling the reaction liquid to room temperature, taking out the obtained reaction precipitate, soaking and cleaning the reaction precipitate by using absolute ethyl alcohol, removing impurities, and finally drying and activating the precipitate in vacuum to obtain white MOF-801 powder, namely the MOF-801 material. Wherein, fumaric acid and zirconium source are solute, and the mixed solution composed of organic solvent and organic acid is solvent.
Further, the molar ratio of the fumaric acid to the zirconium source is 1: (0.5-2.0), preferably 1: (0.5-1.5).
Further, the concentration of fumaric acid and the concentration of the zirconium source in the homogeneous solution are respectively 0.01-0.03 g/mL and 0.05-0.30 g/mL, preferably 0.01-0.02 g/mL and 0.05-0.20 g/mL.
Further, the zirconium source is selected from at least one of zirconium oxychloride, zirconium tetrachloride and zirconium tetraiodide.
Further, the organic solvent is at least one selected from Dimethylformamide (DMF), absolute ethyl alcohol, methanol and diethyl ether, and is preferably Dimethylformamide (DMF); the organic acid is at least one selected from formic acid, acetic acid, propionic acid and trifluoroacetic acid, and is preferably formic acid.
Further, in the mixed solution, the volume ratio of the organic solvent to the organic acid is (20-30): (5-10), preferably 20 (6-8).
Further, the homogeneous solution is put into a hydrothermal reaction kettle for hydrothermal reaction.
Further, the hydrothermal reaction process comprises the following steps: the homogeneous solution is firstly reacted for 0.5 to 1.5 hours at the preheating temperature, then heated to 110 to 140 ℃ for reaction for 3 to 5 hours, and finally cooled to 90 to 100 ℃ for reaction for 0.5 to 1.5 hours; preferably, the hydrothermal reaction process is as follows: the homogeneous solution is firstly reacted for 0.5 to 1.5 hours at a preheating temperature of 90 to 100 ℃, then heated to 120 to 130 ℃ for reaction for 3 to 5 hours, and finally cooled to 90 to 100 ℃ for reaction for 0.5 to 1.5 hours. In the hydrothermal reaction, the reaction is carried out by adjusting the reaction temperature and controlling the temperature in sections, which is beneficial to shortening the reaction time.
Further, after the growth is finished, the reaction solution is slowly cooled to room temperature, so that the formation of high-quality MOF-801 crystals is facilitated.
Further, the reaction precipitate is soaked in absolute ethyl alcohol for 2-4 days, and in the soaking process of the reaction precipitate, the reaction precipitate is washed with absolute ethyl alcohol for 3-5 times every day. Specifically, the reaction precipitate can be soaked in a beaker and washed with ethanol for a fixed number of times per day, which is beneficial to removing various impurities generated in the reaction process.
Further, the vacuum drying temperature is 120-180 ℃, and preferably 140-160 ℃.
Further, the size of the white MOF-801 powder is 100-400 nm, and preferably 150-310 nm.
The present invention will be described in detail with reference to the following specific examples. It should also be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations of the invention described above will occur to those skilled in the art. The specific process parameters and the like of the following examples are also merely examples of suitable ranges, i.e., those skilled in the art can select from suitable ranges through the description herein and are not limited to the specific values of the following examples.
Example 1
The preparation method of the MOF-801 material in the example is as follows:
1) according to the following steps of 1: 1 molar ratio of 2.9g of fumaric acid and 8.0g of ZrOCl were weighed out2·8H2O (zirconium oxychloride, formula ZrOCl2Typically octahydrate, zirconium oxychloride octahydrate) as a reaction precursor.
2) Preparing 100mL of Dimethylformamide (DMF) and 35mL of formic acid into a mixed solution according to the volume ratio of 20:7, dissolving the reaction precursor weighed in the step 1) into the mixed solution, and stirring to form a uniform solution.
3) As shown in fig. 1, the homogeneous solution formed in step 3) is placed in a 300mL hydrothermal reaction kettle, and is placed in a heating device with a preheating temperature of 100 ℃, according to the temperature control curve chart shown in fig. 2, after the homogeneous solution grows at 100 ℃ for 1 hour, the temperature is raised to 125 ℃ for reaction for 4 hours, and finally the temperature of the equipment is lowered to 100 ℃ for reaction for 0.5 hour.
4) After the growth is finished, the heating device is closed, and the mixture is slowly cooled to the room temperature.
5) Taking out the reaction precipitate, placing in a beaker, soaking with anhydrous ethanol for 3 days, and washing with ethanol for 4 times every day during the soaking process.
6) The precipitated material from step 5) was isolated and then dried under vacuum at 150 ℃ to activate the sample, yielding 2.5g of white MOF-801 powder.
FIG. 3 shows the XRD pattern of the MOF-801 powder prepared in this example, with the inset being the molecular structure diagram of the MOF-801 secondary building unit, which shows that the method of the present invention can successfully prepare MOF-801 materials.
