CN114790296A - Preparation method of hollow metal organic framework material - Google Patents
Preparation method of hollow metal organic framework material Download PDFInfo
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- CN114790296A CN114790296A CN202210269948.1A CN202210269948A CN114790296A CN 114790296 A CN114790296 A CN 114790296A CN 202210269948 A CN202210269948 A CN 202210269948A CN 114790296 A CN114790296 A CN 114790296A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention discloses a preparation method of a hollow metal organic framework material, which comprises the following steps: (1) respectively adding metal and an organic ligand into an organic solvent for dissolving, mixing, stirring for reaction, centrifuging, washing and drying to obtain a metal-organic framework material precursor; (2) and carrying out ultrasonic dispersion on the metal-organic framework material precursor, adding a polymer monomer and an initiator to carry out polymerization reaction, carrying out surface protection and internal etching on the metal-organic framework material, and carrying out secondary centrifugation, secondary washing and secondary drying to obtain the hollow metal-organic framework material. The metal organic framework material has a closed hollow structure and a crystal shell, and can obviously enhance the drug delivery and electrocatalysis performance of the metal organic framework material.
Description
Technical Field
The invention belongs to the technical field of new material chemistry, and particularly relates to a preparation method of a hollow metal organic framework material.
Background
The metal-organic framework material is a novel organic-inorganic hybrid crystalline porous material formed by self-assembling organic ligands and metal ions through coordination bonds, has the advantages of large specific surface area, adjustable pore diameter, tailorable structure and the like, and is widely applied to the fields of gas storage, gas separation, catalysis, sensing, drug delivery, electrochemical energy conversion and the like. Particularly, the metal-organic framework material can be used as a micro-reactor and an adsorption carrier of biomolecules or enzyme molecules, and has wide application prospects in enzyme catalysis and drug delivery.
Most of the metal-organic framework materials are of a microporous structure, so that the transportation of macromolecules in the metal-organic framework materials and the accessibility of active sites of the macromolecules are hindered, and the metal-organic framework materials have certain limitations in aspects of drug delivery, catalysis and the like. The hollow metal-organic framework material is a shell-core structure with high specific surface area, low density and hollow interior, and can solve the problem of molecule transportation in the metal-organic framework material. However, the traditional hollow metal-organic framework material is mainly synthesized by epitaxial growth method, template method or two-phase interface induction method, and the like, and has the disadvantages of complex operation, difficult shape control and easy mixture formation, and can only be used for a special metal-organic framework material, and the universality is not high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a hollow metal-organic framework material and a preparation method thereof. Different from the conventional metal-organic framework material, the metal-organic framework material has a closed hollow structure and a crystal shell, and can obviously enhance the drug delivery and electrocatalysis performance of the metal-organic framework material.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a hollow metal organic framework material comprises the following steps:
(1) respectively adding metal and an organic ligand into an organic solvent for dissolving, mixing and stirring the two solutions for reaction, centrifuging, washing and drying to obtain a metal-organic framework material precursor;
(2) and carrying out ultrasonic dispersion on the metal-organic framework material precursor, adding a polymer monomer and an initiator to carry out polymerization reaction, carrying out surface protection and internal etching on the metal-organic framework material, and carrying out secondary centrifugation, secondary washing and secondary drying to obtain the hollow metal-organic framework material.
Preferably, the metal in step (1) is transition metal zinc (Zn) 2+ ) Ionic, metallic cobalt (Co) 2+ ) Ions and metallic iron ions (Fe) 3+ ) (ii) a Preferably, the metal ion compound is a soluble inorganic salt of a transition metal ion, and further preferably a nitrate and a chloride.
Preferably, the organic ligand is a nitrogen heterocyclic ligand and a carboxylic acid ligand, and the nitrogen heterocyclic ligand is 2-methylimidazole.
Preferably, the organic solvent is N, N-Dimethylformamide (DMF), methanol (MeOH) and ethanol (EtOH).
Preferably, the polymer monomer in step (2) is an organic small molecule capable of forming a high molecular polymer through polymerization, including but not limited to pyrrole, aniline, and dopamine.
Preferably, the initiator in step (2) is a compound for polymerizing the organic small molecules, including but not limited to ammonium persulfate, ferric chloride, and benzoyl peroxide.
