CN113845662A - Method for synthesizing metal organic framework - Google Patents
Method for synthesizing metal organic framework Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 14
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- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
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- 238000001035 drying Methods 0.000 claims abstract description 13
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- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000001308 synthesis method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
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- 230000035484 reaction time Effects 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 5
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 239000012229 microporous material Substances 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 239000013096 zirconium-based metal-organic framework Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
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- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000013078 crystal Substances 0.000 description 3
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- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 1
- 239000013336 microporous metal-organic framework Substances 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a metal organic framework material, in particular to a preparation method of the metal organic framework material, which comprises the following steps: (1) adding metal zirconium salt and dicarboxylic acid organic ligand into an aprotic polar solvent, and stirring at room temperature until the solid is completely dissolved to obtain a solution I; (2) adding monocarboxylic organic acid into the solution I, and uniformly stirring to obtain a solution II; (3) adding water into the solution II to obtain a solution III; (4) adding a regulator into the third solution to obtain a fourth solution, wherein the regulator is one of dimethylbenzene, trimethylbenzene or tetramethylbenzene; (5) controlling the temperature of the solution IV within the range of 25-300 ℃ to carry out hydrothermal reaction; (6) after the reaction is finished, the target product is obtained through centrifugal separation, washing and drying. The invention can successfully obtain the small-grain zirconium-based MOFs material by controlling the nucleation and crystallization rate of the metal ions and the organic ligand, thereby improving the mass transfer efficiency of the microporous material.
Description
Technical Field
The invention relates to a metal organic framework material, in particular to a preparation method of the metal organic framework material.
Background
Metal-organic frameworks (MOFs) refer to polymeric materials that self-assemble from metal centers (metal sites) and organic ligands (organic ligands) through coordination bonds into one-, two-, or three-dimensional materials, and have ultra-high specific surface area (7000 m) compared to conventional porous materials such as molecular sieves and activated carbon2Per gram) and porosity (up to 0.9 cm)3And/g), meanwhile, MOFs materials are changed into various forms through different ligand types and coordination forms, and the pore structure and surface property of the MOFs materials can be regulated, controlled and designed, so that the MOFs is widely applied to various fields of gas storage, adsorption and separation, catalytic reaction, biomedicine, intelligent materials and the like.
The pore size distribution of most of the currently reported MOFs is in the micropore range (less than 2nm), which greatly increases the diffusion resistance of the MOFs during mass transfer. In order to improve the diffusion resistance of the microporous MOFS material, the common practice is to increase the size of a ligand to increase the diameter of a pore opening, however, the mesoporous MOFs prepared by the method has poor stability, and the specific surface area is greatly reduced due to easy collapse or penetration of the pore passage; in another method, a template method is adopted to form ordered or unordered mesopores in the crystal, so that the micropore MOFs becomes a hierarchical pore MOFs simultaneously having a mesopore-micropore structure
The prior application number is CN201410079295.6, the invention name is a microchannel of a porous metal organic framework material, and discloses a microchannel chemical preparation method of the porous metal organic framework material, which comprises the steps of respectively injecting one or more liquid-phase media of organic compounds with at least monodentate, liquid-phase media containing one or more metal ions, liquid-phase media containing deprotonation auxiliary agents and inert gases into a microchannel reactor through different inlets, reacting and coordinating the mixed feed liquid in a microchannel at a certain temperature and pressure to form a coordination compound, and finally preparing the porous metal organic framework material after crystallization, filtration, washing and drying; the microchannel reactor is provided with at least two inlets and one outlet; the addition amount of the deprotonation auxiliary agent is 0-50% of the mole number of all metal ions; the volume flow rate of the inert gas added into the microchannel reactor and the total volume flow rate of the liquid phase are in a ratio of 0-100: 1; the crystallization process is not a necessary process. The MOFs material obtained by the application still has the problems of small specific surface area, low porosity, poor stability and the like.
Disclosure of Invention
In order to obtain a metal organic framework with high specific surface area, high porosity and good stability, the invention provides a synthesis method of the metal organic framework, which can successfully obtain small-grain zirconium-based MOFs materials by controlling nucleation and crystallization rate of metal ions and organic ligands, thereby improving mass transfer efficiency of the microporous materials.
The synthesis method provided by the invention specifically comprises the following steps:
a method for synthesizing a metal organic framework comprises the following steps:
(1) adding metal zirconium salt and dicarboxylic acid organic ligand into an aprotic polar solvent, and stirring at room temperature until the solid is completely dissolved to obtain a solution I;
(2) adding monocarboxylic organic acid into the solution I, and uniformly stirring to obtain a solution II;
(3) adding water into the solution II to obtain a solution III;
(4) adding a regulator into the third solution to obtain a fourth solution, wherein the regulator is one of dimethylbenzene, trimethylbenzene or tetramethylbenzene;
(5) controlling the temperature of the solution IV within the range of 25-300 ℃ to carry out hydrothermal reaction;
(6) after the reaction is finished, the target product is obtained through centrifugal separation, washing and drying.
