CN105037444A - Synthetic method of metal organic frameworks Co-MOF-74 - Google Patents
Synthetic method of metal organic frameworks Co-MOF-74 Download PDFInfo
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- 239000013114 Co-MOF-74 Substances 0.000 title claims abstract description 66
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 50
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000000527 sonication Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000001291 vacuum drying Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000013384 organic framework Substances 0.000 abstract description 2
- 229940045029 cobaltous nitrate hexahydrate Drugs 0.000 abstract 2
- 239000002178 crystalline material Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000013118 MOF-74-type framework Substances 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method of metal organic frameworks Co-MOF-74, in particular to a synthetic method of organic frameworks. The synthetic method comprises the following steps: mixing DMF, methyl alcohol with deionized water to obtain mixed liquor A, weighing cobaltous nitrate hexahydrate and 2,5-dihydroxyterephthalic acid, adding cobaltous nitrate hexahydrate and 2,5-dihydroxyterephthalic acid into the mixed liquor A, performing ultrasonic treatment to obtain mixed liquor B; transferring the mixed liquor B into a hydrothermal kettle, placing the hydrothermal kettle in a constant temperature oven for drying; displacing reaction solution in the hydrothermal kettle with methyl alcohol every 12 hours for several times; carrying out vacuum drying, cooling to room temperature to obtain the Co-MOF-74 material. According to the synthetic method of metal organic frameworks Co-MOF-74, provided by the invention, purity-phase rodlike Co-MOF-74 crystalline material is obtained, and the synthetic process is greatly simplified while the experiment cost is reduced.
Description
Technical Field
The invention relates to a synthetic method of an organic framework material.
Background
With the recent great development of industry, the emission amount of carbon dioxide gas is increased, the carbon dioxide gas is the main gas causing the greenhouse effect, and the global warming caused by the carbon dioxide gas has attracted much attention.
Metal-organic frameworks (MOFs) are a new porous network structure material formed by coordination and connection of Metal ions and organic ligands. It is prepared from organic ligand and metalThe ion or metal cluster is self-assembled by coordination bonds or intermolecular interaction force to form the crystal material with a one-dimensional, two-dimensional or three-dimensional infinite network structure. Because of its advantages of large specific surface area, adjustable aperture size, chemical modification according to target requirements, and abundant structure, MOFs is in CO2The adsorption separation aspect shows great application potential.
Compared with other metal organic framework materials, the specific surface area of the MOF-74 material is smaller, but the MOF-74 material has the advantages of excellent thermal stability, high porosity, high gas adsorption capacity under low pressure and the like, so that the MOF-74 material is particularly excellent in low-pressure gas adsorption and storage. Co-MOF-74 material has a specific surface area (about 900 m)2Per g) is less than Co-MOF-74 (about 1100 m)2/g), but the Co-MOF-74 has better gas adsorption, desorption and regeneration performance than the Co-MOF-74, so that the Co-MOF-74 is one of important materials for researching gas adsorption of metal organic framework materials.
The Co-MOF-74 material prepared by the invention has good thermal stability, and the heat-resistant temperature of the material can reach 250 ℃, which is superior to other metal organic framework materials. The good or bad thermal stability determines the width of the application field of the material, and the good thermal stability ensures that the Co-MOF-74 can adsorb CO under the high temperature condition in a factory2The ability to work, has the potential to develop applications.
Meanwhile, the Co-MOF-74 not only has higher porosity and specific surface area, so that the Co-MOF-74 has excellent gas adsorption and storage capacity superior to other porous materials, but also has a great number of metal sites in the Co-MOF-74, so that the efficiency of gas separation is obviously superior to that of the traditional porous materials. Especially at low pressure, the Co-MOF-74 material has superior adsorption properties compared to other materials, enabling its application under normal atmospheric conditions. These characteristics make Co-MOF-74 material one of the most ideal target materials for reducing greenhouse effect, therefore, developing Co-MOF-74 material with higher adsorption and storage capacity has important scientific significance and wide application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organic framework material Co-MOF-74 for absorbing and storing carbon dioxide gas.