Preferably, the reaction time in step (2) is 10 hours, including a low temperature reaction time and a room temperature reaction time, wherein the low temperature reaction time is 2 hours, and the room temperature reaction time is 8 hours.
Preferably, the molar ratio of the metal-organic framework material to ammonium persulfate is 4.6: 1,2.1: 1.
preferably, the washing agent used in the step (1) (2) is methanol, ethanol, acetonitrile, dichloromethane, acetone, DMF, tetrahydrofuran, etc.
Preferably, the second drying method in step (2) is freeze drying, vacuum drying, or the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the transmission rate of the guest molecules in the metal-organic framework material is improved, and the method has important significance for improving the performances of the metal-organic framework material in aspects of drug delivery, electrocatalysis and the like. 2. The formation of high molecular polymer monomer polypyrrole has important influence on the synthesis of the hollow metal organic framework material. The polymerization protection on the surface of the metal-organic framework material can protect the surface shell of the metal-organic framework material from being corroded by an etchant, and meanwhile, the initiator with the etching effect selectively etches the interior of the metal-organic framework material, so that the metal-organic framework material with a hollow structure is obtained, and the application field of the metal-organic framework material is expanded. 3. The metal-organic framework material is taken as a precursor, and the polymer and the oxidant are simply added, so that the collapse of the framework of the metal-organic framework material caused by elimination by a template method is avoided, and the method also reduces the operation steps. 4. The method is suitable for various MOF materials, and is simple to operate and good in controllability; different metal-organic framework materials with hollow structures can be conveniently prepared, and certain universality is achieved. The properties of the metal-organic framework material can be improved. No need of adding organic ligand, low cost.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of a hollow metal organic framework prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope photograph of a hollow metal organic framework prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope photograph of a hollow metal organic framework prepared in example 2 of the present invention;
FIG. 4 is a TEM image of the hollow MOF prepared in example 3 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
The principle of the invention is as follows: the compound as the initiator has the function of initiating polymerization reaction on polymer monomers in the reaction process, and has the function of selectively etching the metal-organic framework material. In addition, the organic polymer is gathered on the surface of the metal-organic framework material, and the surface of the metal-organic framework material is protected and is not easy to be affected by the etchant. The polymer has the functions of surface protection and internal etching of the metal-organic framework material, so that the metal-organic framework is selectively etched, and the hollow metal-organic framework material is formed.
As shown in fig. 1-3, a hollow metal organic framework material comprises an organic ligand and a transition metal ion as reactants, which are self-assembled; after reacting for a certain time, obtaining a precursor of the metal-organic framework material, adding an initiator and a high molecular polymer monomer after the precursor metal-organic framework material is synthesized, reacting at a certain temperature, and carrying out surface protection and selective internal etching on the metal-organic framework material by utilizing polymerization reaction to obtain the hollow metal-organic framework material.
Preferably, the high molecular polymer is a high molecular polymer polymerized in a solution, and includes polypyrrole, polyaniline, polydopamine and the like.
And carrying out surface protection and internal etching on the metal-organic framework material by using polymerization reaction, and carrying out partial etching to obtain the metal-organic framework material. Organic polymer induced etching method: firstly synthesizing MOF materials, then adding organic polymer monomers and an initiator, and polymerizing organic polymers on the surfaces of the MOF materials to generate organic high molecular polymer layers on the MOF surfaces. Simultaneously, the initiator etches the interior of the MOF material to produce a cavity, resulting in a hollow MOF material.
The preparation method of the hollow metal organic framework material comprises the following steps:
(1) respectively adding metal and an organic ligand into an organic solvent for dissolving, mixing and stirring the two solutions for reaction, centrifuging, washing and drying to obtain a metal-organic framework material precursor; the stirring reaction time is 24 hours; the drying temperature is 60-120 ℃.
Preferably, the metal is a transition metal zinc (Zn) 2+ ) Ionic, metallic cobalt (Co) 2+ ) Ions and metallic iron ions (Fe) 3 + ) (ii) a Preferably, the metal ion compound is a soluble inorganic salt of a transition metal ion, and further preferably a nitrate or chloride.