Wherein the metal zirconium salt is one of zirconium tetrachloride, zirconium oxychloride, zirconyl nitrate, n-butyl zirconium, zirconium n-propoxide or zirconium acetate; the dicarboxylic acid organic ligand is terephthalic acid or amino terephthalic acid; the aprotic polar solvent is N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide or 1, 3-dimethyl-imidazolidinone.
Wherein the monocarboxylic organic acid is one or more of formic acid, acetic acid or benzoic acid.
In the step (1), the molar ratio of the metal zirconium salt to the dicarboxylic acid organic ligand is 0.1 to 2: 1, and the molar ratio of the metal zirconium salt to the aprotic polar solvent is 1: 10 to 2000.
In the step (1), the molar ratio of the metal zirconium salt to the dicarboxylic acid organic ligand is preferably 0.5 to 1: 1, and the molar ratio of the metal zirconium salt to the aprotic polar solvent is preferably 1: 500 to 1500.
In the step (2), the molar ratio of the monocarboxylic organic acid to the metal zirconium salt is 10-200: 1.
Wherein the molar ratio of the monocarboxylic organic acid to the metal zirconium salt is 50-150: 1.
Wherein, in the step (3), the molar ratio of the added water to the metal zirconium salt is 1-50: 1.
Wherein the molar ratio of the regulator to the metal zirconium salt in the step (4) is 0.1-10: 1.
wherein, the reaction temperature in the step (5) is preferably 100-150 ℃, and the reaction time is 10-24 h.
Wherein the synthesis method preferably comprises the following steps:
(1) adding one of zirconium n-propoxide or zirconium acetate and amino terephthalic acid into one of dimethyl sulfoxide or 1, 3-dimethyl-imidazolidinone, and stirring at room temperature until the solid is completely dissolved to obtain a solution I;
(2) adding acetic acid into the first solution, and uniformly stirring to obtain a second solution;
(3) adding water into the solution II to obtain a solution III;
(4) adding dimethylbenzene into the solution III to obtain a solution IV;
(5) controlling the temperature of the solution IV within the range of 25-300 ℃ to carry out hydrothermal reaction;
(6) after the reaction is finished, the target product is obtained through centrifugal separation, washing and drying.
Advantageous effects
Compared with the prior art, the method provided by the invention can successfully obtain the small-grain zirconium-based MOFs material by controlling the nucleation and crystallization rate of the metal ions and the organic ligand, thereby improving the mass transfer efficiency of the microporous material. The small grains are easy to contact and accumulate and form a permanent mesoporous structure among the grains due to the higher surface energy. The method has simple and easy synthetic steps, does not need to add a template agent with higher price, does not need a stripping plate, and simplifies the synthetic steps.
Drawings
FIG. 1 is a scanning electron micrograph of the product obtained in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the product obtained in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of the product obtained in example 3 of the present invention.
FIG. 4 is a scanning electron micrograph of the product obtained in example 4 of the present invention.
FIG. 5 is a scanning electron micrograph of the product obtained in example 5 of the present invention.
FIG. 6 is a scanning electron micrograph of a product obtained in example 6 of the present invention.
FIG. 7 is a scanning electron micrograph of a product obtained in comparative example 1 of the present invention.
FIG. 8 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in example 1 of the present invention.
FIG. 9 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in example 2 of the present invention.
FIG. 10 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in example 3 of the present invention
FIG. 11 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in example 4 of the present invention
FIG. 12 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in example 5 of the present invention
FIG. 13 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in example 6 of the present invention
FIG. 14 is a nitrogen adsorption-desorption isotherm diagram of the product obtained in comparative example 1 of the present invention
Detailed Description
Example 1
0.23mmol of ZrCl4And 2.3mmol of terephthalic acid are added into 2.3mmol of N, N-dimethylformamide, stirred at room temperature until the solid is completely dissolved, then 2.3mmol of acetic acid is added, stirred uniformly, and 0.23mmol of water and 0.023mmol of p-xylene are added; transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, controlling the reaction temperature to be 100 ℃, and controlling the reaction time to be 10 hours; after the reaction is finished, the target product 1 is obtained through centrifugal separation, washing and drying, and a scanning electron microscope image and a nitrogen adsorption-desorption isotherm thereof are shown in fig. 1 and fig. 8.
