CN115894955A - Zirconium-based metal organic framework material, and synthesis method and application thereof - Google Patents
Zirconium-based metal organic framework material, and synthesis method and application thereof Download PDFInfo
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- CN115894955A CN115894955A CN202211607463.5A CN202211607463A CN115894955A CN 115894955 A CN115894955 A CN 115894955A CN 202211607463 A CN202211607463 A CN 202211607463A CN 115894955 A CN115894955 A CN 115894955A
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- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 31
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003754 zirconium Chemical class 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 22
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 9
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 9
- 239000013207 UiO-66 Substances 0.000 claims description 67
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- 238000003786 synthesis reaction Methods 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000002140 halogenating effect Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 5
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 112
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 60
- 238000005406 washing Methods 0.000 description 38
- 238000002441 X-ray diffraction Methods 0.000 description 37
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 30
- 238000012512 characterization method Methods 0.000 description 30
- 235000019253 formic acid Nutrition 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
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- -1 10mLN Chemical compound 0.000 description 5
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- XZAWOOAVCQUZBG-UHFFFAOYSA-N 1-iodo-2-methoxynaphthalene Chemical compound C1=CC=CC2=C(I)C(OC)=CC=C21 XZAWOOAVCQUZBG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
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- HZHXGUXTFHBONU-UHFFFAOYSA-N formic acid;zirconium Chemical compound [Zr].OC=O HZHXGUXTFHBONU-UHFFFAOYSA-N 0.000 description 2
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Abstract
The application provides a synthesis method of a zirconium-based metal organic framework material, which comprises the step of reacting zirconium salt, a ligand and a seed crystal to obtain the zirconium-based metal organic framework material. Through seed crystal mediation, the zirconium salt and the ligand can react at a lower temperature, such as 30-70 ℃, so that the energy consumption is reduced, the operation is safe, and the method is beneficial to large-scale production and industrial application. The invention also provides a zirconium-based metal organic framework material and application thereof, the zirconium-based metal organic framework material provided by the invention has strong Lewis acidity, and can be used as Lewis acid for catalytic reaction, such as catalysis of 2-methoxynaphthalene and halogenated reagent for reaction; the zirconium-based metal organic framework material provided by the invention can also be used as a catalyst for Meerwein-Ponndorf reduction reaction, such as catalysis of conversion of cyclohexanone into cyclohexanol.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a zirconium-based metal organic framework material, a synthesis method and application thereof.
Background
Metal organic framework Materials (MOFs) are a class of porous crystalline materials formed by coordinately bonding a metal center to an organic bridging ligand. Since the successful synthesis of MOFs in the nineties of the last century, such materials have attracted much attention due to their excellent crystallinity, porosity and tunability, and have been used in various fields such as catalysis, gas adsorption, separation, sensing and drug delivery. Among many MOFs, a metal-organic framework material (Zr-MOFs material) composed of a metal cluster formed by + 4-valent Zr and a carboxylic acid ligand is widely used due to the stability of Zr-O bonds.
At present, the main synthesis means of Zr-MOFs materials is a solvothermal method, and a precursor is crystallized in a closed system at a higher temperature (not less than 120 ℃) and a longer reaction time (not less than 24 hours), so that the Zr-MOFs materials are obtained. However, the method generates higher energy loss and dangerous autogenous pressure, and is not beneficial to further mass production and industrial application of the Zr-MOFs.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a zirconium-based metal organic framework material, a synthesis method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for synthesizing a zirconium-based metal organic framework material comprises the step of reacting zirconium salt, a ligand and a seed crystal to obtain the zirconium-based metal organic framework material.
Preferably, the seed crystal is selected from the group consisting of UiO-66, MOF-808, uiO-66-NH 2 Or DUT-67.
Preferably, the zirconium salt is selected from zirconium chloride or zirconium oxychloride.
Preferably, the ligand is selected from terephthalic acid, trimesic acid, 2-aminoterephthalic acid or 2, 5-thiophenedicarboxylic acid.
Preferably, the reaction temperature is 30-70 ℃, and the reaction time is 12-24 h.
The invention also provides the application of the zirconium-based metal organic framework material as Lewis acid.
The invention also provides a synthesis method of the 1-iodine-2-methoxynaphthalene, wherein the 2-methoxynaphthalene and the halogenated reagent react under the action of the zirconium-based metal organic framework material to obtain the 2-methoxynaphthalene derivative.
The invention also provides application of the zirconium-based metal organic framework material as a catalyst for Meerwein-Ponndorf reduction reaction.
The invention also provides a method for synthesizing cyclohexanol, wherein the cyclohexanol is obtained by reacting cyclohexanone under the action of a zirconium-based metal organic framework material.
The invention provides a method for synthesizing a zirconium-based metal organic framework material, which comprises the step of reacting zirconium salt, a ligand and a seed crystal to obtain the zirconium-based metal organic framework material. The method adds the crystal seed to ensure that the zirconium salt and the ligand react at a lower temperature, such as 30-70 ℃, so as to obtain the zirconium-based metal organic framework material, thereby reducing energy consumption, having safe operation and being beneficial to large-scale production and industrial application.
In addition, the Zr-MOFs prepared by the method has Lewis acidity, and can be used as Lewis acid in catalytic reaction, such as 2-methoxy naphthalene and halogenated reagent for reaction; can also be used as a catalyst for Meerwein-Ponndorf reduction, for example, for catalyzing the conversion of cyclohexanone into cyclohexanol.