The organic ligand is a nitrogen heterocyclic ligand and a carboxylic acid ligand, and the nitrogen heterocyclic ligand: 2-methylimidazole.
The organic solvent is N, N-Dimethylformamide (DMF), methanol (MeOH) and ethanol (EtOH).
(2) And carrying out ultrasonic dispersion on the metal-organic framework material precursor, adding a polymer monomer and an initiator to carry out polymerization reaction, carrying out surface protection and internal etching on the metal-organic framework material, and carrying out secondary centrifugation, secondary washing and secondary drying to obtain the hollow metal-organic framework material. Preferably, the polymer monomer in step (2) is an organic small molecule which forms a high molecular polymer through polymerization, including but not limited to pyrrole, aniline and dopamine.
Preferably, the initiator in step (2) is a compound for polymerizing the organic small molecules, including but not limited to ammonium persulfate, ferric chloride, benzoyl peroxide and the like.
Preferably, the reaction time in step (2) is 10 hours, including a low-temperature reaction time and a room-temperature reaction time, wherein the low-temperature reaction time is 2 hours, and the room-temperature reaction time is 8 hours.
Preferably, the molar ratio of the metal-organic framework material to ammonium persulfate is 4.6: 1-2.1: 1.
preferably, the washing agent used in the step (1) (2) is methanol, ethanol, acetonitrile, dichloromethane, acetone, DMF, tetrahydrofuran, etc.
Preferably, the second drying method in step (2) is freeze drying or vacuum drying.
Example 1 a method for preparing a hollow metal organic framework material, (1) weighing 2.38 g of zinc nitrate hexahydrate, adding 36 ml of DMF, 12 ml of methanol and 12 ml of ethanol, stirring and dissolving to obtain a solution a. Weighing 4 g of 2-methylimidazole, adding 12 ml of DMF and 8 ml of methanol, and stirring to dissolve to obtain a solution B. And adding the solution B into the solution A, stirring and reacting for 24 hours at room temperature, centrifuging, washing with methanol, and drying at 80 ℃ to obtain the metal-organic framework material ZIF-8.
(2) 250 mg of ZIF-8 was weighed and dissolved in 10.68 ml of deionized water by sonication. Adding 45 microliter of pyrrole, stirring at the low temperature of 0 ℃ for 30 minutes, then dropwise adding 0.675 milliliter (80 mg/milliliter) of ammonium persulfate aqueous solution, continuously stirring at the low temperature of 0 ℃ for reaction for 2 hours, then stirring at the room temperature for reaction for 8 hours, centrifuging, washing with methanol, and freeze-drying to obtain the hollow ZIF-8 metal-organic framework material.
Example 2 a method for preparing a hollow metal organic framework material,
(1) 5.82 g of cobalt nitrate hexahydrate is weighed, 200mL of methanol is added, and the mixture is stirred and dissolved to obtain a solution A. 6.56 g of 2-methylimidazole is weighed and added with 200mL of methanol, and the mixture is stirred and dissolved to obtain a solution B. And adding the solution B into the solution A, performing ultrasonic treatment for 30min, standing at room temperature for 24h, centrifuging, washing with methanol, and drying at 80 ℃ to obtain the metal-organic framework material ZIF-67.
(2) 250 mg of ZIF-67 was weighed and dissolved in 16.5 ml of deionized water by sonication. Adding 100 microliters of pyrrole, stirring at the low temperature of 0 ℃ for 30 minutes, then dropwise adding 1.5 milliliters (with the concentration of 80 milligrams/milliliter) of ammonium persulfate, continuing to stir at the low temperature of 0 ℃ for reaction for 2 hours, then stirring at the room temperature for reaction for 8 hours, centrifuging, washing with methanol, and freeze-drying to obtain the hollow ZIF-67 metal-organic framework material.
Example 3 a method for preparing a hollow metal organic framework material, comprising the steps of
(1) Weighing 1.62 g of ferric chloride hexahydrate and 1 g of terephthalic acid, adding 30mL of DMF, uniformly stirring, transferring the mixed solution into a 100mL high-pressure hydrothermal kettle with a polytetrafluoroethylene lining, putting the kettle into an oven, reacting at 100 ℃ for 12 hours, centrifuging, washing with 50 mL of methanol, and drying at 80 ℃ to obtain the metal-organic framework material MIL-88-Fe.