The particle size of the MOF-801 powder obtained in this example was measured by scanning electron microscopy, and the particle size of the MOF-801 powder obtained in this example was about 150-310nm, as shown in FIG. 4.
Example 2
The preparation method of the MOF-801 material in the example is as follows:
1) according to the following steps of 1: 1 molar ratio of 2.9g of fumaric acid and 8.0g of ZrOCl were weighed out2·8H2O (zirconium oxychloride, formula ZrOCl2Typically octahydrate, zirconium oxychloride octahydrate) as a reaction precursor.
2) Preparing 100mL of Dimethylformamide (DMF) and 30mL of formic acid into a mixed solution according to the volume ratio of 20:6, dissolving the reaction precursor weighed in the step 1) into the mixed solution, and stirring to form a uniform solution.
3) Putting the uniform solution formed in the step 3) into a 300mL hydrothermal reaction kettle, putting the kettle into a heating device with the preheating temperature of 90 ℃, growing for 1.5 hours at 90 ℃, then heating to 120 ℃ for reaction for 5 hours, and finally cooling the equipment to 90 ℃ for reaction for 1.5 hours.
4) After the growth is finished, the heating device is closed, and the mixture is slowly cooled to the room temperature.
5) Taking out the reaction precipitate, placing in a beaker, soaking with anhydrous ethanol for 2 days, and cleaning with ethanol 3 times a day during the soaking process.
6) The precipitated material from step 5) was isolated and then dried under vacuum at 150 ℃ to activate the sample, yielding 1.62g of white MOF-801 powder.
The particle size of the MOF-801 powder obtained in this example was about 100-300 nm.
Example 3
The preparation method of the MOF-801 material in the example is as follows:
1) according to the following steps of 1: 1 molar ratio of 2.9g of fumaric acid and 8.0g of ZrOCl were weighed out2·8H2O (zirconium oxychloride, formula ZrOCl2Typically octahydrate, zirconium oxychloride octahydrate) as a reaction precursor.
2) Preparing 100mL of Dimethylformamide (DMF) and 40mL of formic acid into a mixed solution according to the volume ratio of 20:8, dissolving the reaction precursor weighed in the step 1) into the mixed solution, and stirring to form a uniform solution.
3) Putting the uniform solution formed in the step 3) into a 300mL hydrothermal reaction kettle, putting the kettle into a heating device with the preheating temperature of 95 ℃, growing for 0.5 hour at 95 ℃, then heating to 130 ℃ for reaction for 3 hours, and finally cooling the equipment to 95 ℃ for reaction for 1 hour.
4) After the growth is finished, the heating device is closed, and the mixture is slowly cooled to the room temperature.
5) Taking out the reaction precipitate, placing in a beaker, soaking with anhydrous ethanol for 4 days, and washing with ethanol 5 times a day during the soaking process.
6) The precipitated material from step 5) was isolated and then dried under vacuum at 150 ℃ to activate the sample, yielding 2.0g of white MOF-801 powder.
The particle size of the MOF-801 powder obtained in this example was about 120-400 nm.
Example 4
The preparation method of the MOF-801 material in the example is as follows:
1) according to the following steps of 1: 2.0 molar ratio 2.9g of fumaric acid and 11.6g of zirconium tetrachloride (ZrCl) were weighed out separately4) As a reaction precursor.
2) Preparing 150mL of Dimethylformamide (DMF) and 50mL of formic acid into a mixed solution according to the volume ratio of 3:1, dissolving the reaction precursor weighed in the step 1) into the mixed solution, and stirring to form a uniform solution.
3) Putting the uniform solution formed in the step 3) into a 300mL hydrothermal reaction kettle, putting the kettle into a heating device with the preheating temperature of 100 ℃, growing for 1 hour at the temperature of 100 ℃, then heating to 125 ℃ for reaction for 4 hours, and finally cooling the equipment to 100 ℃ for reaction for 1 hour.
4) After the growth is finished, the heating device is closed, and the mixture is slowly cooled to the room temperature.
5) Taking out the reaction precipitate, placing in a beaker, soaking with anhydrous ethanol for 4 days, and washing with ethanol for 4 times every day during the soaking process.
6) The precipitated material from step 5) was isolated and then dried under vacuum at 150 ℃ to activate the sample, yielding 2.56g of white MOF-801 powder.
The particle size of the MOF-801 powder obtained in this example was about 150-290 nm.
Example 5
The preparation method of the MOF-801 material in the example is as follows:
1) according to the following steps of 1: 0.5 molar ratio 2.9g of fumaric acid and 4.0g of ZrOCl were weighed out separately2·8H2O (zirconium oxychloride, formula ZrOCl2Typically octahydrate, zirconium oxychloride octahydrate) as a reaction precursor.
2) Preparing 100mL of diethyl ether and 25mL of acetic acid into a mixed solution according to the volume ratio of 4:1, dissolving the reaction precursor weighed in the step 1) into the mixed solution, and stirring to form a uniform solution.