Drawings
FIG. 1 is an X-ray diffraction Pattern (PXRD) of seed crystals UiO-66 and UiO-66 of the present invention;
FIG. 2 is a scanning electron microscope image (SEM) of seed crystals UiO-66 and UiO-66 in the present invention;
FIG. 3 shows N of the seed crystals UiO-66 and UiO-66 in the present invention 2 Adsorption curve (BET);
FIG. 4 is a thermogravimetric analysis (TGA) of the seeds UiO-66 and UiO-66 of the present invention;
FIG. 5 is an X-ray diffraction Pattern (PXRD) of the present invention after soaking seeds UiO-66 and UiO-66 in aqueous solutions of different pH values;
FIG. 6 is an X-ray diffraction Pattern (PXRD) of the seed crystals MOF-808 and MOF-808 of the present invention;
FIG. 7 is a scanning electron microscope image (SEM) of seed MOF-808 and MOF-808 according to the invention;
FIG. 8 is a representation of seed MOFs-808 and M of the present inventionN OF-808 2 Adsorption curve (BET);
FIG. 9 is a thermogravimetric analysis (TGA) plot of seed crystals MOF-808 and MOF-808 of the present invention;
FIG. 10 is an X-ray diffraction Pattern (PXRD) of seed crystals MOF-808 and MOF-808 of the present invention after immersion in aqueous solutions of different pH;
FIG. 11 shows a seed crystal UiO-66-NH according to the present invention 2 And UiO-66-NH 2 X-ray diffraction Pattern (PXRD) of (a);
FIG. 12 shows a seed crystal UiO-66-NH according to the present invention 2 And UiO-66-NH 2 Scanning electron microscope images (SEM);
FIG. 13 shows a seed crystal UiO-66-NH according to the present invention 2 And UiO-66-NH 2 N of (A) 2 Adsorption profile (BET);
FIG. 14 shows a seed crystal UiO-66-NH according to the present invention 2 And UiO-66-NH 2 Thermogravimetric analysis curve (TGA);
FIG. 15 shows a seed crystal UiO-66-NH according to the present invention 2 And UiO-66-NH 2 X-ray diffraction Patterns (PXRD) after immersion in aqueous solutions of different pH;
FIG. 16 is an X-ray diffraction Pattern (PXRD) of a seed crystal DUT-67 and DUT-67 of the present invention;
FIG. 17 is a scanning electron microscope image (SEM) of a seed crystal DUT-67 and DUT-67 of the present invention;
FIG. 18 shows N of the seed crystals DUT-67 and DUT-67 of the present invention 2 Adsorption curve (BET);
FIG. 19 is a thermogravimetric analysis (TGA) curve of a seed DUT-67 and DUT-67 of the present invention;
FIG. 20 is an X-ray diffraction Pattern (PXRD) of a seed crystal DUT-67 and DUT-67 of the present invention after immersion in aqueous solutions of different pH;
FIG. 21 is a diagram showing an apparatus for synthesizing Zr-MOFs in an expanded scale gram in the present invention;
FIG. 22 is an X-ray diffraction Pattern (PXRD) of expanded-dose gram-scale synthetic MOF-808 according to the present invention;
FIG. 23 is a graph of N of the expanded gram synthetic seeds MOF-808 and MOF-808 of the present invention 2 Adsorption profile (BET);
FIG. 24 is a comparison of catalytic activities of seed crystals of Zr-MOFs and Zr-MOFs in the present invention for the reaction of 2-methoxynaphthalene with a halogenating agent;
FIG. 25 is a comparison of catalytic activity of recovered and recycled MOF-808 on the reaction of 2-methoxynaphthalene with a halogenating agent;
FIG. 26 is a comparison of the reduction activities of seed crystals MOF-808 and MOF-808 in catalyzing Meerwein-Ponndorf reduction reactions in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for synthesizing a zirconium-based metal organic framework material, which comprises the step of reacting zirconium salt, a ligand and a seed crystal to obtain the zirconium-based metal organic framework material.
The method adds the seed crystal in the reaction process of the zirconium salt and the ligand, and can obviously reduce the reaction temperature. In the present invention, the seed crystal is selected from the group consisting of UiO-66, MOF-808, uiO-66-NH 2 Or DUT-67. The source of the seed crystal is not particularly limited, and the seed crystal can be purchased in the market and also can be prepared according to the following method:
the zirconium salt and the ligand are mixed and then react at 100-120 ℃.
Specifically, in the seed crystal synthesis process, a zirconium salt and a ligand are first mixed with a solvent to obtain a mixed solution. In some possible implementations, the zirconium salt is selected from zirconium chloride or zirconium oxychloride. In some possible implementations, the ligand is selected from terephthalic acid, trimesic acid, 2-aminoterephthalic acid, or 2, 5-thiophenedicarboxylic acid. In some possible implementations, the solvent is selected from one or more of N, N-dimethylformamide, N-methylpyrrolidone, or formic acid, preferably a mixture of N, N-dimethylformamide and formic acid or a mixture of N, N-dimethylformamide, N-methylpyrrolidone, and formic acid. When the solvent is a mixed solution of N, N-dimethylformamide and formic acid, the ratio of N, N-dimethylformamide: the volume ratio of formic acid is 1 to 5, and for example, 1; when the solvent is a mixed solution of N, N-dimethylformamide, N-methylpyrrolidone and formic acid, the ratio of N, N-dimethylformamide: n-methylpyrrolidone: the volume ratio of formic acid is 1-2.
In some possible implementations, the molar ratio of zirconium salt to ligand is 1 to 3, preferably 1, 3. In some possible implementations, the ratio of the amount of the zirconium salt to the solvent is 0.01mmol/mL to 0.06mmol/mL, preferably 0.017mmol/mL, 0.031mmol/mL, 0.045mmol/mL, or 0.050mmol/mL.