(2) 250 mg of MIL-88-Fe was weighed and dissolved in 16.5 ml of deionized water by sonication. Adding 100 microliters of pyrrole, stirring at 0 ℃ for 30 minutes at low temperature, then dropwise adding 1.5 milliliters (with the concentration of 80 milligrams/milliliter) of ammonium persulfate, continuing to stir at 0 ℃ for 2 hours at low temperature, then stirring at room temperature for 8 hours, centrifuging, washing with methanol, and freeze-drying to obtain the hollow MIL-88-Fe metal-organic framework material.
Test examples:
1. as shown in FIG. 1, PXRD patterns of samples ZIF-8 and hollow ZIF-8 were tested using an X-ray Powder (PXRD) diffractometer. The result shows that the prepared hollow ZIF-8 keeps the crystal structure of the original ZIF-8 material, the crystal structure of the hollow ZIF-8 material is not changed, and no impurity phase exists.
2. As shown in fig. 2, a Transmission Electron Microscope (TEM) image of the hollow ZIF-8 material prepared in example 1 was tested. TEM image shows that the prepared hollow ZIF-8 material has a polyhedral structure, but the interior of the material is of a hollow structure. The method shows that the hollow metal organic framework material ZIF-8 is successfully prepared by the method.
3. A Transmission Electron Microscope (TEM) image of the hollow ZIF-67 material prepared in example 2 was tested as shown in fig. 3. TEM image shows that the prepared hollow ZIF-67 material has a polyhedral structure, but the interior of the material is a hollow structure. The method shows that the hollow metal organic framework material ZIF-67 is successfully prepared by the method.
4. TEM images of the hollow MIL-88-Fe material prepared in example 3 were tested using a Transmission Electron Microscope (TEM) as shown in FIG. 4.
It will be appreciated by those skilled in the art that the foregoing is merely exemplary of the present invention and is not intended to limit the invention, which is defined by the appended claims and any changes, substitutions or alterations that fall within the true spirit and scope of the invention.
Claims (9)
1. The preparation method of the hollow metal organic framework material is characterized by comprising the following steps:
(1) respectively adding metal and an organic ligand into an organic solvent for dissolving, mixing and stirring the two solutions for reaction, and then carrying out centrifugation, washing and drying treatment to obtain a metal-organic framework material precursor;
(2) and performing ultrasonic dispersion on the metal-organic framework material precursor, adding a polymer monomer and an initiator to perform polymerization reaction, performing surface protection and internal etching on the metal-organic framework material, and performing secondary centrifugation, secondary washing and secondary drying to obtain the hollow metal-organic framework material.
2. The method for preparing a hollow metal organic framework material according to claim 1, wherein the metal in step (1) is transition metal zinc ion, metal cobalt ion and metal iron ion.
3. The method for preparing the hollow metal organic framework material according to claim 1, wherein the organic ligand is a nitrogen heterocyclic ligand and a carboxylic acid ligand.
4. The method for preparing a hollow metal organic framework material according to claim 1, wherein the organic solvent is N, N-dimethylformamide, methanol and ethanol.
5. The method for preparing a hollow metal organic framework material according to claim 1, wherein the polymer monomer in step (2) is an organic small molecule which forms a high molecular polymer through polymerization reaction, and comprises pyrrole, aniline and dopamine.
6. The method for preparing a hollow metal organic framework material according to claim 1, wherein the initiator in the step (2) is a compound for polymerizing the organic small molecules, and comprises ammonium persulfate, ferric chloride and benzoyl peroxide.
7. The method for preparing a hollow metal-organic framework material according to claim 6, wherein the molar ratio of the metal-organic framework material to ammonium persulfate is 4.6: 1-2.1: 1.
8. the method of claim 1, wherein the detergent is methanol, ethanol, acetonitrile, dichloromethane, acetone, DMF, or tetrahydrofuran.
9. The method for preparing a hollow metal organic framework material according to claim 1, wherein the second drying in step (2) is freeze drying or vacuum drying.
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| CN115212856A (en) * | 2022-08-29 | 2022-10-21 | 中国科学院兰州化学物理研究所 | Preparation and application of surface polymer functionalized spherical metal organic framework material |
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