Example 2
Adding 0.46mmol of ZrOCl2 & 8H2O and 0.23mmol of terephthalic acid into 920mmol of N, N-dimethylacetamide, stirring at room temperature until all solids are dissolved, adding 92mmol of formic acid, adding 23mmol of water and 0.23mmol of mesitylene, and stirring uniformly at room temperature; transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, controlling the reaction temperature to be 120 ℃, and controlling the reaction time to be 12 hours; after the reaction is finished, the target product 2 is obtained through centrifugal separation, washing and drying, and a scanning electron microscope image and a nitrogen adsorption-desorption isotherm thereof are shown in fig. 2 and fig. 9.
Example 3
Adding 0.23mmol of zirconyl nitrate and 0.46mmol of terephthalic acid into 115mmol of acetonitrile, stirring at room temperature until the solid is completely dissolved, adding 11.5mmol of benzoic acid, stirring uniformly, adding 11.5mmol of water and 2.3mmol of durene; then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, controlling the reaction temperature to be 150 ℃, and controlling the reaction time to be 24 hours; after the reaction is finished, the target product 3 is obtained through centrifugal separation, washing and drying, and a scanning electron microscope image and a nitrogen adsorption-desorption isotherm thereof are shown in fig. 3 and fig. 10.
Example 4
Adding 0.23mmol of n-butyl zirconium and 0.23mmol of amino terephthalic acid into 345mmol of dimethyl sulfoxide, stirring at room temperature until all solids are dissolved, adding 34.5mmol of benzoic acid, stirring uniformly, adding 11.5mmol of water and 2.3mmol of trimethylbenzene; then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, controlling the reaction temperature to be 150 ℃, and controlling the reaction time to be 24 hours; after the reaction is finished, the target product 4 is obtained through centrifugal separation, washing and drying, and a scanning electron microscope image and a nitrogen adsorption-desorption isotherm thereof are shown in fig. 4 and 11.
Example 5
Adding 0.23mmol of zirconium n-propoxide and 0.46mmol of aminoterephthalic acid into 345mmol of 1, 3-dimethyl-imidazolidinone, stirring at room temperature until all solids are dissolved, adding 25mmol of acetic acid, stirring uniformly, and adding 11.5mmol of water and 2.3mmol of p-xylene; then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, controlling the reaction temperature to be 150 ℃, and controlling the reaction time to be 24 hours; after the reaction is finished, the target product 5 is obtained through centrifugal separation, washing and drying, and a scanning electron microscope image and a nitrogen adsorption-desorption isotherm thereof are shown in fig. 5 and 12.
Example 6
Adding 0.23mmol of zirconium acetate and 0.46mmol of amino terephthalic acid into 200mmol of 1, 3-dimethyl-imidazolidinone, stirring at room temperature until all solids are dissolved, adding 34.5mmol of acetic acid, stirring uniformly, and adding 11.5mmol of water and 2.3mmol of p-xylene; then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, controlling the reaction temperature to be 150 ℃, and controlling the reaction time to be 24 hours; after the reaction is finished, the target product 6 is obtained through centrifugal separation, washing and drying, and a scanning electron microscope image and a nitrogen adsorption-desorption isotherm thereof are shown in fig. 6 and fig. 13.
Comparative example 1
Putting 0.23mmol of ZrCl4 and 0.23mmol of terephthalic acid into a reaction kettle with a polytetrafluoroethylene lining, adding 25mL of DMF, uniformly mixing, controlling the reaction temperature at 120 ℃, and reacting for 12 h; after the reaction is finished, the comparative product is obtained by centrifugal separation, washing and drying, and the scanning electron microscope picture and the nitrogen adsorption-desorption isotherm are shown in figures 7 and 14.
As can be seen from the measurement of FIGS. 1 to 7, as the scales of FIGS. 1 to 7 are all 500nm, the grain size of the samples obtained in examples 1 to 6 is obviously smaller than that of the product of comparative example 1, the grain size of the MOFs in examples 1 to 6 is reduced to about 20nm, the MOFs material with small grains is successfully obtained, and the grain size of the MOFs material in the comparative example is about 200 nm. As can be seen from fig. 8 to 14, the nitrogen adsorption and desorption isotherms of the samples obtained in examples 1 to 6 all showed significant hysteresis loops, indicating that there is a mesopore, while the nitrogen adsorption and desorption isotherms of the samples obtained in comparative example 1 did not show significant hysteresis loops, indicating that there is no mesopore. The existence of the mesopores can reduce the diffusion resistance in the adsorption and desorption processes and improve the mass transfer efficiency. In conclusion, the metal organic framework material with small crystal grains can be obtained by adopting the method provided by the invention, and simultaneously, a mesoporous structure is formed among the crystal grains.