The invention discloses a method for synthesizing a metal organic framework material Co-MOF-74, which is carried out by the following steps:
firstly, respectively taking DMF, methanol and deionized water, and mixing to prepare a mixed solution A, wherein the volume ratio of the DMF, the methanol and the water is 1 (0.25-4) to 0-4;
secondly, respectively weighing cobalt nitrate hexahydrate and 2, 5-dihydroxy terephthalic acid, placing the cobalt nitrate hexahydrate and the 2, 5-dihydroxy terephthalic acid into the mixed solution A obtained in the first step, and carrying out ultrasonic treatment for 10-60 minutes under the condition that the ultrasonic frequency is 30-100 kHz to obtain a mixed solution B; wherein the molar ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is (0.25-5): 1;
thirdly, transferring the mixed solution B obtained in the second step into a stainless steel water heating kettle with a polytetrafluoroethylene lining, then putting the stainless steel water heating kettle into a constant-temperature drying oven, carrying out water heating for 8-40 hours at the temperature of 90-150 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
fourthly, replacing the reaction solution in the hydrothermal kettle with methanol every 12 hours for 2-6 times;
fifthly, drying the sample after the replacement in the fourth step in vacuum at 100-250 ℃ for 2-12 hours, and cooling to room temperature to obtain the Co-MOF-74 material.
The invention has the following beneficial effects:
the invention adopts a solvothermal synthesis method to successfully prepare a pure-phase rod-shaped Co-MOF-74 crystal material, optimizes the process conditions and obtains a method for preparing Co-MOF-74 crystals with large grain size and uniform grain size. The invention discovers that the Co-MOF-74 material can be prepared into Co-MOF-74 crystals with good crystallinity, complete solvent removal and good thermal stability only by vacuum drying for 6 hours at 100 ℃, thereby greatly simplifying the synthesis process and simultaneously reducing the experiment cost.
Drawings
FIG. 1 is a comparison of the phase diagrams of Co-MOF-74 materials prepared in example 1 with simulated XRD;
FIG. 2 is an SEM topography of Co-MOF-74 made in example 1;
FIG. 3 is a DSC-TGA plot of the Co-MOF-74 crystals made in example 1;
FIG. 4 is a 2000-fold Scanning Electron Microscope (SEM) image of Co-MOF-74 made in example 1;
FIG. 5 is a graph of the isothermal adsorption-desorption of nitrogen for Co-MOF-74 made in example 1; wherein,is an adsorption curve;the desorption curve is shown.
Detailed Description
The first embodiment is as follows: the method for synthesizing the metal-organic framework material Co-MOF-74 is carried out by the following steps:
firstly, respectively taking DMF, methanol and deionized water, and mixing to prepare a mixed solution A, wherein the volume ratio of the DMF, the methanol and the water is 1 (0.25-4) to 0-4;
secondly, respectively weighing cobalt nitrate hexahydrate and 2, 5-dihydroxy terephthalic acid, placing the cobalt nitrate hexahydrate and the 2, 5-dihydroxy terephthalic acid into the mixed solution A obtained in the first step, and carrying out ultrasonic treatment for 10-60 minutes under the condition that the ultrasonic frequency is 30-100 kHz to obtain a mixed solution B; wherein the molar ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is (0.25-5): 1;
thirdly, transferring the mixed solution B obtained in the second step into a stainless steel water heating kettle with a polytetrafluoroethylene lining, then putting the stainless steel water heating kettle into a constant-temperature drying oven, carrying out water heating for 8-40 hours at the temperature of 90-150 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
fourthly, replacing the reaction solution in the hydrothermal kettle with methanol every 12 hours for 2-6 times;
fifthly, drying the sample after the replacement in the fourth step in vacuum at 100-250 ℃ for 2-12 hours, and cooling to room temperature to obtain the Co-MOF-74 material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the temperature of the solution in the ultrasonic treatment process in the second step is not more than 30 ℃. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the molar ratio of cobalt nitrate hexahydrate to 2, 5-dihydroxyterephthalic acid was 3.3: 1. the rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the time for cooling the reaction kettle to room temperature is 6-8 h. The rest is the same as the first embodiment.
The fifth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the replacement of the reaction solution in the hydrothermal kettle by the methanol is completed in the hydrothermal kettle. The rest is the same as the first embodiment.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is: and fifthly, after cooling to room temperature, taking out the hydrothermal kettle, and scraping a sample in the hydrothermal kettle to obtain the Co-MOF-74 material. The rest is the same as the first embodiment.
The seventh embodiment: the first difference between the present embodiment and the specific embodiment is: the volume ratio of DMF, methanol and water is 1:1: 1. the rest is the same as the first embodiment.
The specific implementation mode is eight: the first difference between the present embodiment and the specific embodiment is: the ultrasonic frequency is 40-80 kHz. The rest is the same as the first embodiment.
The specific implementation method nine: the first difference between the present embodiment and the specific embodiment is: the ultrasonic frequency is 50-70 kHz. The rest is the same as the first embodiment.