After mixing the zirconium salt, the ligand and the solvent, preferably, the mixed solution is subjected to ultrasonic treatment to fully dissolve the zirconium salt, and the obtained mixed solution is subjected to reaction at the temperature of 100-120 ℃, wherein the reaction time is preferably 24-48 h.
After the completion of the reaction, the obtained reaction solution is preferably subjected to separation, washing and drying. In some possible implementations, the separation may be a centrifugation. In some possible implementations, the washing is in particular: firstly, washing with N, N-dimethylformamide for three times; then washed with ethanol three times. After washing, the product obtained is dried, preferably in an oven, at a temperature of 70 ℃ to 90 ℃, preferably 85 ℃. After drying, seed crystals are obtained.
Specifically, zirconium chloride and terephthalic acid are used as raw materials, and seed crystal UiO-66 can be synthesized in N, N-dimethylformamide and formic acid; zirconium oxychloride and trimesic acid are taken as raw materials, and crystal seeds MOF-808 can be synthesized in N, N-dimethylformamide and formic acid; zirconium chloride and 2-amino terephthalic acid are used as raw materials, and seed crystal UiO-66-NH can be synthesized in N, N-dimethylformamide and formic acid 2 (ii) a The seed crystal DUT-67 can be synthesized by using zirconium chloride and 2, 5-thiophenedicarboxylic acid as raw materials in N, N-dimethylformamide, N-methylpyrrolidone and formic acid.
After the seed crystal is obtained, the zirconium salt, the ligand and the seed crystal are mixed to carry out a reaction, and the reaction is actually a process for synthesizing the Zr-MOFs under low energy by adopting the seed crystal mediation.
Specifically, in the process of preparing Zr-MOFs by adopting the seed crystal, the zirconium salt, the ligand and the seed crystal are mixed with the solvent to obtain a mixed solution. In some possible implementations, the zirconium salt is selected from zirconium chloride or zirconium oxychloride. In some possible implementations, the ligand is selected from terephthalic acid, trimesic acid, 2-aminoterephthalic acid, or 2, 5-thiophenedicarboxylic acid. In some possible implementations, the seed crystal is selected from the group consisting of UiO-66, MOF-808, uiO-66-NH 2 Or DUT-67. In some possible implementations, the solvent is selected from one or more of N, N-dimethylformamide, N-methylpyrrolidone, or formic acid, preferably a mixture of N, N-dimethylformamide and formic acid or a mixture of N, N-dimethylformamide, N-methylpyrrolidone, and formic acid. When the solvent is a mixed solution of N, N-dimethylformamide and formic acid, the ratio of N, N-dimethylformamide: the volume ratio of formic acid is 1 to 5, and for example, 1; when the solvent is a mixed solution of N, N-dimethylformamide, N-methylpyrrolidone and formic acid, the ratio of N, N-dimethylformamide: n-methylpyrrolidone: the volume ratio of formic acid is 1-2.
In some possible implementations, the ratio of zirconium salt: the molar ratio of the ligand is 1 to 3, and preferably 1. In some possible implementations, the zirconium salt: the mass ratio of the seed crystal is 4 to 25, preferably 4.8. In some possible implementations, the ratio of the amount of the zirconium salt to the solvent is 0.01mmol/mL to 0.06mmol/mL, preferably 0.017mmol/mL, 0.031mmol/mL, 0.045mmol/mL, or 0.050mmol/mL.
After mixing the zirconium salt, the ligand and the seed crystal with the solvent, the mixed solution is preferably subjected to ultrasonic treatment to sufficiently dissolve the zirconium salt, and the obtained mixed solution is reacted at a temperature of 30 to 70 ℃, preferably 35 to 65 ℃, 40 to 60 ℃, or 45 to 55 ℃, more preferably 50 ℃. The reaction time is 12-24 h, preferably 24h.
After the completion of the reaction, the obtained reaction solution is preferably subjected to separation, washing and drying. In some possible implementations, the separation may be a centrifugation. In some possible implementations, the washing is in particular: firstly, washing with N, N-dimethylformamide for three times; then washing with ethanol for three times; after washing, the product obtained is dried, preferably in an oven, at a temperature of 70 ℃ to 90 ℃, preferably 85 ℃. And after drying, obtaining the crystal seed mediated low-energy synthesized Zr-MOFs.
In the process of preparing the UiO-66, a seed crystal UiO-66 is used for mediating, zirconium chloride and terephthalic acid are used as raw materials, and the raw materials react in N, N-dimethylformamide and formic acid; in the process of preparing the MOF-808, mediating by using seed crystal MOF-808, taking zirconium oxychloride and trimesic acid as raw materials to react in N, N-dimethylformamide and formic acid; in the preparation of UiO-66-NH 2 In the process of (1), a seed crystal UiO-66-NH is used 2 Mediating, using zirconium chloride and 2-amino terephthalic acid as raw materials to react in N, N-dimethylformamide and formic acid; in the process of preparing DUT-67, the crystal seed DUT-67 is used to mediate the reaction of zirconium chloride and 2, 5-thiophenedicarboxylic acid as raw materials in N, N-dimethylformamide, N-methylpyrrolidone and formic acid.
The invention utilizes crystal seed mediation to synthesize Zr-MOFs at low temperature, the Zr-MOFs has increased surface structure defects, higher porosity and higher specific surface area, and can be used as Lewis acid.