The above-described embodiments are merely preferred embodiments and are not intended to limit the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. All equivalent changes and modifications made according to the content of the claims of the present invention should be regarded as the technical scope of the present invention.
Claims (10)
1. A method for synthesizing a metal organic framework is characterized by comprising the following steps:
(1) adding metal zirconium salt and dicarboxylic acid organic ligand into an aprotic polar solvent, and stirring at room temperature until the solid is completely dissolved to obtain a solution I;
(2) adding monocarboxylic organic acid into the solution I, and uniformly stirring to obtain a solution II;
(3) adding water into the solution II to obtain a solution III;
(4) adding a regulator into the third solution to obtain a fourth solution, wherein the regulator is one of dimethylbenzene, trimethylbenzene or tetramethylbenzene;
(5) controlling the temperature of the solution IV within the range of 25-300 ℃ to carry out hydrothermal reaction;
(6) after the reaction is finished, the target product is obtained through centrifugal separation, washing and drying.
2. The synthesis method according to claim 1, wherein the metallic zirconium salt is one of zirconium tetrachloride, zirconium oxychloride, zirconyl nitrate, zirconium n-butoxide, zirconium n-propoxide or zirconium acetate; the dicarboxylic acid organic ligand is terephthalic acid or amino terephthalic acid; the aprotic polar solvent is N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide or 1, 3-dimethyl-imidazolidinone; the monocarboxylic organic acid is one or more of formic acid, acetic acid or benzoic acid.
3. The synthesis method according to claim 1, wherein in step (1), the molar ratio of the metal zirconium salt to the dicarboxylic acid organic ligand is 0.1 to 2: 1, and the molar ratio of the metal zirconium salt to the aprotic polar solvent is 1: 10 to 2000.
4. The synthesis method according to claim 3, wherein in the step (1), the molar ratio of the metal zirconium salt to the dicarboxylic acid organic ligand is 0.5 to 1: 1, and the molar ratio of the metal zirconium salt to the aprotic polar solvent is 1: 500 to 1500.
5. The synthesis method according to claim 1, wherein in the step (2), the molar ratio of the metal zirconium salt to the monocarboxylic organic acid is 1: 10 to 200.
6. The synthesis method according to claim 5, wherein in the step (2), the molar ratio of the metal zirconium salt to the monocarboxylic organic acid is 1: 50 to 150.
7. The synthesis method according to claim 1, wherein in the step (3), the molar ratio of the metal zirconium salt to the water is 1: 1 to 50.
8. The synthesis method according to claim 1, wherein the molar ratio of the zirconium metal salt to the regulator in step (4) is 1: 0.1 to 10.
9. The synthesis method according to claim 1, wherein the reaction temperature in the step (5) is preferably 100-150 ℃ and the reaction time is 10-24 h.
10. The method of synthesis according to claim 1, comprising the steps of:
(1) adding one of zirconium n-propoxide or zirconium acetate and amino terephthalic acid into one of dimethyl sulfoxide or 1, 3-dimethyl-imidazolidinone, and stirring at room temperature until the solid is completely dissolved to obtain a solution I;
(2) adding acetic acid into the first solution, and uniformly stirring to obtain a second solution;
(3) adding water into the solution II to obtain a solution III;
(4) adding dimethylbenzene into the solution III to obtain a solution IV;
(5) controlling the temperature of the solution IV within the range of 25-300 ℃ to carry out hydrothermal reaction;
(6) after the reaction is finished, the target product is obtained through centrifugal separation, washing and drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452941A (en) * | 2022-02-14 | 2022-05-10 | 南京工业大学 | Hydrophobic mesoporous nano material and preparation method thereof |
| CN114773864A (en) * | 2022-04-18 | 2022-07-22 | 宁波长阳科技股份有限公司 | Composite material based on zirconium-based organic framework compound and preparation method and application thereof |
| CN115007210A (en) * | 2022-04-28 | 2022-09-06 | 华南理工大学 | Hollow UiO-66-NH 2 (MZr) packaging metal particle and preparation method and application thereof |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452941A (en) * | 2022-02-14 | 2022-05-10 | 南京工业大学 | Hydrophobic mesoporous nano material and preparation method thereof |
| CN114773864A (en) * | 2022-04-18 | 2022-07-22 | 宁波长阳科技股份有限公司 | Composite material based on zirconium-based organic framework compound and preparation method and application thereof |
| CN115007210A (en) * | 2022-04-28 | 2022-09-06 | 华南理工大学 | Hollow UiO-66-NH 2 (MZr) packaging metal particle and preparation method and application thereof |
| CN115007210B (en) * | 2022-04-28 | 2023-11-24 | 华南理工大学 | Hollow UiO-66-NH 2 (MZr) encapsulated metal particles, and preparation method and application thereof |
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