The detailed implementation mode is ten: the first difference between the present embodiment and the specific embodiment is: the ultrasonic frequency was 60 kHz. The rest is the same as the first embodiment.
The concrete implementation mode eleven: the first difference between the present embodiment and the specific embodiment is: the sonication time was 30 minutes. The rest is the same as the first embodiment.
The specific implementation mode twelve: the first difference between the present embodiment and the specific embodiment is: the molar ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is 1-4: 1. the rest is the same as the first embodiment.
The specific implementation mode is thirteen: the first difference between the present embodiment and the specific embodiment is: the molar ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is (2-4): 1. the rest is the same as the first embodiment.
The specific implementation mode is fourteen: the first difference between the present embodiment and the specific embodiment is: the molar ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is 3-4: 1. the rest is the same as the first embodiment.
The concrete implementation mode is fifteen: the first difference between the present embodiment and the specific embodiment is: the molar ratio of cobalt nitrate hexahydrate to 2, 5-dihydroxyterephthalic acid was 3.3: 1. the rest is the same as the first embodiment.
The specific implementation mode is sixteen: the first difference between the present embodiment and the specific embodiment is: hydrothermal for 10-30 hours at 90-140 ℃. The rest is the same as the first embodiment.
Seventeenth embodiment: the first difference between the present embodiment and the specific embodiment is: hydrothermal for 20-30 hours at 90-130 ℃. The rest is the same as the first embodiment.
The specific implementation mode is eighteen: the first difference between the present embodiment and the specific embodiment is: hydrothermal at 100 deg.c for 24 hr. The rest is the same as the first embodiment.
The specific implementation mode is eighteen: the first difference between the present embodiment and the specific embodiment is: the replacement was performed 4 times. The rest is the same as the first embodiment.
The detailed embodiment is nineteen: the first difference between the present embodiment and the specific embodiment is: and (4) drying the hydrothermal kettle after the replacement in the fourth step for 6 hours in vacuum at the temperature of 100 ℃, and cooling to room temperature to obtain the Co-MOF-74 material. The rest is the same as the first embodiment.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1
The method for synthesizing the metal-organic framework material Co-MOF-74 is carried out by the following steps:
firstly, respectively mixing DMF, methanol and deionized water to prepare a mixed solution, wherein the volume ratio of the DMF to the methanol to the water is 1:1: 1;
secondly, 0.3605g of cobalt nitrate hexahydrate and 0.0742g of 2, 5-dihydroxy terephthalic acid (DHTA) are respectively weighed and placed in the mixed solution obtained in the first step, and ultrasonic treatment is carried out for 30 minutes under the conditions that the ultrasonic frequency is 60kHz and the solution temperature is not more than 30 ℃ to obtain mixed solution;
thirdly, transferring the mixed liquid obtained in the second step into a stainless steel water heating kettle with a polytetrafluoroethylene lining, putting the stainless steel water heating kettle and the stainless steel water heating kettle into a constant-temperature drying box, carrying out water heating for 24 hours at the temperature of 100 ℃, cooling the reaction kettle to room temperature within 6-8, and taking out the reaction kettle;
fourthly, replacing the reaction solution in the hydrothermal kettle with methanol every 12 hours for 4 times;
and fifthly, drying the hydrothermal kettle replaced in the fourth step for 6 hours in vacuum at the temperature of 100 ℃, and cooling to room temperature to obtain the Co-MOF-74 material.
The comparison result of the phase diagram of the Co-MOF-74 material obtained in the example and the simulated XRD is shown in FIG. 1, and as can be seen from FIG. 1, the positions of the diffraction peaks of the phase diagram of the crystal structure of the Co-MOF-74 obtained in the example are consistent, and the obtained sample is proved to be pure-phase Co-MOF-74 crystals.
The SEM topography of the Co-MOF-74 material prepared in this example is shown in FIG. 2, and it can be seen that the Co-MOF-74 prepared by the experimental method is hexagonal rod-shaped crystals.
Methanol molecules are easy to volatilize, and heating and drying can remove part of solvent molecules with lower boiling points, so that the method adopts a methanol replacement mother liquor and a vacuum drying mode to remove object molecules and part of reactants. As shown in the DSC-TGA graph of Co-MOF-74 crystal in FIG. 3, it can be seen that Co-MOF-74 has a large weight loss before 100 ℃, has substantially no change in the matrix mass between 100 ℃ and 300 ℃, and has a further decrease in the mass of the Co-MOF-74 after 300 ℃, which indicates that the Co-MOF-74 can substantially eliminate the guest molecules at 100 ℃, and the Co-MOF-74 structure is damaged after 300 ℃.