For example, zr-MOFs is used as a catalyst and can catalyze 2-methoxy naphthalene to react with a halogenated reagent, and the specific steps are as follows:
mixing 2-methoxy naphthalene and a halogenated reagent, and reacting under the action of a catalyst to obtain the 2-methoxy naphthalene derivative.
Mixing 2-methoxy naphthalene, a halogenated reagent, a catalyst and an organic solvent to obtain a mixed solution. In some possible implementations, the halo reagent is selected from an iodo reagent, preferably N-iodo succinimide. In some possible implementations, the catalyst is selected from UiO-66 or MOF-808, which is preferably activated overnight at 120 ℃ under vacuum. In some possible implementations, the solvent is selected from organic solvents, preferably acetonitrile.
In some possible implementations, the ratio of 2-methoxynaphthalene: the molar ratio of the halogenating agent is 1 to 1.5, preferably 1:1.1. in some possible implementations, the ratio of 2-methoxynaphthalene: the mass ratio of the catalyst is 1-2, preferably 1.58. In some possible implementations, the ratio of 2-methoxynaphthalene: the dosage proportion of the acetonitrile is 10-20mg.
Mixing 2-methoxy naphthalene, a halogenated reagent, a catalyst and an organic solvent to obtain a mixed solution. Preferably, the mixture is subjected to ultrasonic treatment to sufficiently dissolve the mixture, thereby effecting the reaction. The process is preferably carried out under anaerobic conditions, for example by evacuation or by backfilling with nitrogen, repeated 3 to 5 times, preferably by backfilling with nitrogen, preferably 5 times. The invention preferably reacts under shade conditions, such as shading with tinfoil; the reaction temperature is 25-30 ℃, and the reaction time is preferably 4-24 h; after the reaction is finished, the 2-methoxy naphthalene derivative is obtained.
Compared with Zr-MOFs prepared by a solvothermal method, the Zr-MOFs synthesized by the method has stronger Lewis acid catalytic performance, can catalyze 2-methoxynaphthalene to react with a halogenated reagent, and has higher reaction conversion rate.
The Zr-MOFs provided by the invention can also be applied as a catalyst for Meerwein-Ponndorf reduction reaction, for example, the Zr-MOFs is used for catalyzing cyclohexanone to be converted into cyclohexanol, and the specific steps are as follows:
and (3) mixing cyclohexanone and a reducing agent, and reacting under the action of Zr-MOFs in the technical scheme to obtain cyclohexanol.
Specifically, cyclohexanone, a reducing agent, and a catalyst are mixed to obtain a mixed solution. In some possible implementations, the reducing agent is a liquid alcohol, preferably an alcohol containing 1 to 6 carbon atoms, such as propanol, butanol, etc., more preferably isopropanol. In some possible implementations, the catalyst is preferably MOF-808. In some possible implementations, the ratio of cyclohexanone: the volume ratio of the reducing agent is 1 to 3, preferably 2.1. Cyclohexanone: the proportional relation of the dosage of the catalyst is 10-30 mu L:5 to 15mg, preferably 21 μ L:10mg.
And mixing cyclohexanone, a reducing agent and a catalyst to obtain a mixed solution. In some possible implementations, it is preferable to sonicate the mixed solution to sufficiently dissolve it. After the mixed solution is obtained, the mixed solution is reacted in an oil bath kettle, the reaction temperature is 70-90 ℃, the preferential reaction temperature is 80 ℃, and the reaction time is 1-3 h. After the reaction is completed, cyclohexanol is obtained.
The Zr-MOFs synthesized by the method can be used as a catalyst for catalyzing Meerwein-Ponndorf reduction reaction, and experimental results show that compared with Zr-MOFs prepared by a solvothermal method, the Zr-MOFs synthesized by the method can shorten the reaction time and improve the reaction efficiency.
The invention is further illustrated below with reference to examples and figures.
Example 1 seed mediated Low energy Synthesis of UiO-66
(1) Synthetic seed crystal UiO-66
Adding 48mg of zirconium chloride, 34mg of terephthalic acid, 10mLN, N-dimethylformamide and 2mL of formic acid into a 20mL small bottle, ultrasonically dissolving for 1min at 25 ℃, transferring the bottle into a constant-temperature oven at 120 ℃, standing for 24h, centrifuging, washing 3 times by using N, N-dimethylformamide, washing 3 times by using ethanol, performing centrifugal separation after each washing, transferring the product into an oven at 85 ℃ after the washing is finished, and standing for 6h to obtain seed crystal UiO-66, namely white powder, wherein the yield is 72%.
(2) Seed-mediated low-energy synthesis of UiO-66
Adding 48mg of zirconium chloride, 34mg of terephthalic acid, 10mg of seed crystal UiO-66 obtained in the step (1), 10mLN, N-dimethylformamide and 2mL of formic acid into a 25mL round-bottom flask, ultrasonically dissolving for 1min at 25 ℃, transferring into an oil bath kettle at 50 ℃, stirring for reacting for 24h, centrifuging after the reaction is finished, washing for 3 times by using N, N-dimethylformamide and washing for 3 times by using ethanol, performing centrifugal separation after each washing, transferring the product into an oven at 85 ℃ after the reaction is finished, standing for 6h to obtain the seed crystal-mediated low-energy synthesized UiO-66, wherein the obtained UiO-66 is a pure-phase crystal, is in a white powder shape and has the yield of 45%.
PXRD characterization is carried out on the seed crystal UiO-66 obtained in the step (1) and the UiO-66 obtained in the step (2), the characterization results are shown in figure 1, figure 1 is PXRD spectra of the seed crystal UiO-66 and the UiO-66, and as can be seen from figure 1, the seed crystal mediated low-energy synthesis UiO-66 and the seed crystal UiO-66 have the same X-ray diffraction structure and have excellent crystallinity.