3) Putting the uniform solution formed in the step 3) into a 300mL hydrothermal reaction kettle, putting the kettle into a heating device with the preheating temperature of 100 ℃, growing for 1 hour at the temperature of 100 ℃, then heating to 140 ℃ for reaction for 3 hours, and finally cooling the equipment to 100 ℃ for reaction for 1 hour.
4) After the growth is finished, the heating device is closed, and the mixture is slowly cooled to the room temperature.
5) Taking out the reaction precipitate, placing in a beaker, soaking with anhydrous ethanol for 3 days, and washing with ethanol for 4 times every day during the soaking process.
6) The precipitated material from step 5) was isolated and then dried under vacuum at 150 ℃ to activate the sample, yielding 1.50g of white MOF-801 powder.
The particle size of the MOF-801 powder obtained in this example was approximately 160-350 nm.
Example 6
The preparation method of the MOF-801 material in the example is as follows:
1) according to the following steps of 1: 1.5 molar ratio 2.9g of fumaric acid and 12.0g of ZrOCl were weighed out separately2·8H2O (zirconium oxychloride, formula ZrOCl2Typically octahydrate, zirconium oxychloride octahydrate) as a reaction precursor.
2) Preparing 100mL of Dimethylformamide (DMF) and 32mL of formic acid into a mixed solution according to the volume ratio of 25:8, dissolving the reaction precursor weighed in the step 1) into the mixed solution, and stirring to form a uniform solution.
3) Putting the uniform solution formed in the step 3) into a 300mL hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a heating device with the preheating temperature of 95 ℃, growing for 1 hour at 95 ℃, then heating to 110 ℃ for reaction for 5 hours, and finally cooling the equipment to 100 ℃ for reaction for 1 hour.
4) After the growth is finished, the heating device is closed, and the mixture is slowly cooled to the room temperature.
5) Taking out the reaction precipitate, placing in a beaker, soaking with anhydrous ethanol for 3 days, and washing with ethanol for 4 times every day during the soaking process.
6) The precipitated material from step 5) was isolated and then dried under vacuum at 150 ℃ to activate the sample, yielding 2.36g of white MOF-801 powder.
The particle size of the MOF-801 powder obtained in this example was about 150-320 nm.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a small-size MOF-801 material is characterized by comprising the following steps: fumaric acid and a zirconium source are used as reaction precursors, the reaction precursors are prepared into a uniform solution by using a mixed solution consisting of an organic solvent and organic acid, and a hydro-thermal reaction is carried out to grow the MOF-801 material; and after the reaction is finished, cooling the reaction liquid to room temperature, then soaking and cleaning the obtained reaction precipitate by using absolute ethyl alcohol, removing impurities, and finally drying and activating the precipitate in vacuum to obtain white MOF-801 powder, namely the MOF-801 material.
2. The method of claim 1, wherein: the molar ratio of fumaric acid to zirconium source is 1: (0.5-2.0);
and/or the concentration of fumaric acid and the concentration of a zirconium source in the uniform solution are respectively 0.01-0.03 g/mL and 0.05-0.30 g/mL;
and/or the zirconium source is selected from at least one of zirconium oxychloride, zirconium tetrachloride and zirconium tetraiodide.
3. The method of claim 1, wherein: the organic solvent is at least one of dimethylformamide, absolute ethyl alcohol, methanol and diethyl ether;
and/or, the organic acid is selected from at least one of formic acid, acetic acid, propionic acid and trifluoroacetic acid;
and/or the volume ratio of the organic solvent to the organic acid in the mixed solution is (20-30): (5-10).
4. The production method according to claim 3, characterized in that: the organic solvent is dimethylformamide, the organic acid is formic acid, and the volume ratio of the dimethylformamide to the formic acid in the mixed solution is 20 (6-8).
5. The method of claim 1, wherein: and putting the uniform solution into a hydrothermal reaction kettle for hydrothermal reaction.
6. The method of claim 5, wherein: the hydrothermal reaction process comprises the following steps: the homogeneous solution is firstly reacted for 0.5 to 1.5 hours at the preheating temperature, then heated to 110 to 140 ℃ for reaction for 3 to 5 hours, and finally cooled to 90 to 100 ℃ for reaction for 0.5 to 1.5 hours.
7. The method of claim 6, wherein: the preheating temperature is 90-100 ℃.
8. The method of claim 1, wherein: after the growth is finished, slowly cooling the reaction solution to room temperature;
and/or soaking the reaction precipitate in absolute ethyl alcohol for 2-4 days; washing the reaction precipitate with absolute ethyl alcohol for 3-5 times every day in the soaking process;
and/or the vacuum drying temperature is 120-180 ℃.
9. The method of claim 1, wherein: the size of the white MOF-801 powder is 100-400 nm.
10. A MOF-801 material produced according to the method of any one of claims 1 to 9.
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| CN114832791A (en) * | 2022-04-25 | 2022-08-02 | 西安交通大学 | Nitrogen-doped zirconium-based organic metal framework adsorbent containing mixed ligand, preparation method and application |
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