FIG. 4 is a crystal morphology diagram of the best synthesis process of Co-MOF-74 prepared in this example, the best process is: the mixture ratio of reactants is 3:1, the solvothermal temperature is 100 ℃, the solvothermal time is 24 hours, and the vacuum drying temperature is 100 ℃. It can be seen that under this condition, the crystal morphology of Co-MOF-74 is hexagonal rod-like with a diameter of about 4um and the crystal grain size is uniform. The product under the condition is proved to have a good crystal structure and is suitable for the adsorption of the material gas.
The BET test results of the Co-MOF-74 prepared in this example are shown in FIG. 5, which is a nitrogen adsorption-desorption isotherm of the Co-MOF-74 crystals synthesized under optimal process conditions. The adsorption of nitrogen in the Co-MOF-74 crystals in the low-pressure region is quickly saturated, which indicates that the prepared Co-MOF-74 is a microporous material, and the distribution of the pore diameters also indicates that the pore diameters are mainly distributed inLeft and right.
The BET test result shows that the BET single-point method specific surface of the Co-MOF-74 crystal material is about 780m2The specific surface area of the Langmuir method is about 1000m2Per g, specific micropore surface area of about 450m2The values of the ratio of the pore volume of the micropores to the total pore volume of the material are 73%, and these data prove that the material is favorable for CO2And (4) adsorbing the gas.
Claims (10)
1. A method for synthesizing a metal organic framework material Co-MOF-74, which is characterized by comprising the following steps:
firstly, respectively taking DMF, methanol and deionized water, and mixing to prepare a mixed solution A, wherein the volume ratio of the DMF, the methanol and the water is 1 (0.25-4) to 0-4;
secondly, respectively weighing cobalt nitrate hexahydrate and 2, 5-dihydroxy terephthalic acid, placing the cobalt nitrate hexahydrate and the 2, 5-dihydroxy terephthalic acid into the mixed solution A obtained in the first step, and carrying out ultrasonic treatment for 10-60 minutes under the condition that the ultrasonic frequency is 30-100 kHz to obtain a mixed solution B; wherein the molar ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is (0.25-5): 1;
thirdly, transferring the mixed solution B obtained in the second step into a stainless steel water heating kettle with a polytetrafluoroethylene lining, then putting the stainless steel water heating kettle into a constant-temperature drying oven, carrying out water heating for 8-40 hours at the temperature of 90-150 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
fourthly, replacing the reaction solution in the hydrothermal kettle with methanol every 12 hours for 2-6 times;
fifthly, drying the sample after the replacement in the fourth step in vacuum at 100-250 ℃ for 2-12 hours, and cooling to room temperature to obtain the Co-MOF-74 material.
2. A method for synthesizing a metal organic framework material Co-MOF-74 as claimed in claim 1 wherein the temperature of the solution during the sonication in step two does not exceed 40 ℃.
3. The method for synthesizing the metal-organic framework material Co-MOF-74 according to claim 1, wherein the molar ratio of cobalt nitrate hexahydrate to 2, 5-dihydroxyterephthalic acid is 2-4: 1.
4. a method of synthesising a metal-organic framework material Co-MOF-74 as claimed in claim 3 characterised in that the molar ratio of cobalt nitrate hexahydrate and 2, 5-dihydroxyterephthalic acid is 3.3: 1.
5. the method for synthesizing the metal organic framework material Co-MOF-74 as claimed in claim 1, wherein the time for cooling the reaction kettle to room temperature is 6-8 h.
6. The method for synthesizing metal organic framework material Co-MOF-74 as claimed in claim 1, wherein said displacement of the reaction solution with methanol is performed in a polytetrafluoroethylene inner lining.
7. The method for synthesizing the metal organic framework material Co-MOF-74, according to claim 1, is characterized in that after cooling to room temperature in the fifth step, the hydrothermal kettle is taken out, and a sample in the hydrothermal kettle is scraped out, so that the Co-MOF-74 material is obtained.
8. The method for synthesizing the metal-organic framework material Co-MOF-74 according to claim 1, wherein the volume ratio of DMF, methanol and water is 1:1: 1.
9. The method for synthesizing the metal-organic framework material Co-MOF-74 as claimed in claim 1, wherein the ultrasonic treatment is carried out for 30 minutes under the condition that the ultrasonic frequency is 60 kHz.
10. A method for synthesizing a metal-organic framework material Co-MOF-74 as claimed in claim 1 wherein the number of substitutions is 4.
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