SEM representation is carried out on the seed crystal UiO-66 obtained in the step (1) and the UiO-66 obtained in the step (2), the representation result is shown in figure 2, figure 2 is an SEM image of the seed crystal UiO-66 and the UiO-66, and as can be seen from figure 2, the shape of the UiO-66 evolves towards a cuboctahedron, and a special shape different from that of the seed crystal UiO-66 is generated.
And (3) performing BET characterization on the seed crystal UiO-66 obtained in the step (1) and the UiO-66 obtained in the step (2), wherein the characterization results are shown in FIG. 3, FIG. 3 is a BET spectrum of the seed crystals UiO-66 and UiO-66, and as can be seen from FIG. 3, the seed crystals UiO-66 and UiO-66 both have porosity, and the UiO-66 shows the adsorption characteristics of mesopores, which indicates that the UiO-66 has additional structural defects and is beneficial to improving the adsorption and catalysis performances of the UiO-66.
TGA characterization is carried out on the seed crystal UiO-66 obtained in the step (1) and the UiO-66 obtained in the step (2), the characterization results are shown in figure 4, figure 4 is a TGA spectrum of the seed crystal UiO-66 and the UiO-66, and as can be seen from figure 4, the seed crystal UiO-66 and the UiO-66 have approximate weight-loss platform temperatures, which indicates that the seed crystal UiO-66 and the UiO-66 have approximate thermal stability.
PXRD test is carried out after the seed crystal UiO-66 obtained in the step (1) and the UiO-66 obtained in the step (2) are soaked in water solutions with different pH values, the test result is shown in figure 5, figure 5 is a PXRD pattern of the seed crystal UiO-66 and the UiO-66 after being soaked in the water solutions with different pH values, and as can be seen from figure 5, the seed crystal UiO-66 and the UiO-66 both have good diffraction intensity and peak pattern, which shows that the seed crystal UiO-66 and the UiO-66 have approximate stability to acid and alkali.
Example 2 seed mediated Low energy Synthesis of MOF-808
(1) Synthesis of seed MOF-808
Adding 242mg of zirconium oxychloride octahydrate, 52.5mg of trimesic acid, 7.5mLN, N-dimethylformamide and 7.5mL of formic acid into a 20mL bottle, ultrasonically dissolving for 1min at 25 ℃, transferring the bottle into a constant-temperature oven at 100 ℃, standing for 24h, centrifuging, washing 3 times with N, N-dimethylformamide, washing 3 times with ethanol, centrifugally separating after each washing, transferring the product into an oven at 85 ℃ after the completion of the centrifugal separation, standing for 6h to obtain seed crystals MOF-808, white powder and the yield of 80%.
(2) Seed-mediated low energy synthesis of MOF-808
Adding 242mg of zirconium oxychloride octahydrate, 52.5mg of trimesic acid, 10mg of seed crystals MOF-808, 7.5mLN, N-dimethylformamide and 7.5mL of formic acid obtained in the step (1) into a 25mL round-bottom flask, ultrasonically dissolving for 1min at 25 ℃, transferring into a 50 ℃ oil bath pot, stirring for reacting for 24h, centrifuging after the reaction is finished, washing for 3 times by using the N, N-dimethylformamide, washing for 3 times by using ethanol, centrifugally separating after each washing, transferring the product into an oven at 85 ℃ after the reaction is finished, standing for 6h to obtain the seed crystal mediated low-energy synthesized MOF-808, wherein the obtained MOF-808 is a pure-phase crystal, is white powder and has the yield of 41%.
PXRD characterization is carried out on the seed MOF-808 obtained in the step (1) and the MOF-808 obtained in the step (2), the characterization results are shown in figure 6, figure 6 is a PXRD spectrum of the seed MOF-808 and the MOF-808, and as can be seen from figure 6, the seed MOF-808 and the MOF-808 have the same X-ray diffraction structure and have excellent crystallinity.
SEM representation is carried out on the seed MOF-808 obtained in the step (1) and the MOF-808 obtained in the step (2), the representation result is shown in figure 7, figure 7 is an SEM image of the seed MOF-808 and the MOF-808, and as can be seen from figure 7, the appearance of the seed-mediated low-energy synthesized MOF-808 evolves towards a cuboctahedron, so that a special appearance different from the seed MOF-808 is generated.
And (3) performing BET characterization on the seed MOF-808 obtained in the step (1) and the MOF-808 obtained in the step (2), wherein the characterization results are shown in FIG. 8, FIG. 8 is a BET spectrum of the seed MOF-808 and the MOF-808, and as can be seen from FIG. 8, both the seed MOF-808 and the MOF-808 have porosity, and the MOF-808 shows a higher specific surface area than the seed MOF-808, which indicates that the MOF-808 has high porosity and increased structural defects, and is beneficial to improving the performance of the MOF-808 in adsorption and catalysis.
TGA characterization is carried out on the seed MOF-808 obtained in the step (1) and the MOF-808 obtained in the step (2), the characterization result is shown in figure 9, figure 9 is a TGA spectrum of the seed MOF-808 and the MOF-808, and as can be seen from figure 9, the seed MOF-808 and the MOF-808 have approximate weight-loss platform temperatures, which indicates that the seed MOF-808 and the MOF-808 have approximate thermal stability.
PXRD test is carried out on the seed MOF-808 obtained in the step (1) and the MOF-808 obtained in the step (2) after soaking in water solutions with different pH values, the test result is shown in figure 10, figure 10 is a PXRD pattern of the seed MOF-808 and the MOF-808 after soaking in the water solutions with different pH values, and as can be seen from figure 10, the seed MOF-808 and the MOF-808 both have better diffraction intensity and peak pattern, which indicates that the seed MOF-808 and the MOF-808 have similar stability to acid and alkali.
Example 3 seed mediated Low energy Synthesis of UiO-66-NH 2
(1) Synthetic seed crystal UiO-66-NH 2
Adding 125mg of zirconium chloride, 134mg of 2-amino terephthalic acid, 10mL LN, N-dimethylformamide and 2mL of formic acid into a 20mL small bottle, ultrasonically dissolving for 1min at 25 ℃, transferring the bottle into a constant-temperature oven at 120 ℃, standing for 24h, centrifuging, washing 3 times by using N, N-dimethylformamide, washing 3 times by using ethanol, centrifugally separating after each washing, transferring the product into an oven at 85 ℃ after the completion of the washing, standing for 6h to obtain seed crystals UiO-66-NH 2 Pale yellow powder, yield 55%.
(2) Seed-mediated low-energy synthesis of UiO-66-NH 2
125mg of zirconium chloride, 134mg of 2-aminoterephthalic acid and 10mg of seed crystal UiO-66-NH obtained in the step (1) 2 Adding 10mLN, N-dimethylformamide and 2mL formic acid into a 25mL round-bottom flask, ultrasonically dissolving for 1min at 25 ℃, transferring into an oil bath kettle at 50 ℃, stirring for reacting for 24h, centrifuging after the reaction is finished, washing for 3 times by using N, N-dimethylformamide, washing for 3 times by using ethanol, centrifugally separating after each washing, transferring the product into an oven at 85 ℃ after the reaction is finished, standing for 6h, and obtaining the seed crystal-mediated low-energy synthesized UiO-66-NH 2 Obtaining UiO-66-NH 2 Pure phase crystals were obtained in the form of a pale yellow powder with a yield of 22%.
Seed crystal UiO-66-NH obtained in the step (1) 2 And UiO-66-NH obtained in step (2) 2 PXRD characterization was performed, and the characterization results are shown in FIG. 11, in which FIG. 11 is the seed crystal UiO-66-NH 2 And UiO-66-NH 2 The PXRD pattern of (A) is shown in FIG. 11, the seed crystal UiO-66-NH 2 And UiO-66-NH 2 Has the same X-ray diffraction structure and excellent crystallinity.
Seed crystal UiO-66-NH obtained in the step (1) 2 And UiO-66-NH obtained in the step (2) 2 SEM characterization is carried out, the characterization result is shown in figure 12, and figure 12 shows that the seed crystal UiO-66-NH 2 And UiO-66-NH 2 FIG. 12 shows that the seed-mediated low-energy synthesis of UiO-66-NH 2 The morphology of (A) evolves towards a cubo-octahedron, which generates a crystal seed UiO-66-NH 2 The special morphology of (2).
Seed crystal UiO-66-NH obtained in the step (1) 2 And UiO-66-NH obtained in step (2) 2 BET characterization was performed, and the results are shown in FIG. 13, in which FIG. 13 shows the seed crystal UiO-66-NH 2 And UiO-66-NH 2 The BET spectrum of (A) is shown in FIG. 13, and the seed crystal UiO-66-NH 2 And seed-mediated low energy synthetic UiO-66-NH 2 All have porosity.
Seed crystal UiO-66-NH obtained in the step (1) 2 And UiO-66-NH obtained in step (2) 2 TGA characterization was performed and the results are shown in FIG. 14, where FIG. 14 is the seed crystal UiO-66-NH 2 And UiO-66-NH 2 The TGA spectrum of (A) is shown in FIG. 14, and the seed crystal UiO-66-NH 2 And UiO-66-NH 2 Has approximate weight loss platform temperature, which indicates that the seed crystal UiO-66-NH 2 And UiO-66-NH 2 Has approximate thermal stability.
Seed crystal UiO-66-NH obtained in the step (1) 2 And UiO-66-NH obtained in the step (2) 2 PXRD test was performed after soaking in different pH aqueous solutions, and the test results are shown in FIG. 15, in which FIG. 15 shows the seed crystal UiO-66-NH 2 And UiO-66-NH 2 PXRD (X ray diffraction pattern) after soaking in water solution with different pH values is shown in figure 15, and the seed crystal UiO-66-NH 2 And UiO-66-NH 2 All have better diffraction intensity and peak type, which shows that the seed crystal UiO-66-NH 2 And UiO-66-NH 2 Have similar stability to acids and bases.
EXAMPLE 4 Synthesis of seed-mediated Low energy Synthesis of DUT-67
(1) Solvothermal synthesis of seed crystal DUT-67
86.3mg of zirconium chloride, 46.2mg of 2, 5-thiophenedicarboxylic acid, 4.7mLN, N-dimethylformamide, 4.7 mLN-methylpyrrolidone and 2.63mL of formic acid were added to a 20mL vial, ultrasonically dissolved at 25 ℃ for 1min, transferred to a constant-temperature oven at 120 ℃, centrifuged after 24 hours of standing, washed 3 times with N, N-dimethylformamide and 3 times with ethanol, centrifuged after each washing, and after completion, the product was transferred to an oven at 85 ℃ and allowed to stand for 6 hours to obtain seed crystal DUT-67 as a white powder with a yield of 82%.
(2) Seed-mediated Low energy Synthesis of DUT-67
Adding 86.3mg of zirconium chloride, 46.2mg of 2, 5-thiophenedicarboxylic acid, 10mg of seed crystal DUT-67 obtained in the step (1), 4.7mLN, N-dimethylformamide, 4.7 mLN-methylpyrrolidone and 2.63mL of formic acid into a 25mL round-bottom flask, ultrasonically dissolving at 25 ℃ for 1min, transferring into an oil bath kettle at 50 ℃, stirring for reacting for 24h, centrifuging after the reaction is finished, washing 3 times by using N, N-dimethylformamide and 3 times by using ethanol, centrifuging after each washing, transferring the product into an oven at 85 ℃ for standing for 6h after the reaction is finished, and obtaining the DUT-67 synthesized by the seed crystal with low energy, wherein the obtained DUT-67 is a pure-phase crystal and is in a white powder shape, and the yield is 43%.
PXRD characterization is carried out on the seed crystal DUT-67 obtained in the step (1) and the DUT-67 obtained in the step (2), the characterization result is shown in FIG. 16, FIG. 16 is a PXRD spectrum of the seed crystal DUT-67 and the DUT-67, and as can be seen from FIG. 16, the seed crystal DUT-67 and the DUT-67 have the same X-ray diffraction structure and both have excellent crystallinity.
And (3) performing SEM characterization on the seed crystal DUT-67 obtained in the step (1) and the DUT-67 obtained in the step (2), wherein the characterization result is shown in FIG. 17, FIG. 17 is an SEM image of the seed crystal DUT-67 and the DUT-67, and as can be seen from FIG. 17, the morphology of the seed crystal mediated low-energy synthesis DUT-67 evolves towards a cuboctahedron, so that a special morphology different from that of the seed crystal DUT-67 is generated.
The seed crystal DUT-67 obtained in the step (1) and the DUT-67 obtained in the step (2) are subjected to BET characterization, the characterization results are shown in FIG. 18, FIG. 18 is a BET spectrum of the seed crystal DUT-67 and the DUT-67, and as can be seen from FIG. 18, both the seed crystal DUT-67 and the DUT-67 have porosity.
TGA characterization of the seed DUT-67 obtained in step (1) and the DUT-67 obtained in step (2) is performed, and the characterization result is shown in FIG. 19, FIG. 19 is a TGA graph of the seed DUT-67 and the DUT-67, and as can be seen in FIG. 19, the seed DUT-67 and the DUT-67 have approximate weight loss plateau temperatures, indicating that the seed DUT-67 and the DUT-67 have approximate thermal stability.
After the seed crystal DUT-67 obtained in the step (1) and the DUT-67 obtained in the step (2) are soaked in the water solutions with different pH values, PXRD test is carried out, the test result is shown in FIG. 20, FIG. 20 is a PXRD pattern of the seed crystal DUT-67 and the DUT-67 after being soaked in the water solutions with different pH values, and as can be seen from FIG. 20, the seed crystal DUT-67 and the DUT-67 both have better diffraction intensity and peak patterns, which shows that the seed crystal DUT-67 and the DUT-67 have similar stability to acid and alkali.
Example 5 seed mediated Synthesis of MOF-808 on gram scale at Low energy
(1) Synthesis of seed MOF-808
Adding 242mg of zirconium oxychloride octahydrate, 52.5mg of trimesic acid, 7.5mLN, N-dimethylformamide and 7.5mL of formic acid into a 20mL bottle, ultrasonically dissolving for 1min at 25 ℃, transferring the bottle into a constant-temperature oven at 100 ℃, standing for 24h, centrifuging, washing 3 times with N, N-dimethylformamide, washing 3 times with ethanol, centrifugally separating after each washing, transferring the product into an oven at 85 ℃ after the completion of the centrifugal separation, standing for 6h to obtain seed crystals MOF-808, white powder and the yield of 80%.
(2) Seed-mediated low energy synthesis of MOF-808
As shown in fig. 21, 16.13g of zirconium oxychloride octahydrate, 3.5g of trimesic acid, 1g of seed MOF-808, 500mln, N-dimethylformamide and 500mL of formic acid obtained in step (1) were added into a 2L reaction flask, the mixture was ultrasonically treated at 25 ℃ to uniformly disperse the raw materials and the seed, the mixture was transferred into a 50 ℃ oil bath pan, stirred and reacted for 24 hours, and after the reaction was completed, the mixture was centrifuged, washed 3 times with N, N-dimethylformamide and 3 times with ethanol, and after each washing, the product was centrifuged and separated, and after the completion, the product was transferred into an oven at 85 ℃ to stand for 6 hours, so as to obtain seed MOF-808 for low-energy synthesis, wherein the obtained MOF-808 was a pure-phase crystal and was white powder, and the yield was 40.7%.
PXRD characterization is carried out on the gram-scale synthetic MOF-808 obtained in the step (2), the characterization result is shown in figure 22, figure 22 is a PXRD spectrum of the gram-scale synthetic MOF-808, and as can be seen from figure 22, the gram-scale synthetic MOF-808 still has excellent crystallinity.
The gram-scale synthesized MOF-808 obtained in the step (2) is subjected to BET characterization, the characterization result is shown in FIG. 23, FIG. 23 is a BET spectrum of the gram-scale synthesized MOF-808 and a small-scale seed crystal method low-energy synthesized MOF-808, and as can be seen from FIG. 23, MOFs-808 in different production scales have similar adsorption characteristics, which indicates that the gram-scale synthesized MOF-808 maintains excellent adsorption performance and porous structure.
Example 6: the application of Zr-MOFs synthesized by seed crystal mediated low energy as Lewis acid provides a synthetic method of 1-iodine-2-methoxynaphthalene
(1) Application of Zr-MOFs as Lewis acid in synthesis reaction of 1-iodo-2-methoxynaphthalene
To 3mL of acetonitrile were added 15.8mg2-methoxynaphthalene, 24.7 mgN-iodosuccinimide, and 10mg of seed UiO-66 prepared in example 1, seed MOF-808 prepared in example 2, or MOF-808 prepared in example 2, and the mixture was placed in a 10mL round-bottomed flask, sufficiently dissolved by sonication for 1min, and N was used 2 Backfilling 5 times, wrapping the flask with tinfoil paper to block light. The round bottom flask is put in an oil bath kettle at the temperature of 30 ℃, the stirring speed is set to be 500rpm, and after 24 hours of reaction, the 1-iodine-2-methoxynaphthalene is obtained. The reaction formula is shown below, and the conversion of the reaction is shown in table 1.
TABLE 1
| Catalyst and process for preparing same | Yield (%) |
| UiO-66 seed | 2.0 |
| UiO-66 | 98.5 |
| MOF-808 seed | 5.1 |
| MOF-808 | 92.5 |
As can be seen from Table 1 and FIG. 24, when the seed crystal UiO-66 or seed crystal MOF-808 synthesized by the solvothermal method is used for catalysis, the reaction yield is low, and when the seed crystal-mediated low-energy synthesis UiO-66 or seed crystal MOF-808 is used for catalysis, the reaction yield is very high, which indicates that the Zr-MOFs synthesized by the seed crystal-mediated low-energy method has strong Lewis acid catalytic activity and can be used for catalyzing the synthesis reaction of 1-iodo-2-methoxynaphthalene.
(2) Recyclable reusability of seed-mediated low energy synthesized MOF-808
And (2) after the reaction in the step (1) is finished, centrifugally recovering the precipitate at the bottom of the flask, washing twice with acetonitrile, washing twice with acetone, and drying to obtain the recovered MOF-808.
Adding 15.8mg2-methoxynaphthalene and 24.7 mgN-iodosuccinimide into 3mL acetonitrile, adding recovered MOF-808, placing in a 10mL round bottom flask, ultrasonic treating for 1min for full dissolution, and dissolving with N 2 Backfilling 5 times, wrapping the flask with tinfoil paper to shield the flask from light. The round bottom flask was transferred to a 30 ℃ oil bath with a stirring rate set at 500rpm and reacted for 24h to give 1-iodo-2-methoxynaphthalene.
As shown in FIG. 25, FIG. 25 shows that three cycles of cycle experiments are carried out on the seed crystal-mediated low-energy synthesized MOF-808, and the synthesis reaction of 1-iodo-2-methoxynaphthalene still has stable conversion rate, which indicates that the synthesized MOF-808 has excellent recycling performance.
Example 7: the application of Zr-MOFs synthesized by seed crystal mediated low energy as a catalyst for Meerwein-Ponndorf reduction reaction provides a method for synthesizing cyclohexanol
Adding 21 mu L of cyclohexanone into 1mL of isopropanol, adding 10mg of seed MOF-808 or MOF-808 prepared in example 2, placing the solution in a 10mL round-bottom flask, carrying out ultrasonic dissolution for 1min, placing the round-bottom flask in an oil bath kettle at 80 ℃, setting the stirring speed to be 500rpm, and reacting for 1-3 h. Under the catalysis of seed crystal MOF-808, the conversion rate of cyclohexanone after 3h is 94.3%, under the catalysis of seed crystal mediated low energy synthesis MOF-808, cyclohexanone after 1h is completely converted, the reaction formula is as follows, the dynamics test is shown in figure 26, and the result shows that the Zr-MOFs synthesized by the method can improve the conversion efficiency of Meerwein-Ponndorf reduction reaction.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. The method for synthesizing the zirconium-based metal organic framework material is characterized in that zirconium salt, a ligand and a seed crystal are reacted to obtain the zirconium-based metal organic framework material.
2. A synthesis method according to claim 1, characterized in that the seeds are selected from UiO-66, MOF-808, uiO-66-NH 2 Or DUT-67.
3. The synthesis method according to claim 1, characterized in that the zirconium salt is selected from zirconium chloride or zirconium oxychloride.
4. The method of claim 1, wherein the ligand is selected from the group consisting of terephthalic acid, trimesic acid, 2-aminoterephthalic acid, and 2, 5-thiophenedicarboxylic acid.
5. The synthesis method according to claim 1, wherein the reaction temperature is 30-70 ℃ and the reaction time is 12-24 h.
6. A zirconium-based metal organic framework material obtainable by a synthesis process according to any one of claims 1 to 5.
7. Use of a zirconium-based metal organic framework material according to claim 6 as a Lewis acid.
8. A method for synthesizing 2-methoxy naphthalene derivatives, which is characterized in that 2-methoxy naphthalene reacts with a halogenating agent under the action of the zirconium-based metal organic framework material as claimed in claim 6 to obtain the 2-methoxy naphthalene derivatives.
9. Use of a zirconium-based metal organic framework material according to claim 6 as catalyst for a Meerwein-Ponndorf reduction reaction.
10. A process for the synthesis of cyclohexanol, wherein cyclohexanone is reacted under the action of a zirconium-based metal organic framework material according to claim 6, to obtain cyclohexanol.
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| CN114887502A (en) * | 2022-03-24 | 2022-08-12 | 大连理工大学 | Method for preparing Zr-MOF molecular sieve membrane by using zirconium cluster as metal source under mild reaction condition |
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