CN112705129B - Metal organic framework composite aerogel material and preparation method thereof - Google Patents

Metal organic framework composite aerogel material and preparation method thereof Download PDF

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CN112705129B
CN112705129B CN202011248836.5A CN202011248836A CN112705129B CN 112705129 B CN112705129 B CN 112705129B CN 202011248836 A CN202011248836 A CN 202011248836A CN 112705129 B CN112705129 B CN 112705129B
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metal
organic framework
organic
composite aerogel
fiber
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CN112705129A (en
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仇若翔
赵园
魏欢怡
段承杰
林继铭
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China General Nuclear Power Corp
China Nuclear Power Technology Research Institute Co Ltd
CGN Power Co Ltd
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China General Nuclear Power Corp
China Nuclear Power Technology Research Institute Co Ltd
CGN Power Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention relates to a metal organic framework composite aerogel material and a preparation method and application thereof. The metal organic framework composite aerogel material comprises an organic fiber material and a metal organic framework material, wherein the organic fiber material with carboxyl groups is connected with the metal organic framework material through a metal coordination bond formed by the carboxyl groups, and the metal organic framework material grows and extends in situ on the surface of the organic fiber material with the carboxyl groups to form a mesoporous structure. The organic fiber material is used as a matrix, and the problem that the traditional inorganic material is insufficient in toughness is solved. The metal organic framework material with a mesoporous structure is formed on the surface of the fiber, so that the heat resistance of the aerogel material is improved. The organic fiber material and the metal organic framework material are connected with each other through the coordination of carboxyl and a metal center, so that the organic fiber material and the metal organic framework material are tightly combined, the combination degree is far higher than that of a conventional physically combined composite aerogel material, and the problems of powder falling, frangibility and the like are not easy to occur.

Description

Metal organic framework composite aerogel material and preparation method thereof
Technical Field
The invention relates to the field of functional materials, in particular to a metal organic framework composite aerogel material and a preparation method thereof.
Background
Nuclear power plants generally use silicic acid-based fiber materials as insulating materials. In recent years, the use of inorganic aerogel as a material for insulation layers has been proposed. Specifically, aerogel is a solid substance with the lowest density in the world, and has very good heat insulation effect because more than 80% of the aerogel is air. The inorganic aerogel is a material with a nano-scale porous structure formed by mutually aggregating nano particles, and the high porosity of the inorganic aerogel reduces the heat conduction of a solid phase material, so that the inorganic aerogel can be used as a heat insulation layer material.
The silica aerogel material is an inorganic aerogel material which is researched more at present, but the brittleness of pure silica aerogel is larger, and the mechanical property is relatively poorer, so that the silica aerogel fiber composite material is developed. The silica aerogel fiber composite material has the advantages of low heat conductivity coefficient, good mechanical property and the like, but the phenomenon of powder falling of the silica aerogel fiber composite material is easily caused because the aerogel can not be in full contact with and combined with fibers.
Disclosure of Invention
Based on the above, it is necessary to provide a metal organic framework composite aerogel material with tightly combined components and good high temperature resistance, and a preparation method and an application thereof.
The invention provides a metal organic framework composite aerogel material, which comprises a metal organic framework material and an organic fiber material with a carboxyl group, wherein the organic fiber material with the carboxyl group is connected with the metal organic framework material through a metal coordination bond formed by the carboxyl group, and the metal organic framework material grows and extends in situ on the surface of the organic fiber material with the carboxyl group to form a mesoporous structure.
In some of these embodiments, the mesoporous structure has a pore size of 20nm to 50 nm.
In some of these embodiments, the organic fibrous material having carboxyl groups is a carboxyl-modified wood fiber.
In some of these embodiments, the organic fibrous material having carboxyl groups has a diameter of 30nm to 100 nm.
In some of these embodiments, the metal-organic framework material is selected from one of an aluminum-based metal-organic framework material and an iron-based metal-organic framework material.
In some of these embodiments, the organic fiber material having carboxyl groups is a carboxyl-modified wood fiber, and the metal-organic framework material is an aluminum-based metal-organic framework material.
In some of these embodiments, the organic fibrous material having carboxyl groups is carbonized to inorganic fibers.
The metal organic framework composite aerogel material comprises an organic fiber material and a metal organic framework material, wherein the organic fiber material is connected with the metal organic framework material through carboxyl. The organic fiber material is adopted as the matrix, so that the problem of insufficient forming toughness of the traditional inorganic material is solved. The metal organic framework material forms a mesoporous structure on the surface of the organic fiber, the hollow mesoporous structure effectively improves the overall heat resistance of the aerogel material, and the integrity of the material can be ensured even if the aerogel material bears high temperature of more than 350 ℃. The organic fiber and the metal organic framework material are connected through coordination of carboxyl and a metal center, and the organic fiber and the metal organic framework material are tightly combined in a chemical bonding mode, and the combination degree of the organic fiber and the metal organic framework material is far greater than that of a composite aerogel material combined in a conventional physical mode, so that the problems of powder falling, frangibility and the like are not easy to occur.
Because the organic fiber material is not resistant to high temperature, the organic fiber of the metal organic framework composite aerogel material is carbonized into inorganic fiber through annealing treatment, so that the metal organic framework composite aerogel material can keep the integrity of the material form at the high temperature of 1300 ℃, and can meet the heat insulation requirement at higher temperature.
The invention also provides a preparation method of the metal organic framework composite aerogel material, which is characterized by comprising the following steps:
modifying the organic fiber material with carboxyl groups;
growing a metal organic framework material on the organic fiber material with the carboxyl group in situ to obtain an organic fiber-metal organic framework material intermediate, wherein the organic fiber material with the carboxyl group forms a metal coordination bond with the metal organic framework material through the carboxyl group;
and growing a metal organic framework material on the organic fiber-metal organic framework material intermediate in situ, and extending the organic metal organic framework material to form a mesoporous structure.
In some of these embodiments, the agent used to modify the carboxyl groups of the organic fibrous material is an oxidizing agent.
In some of these embodiments, the step of growing a metal-organic framework material in situ on the organic fibrous material having carboxyl groups comprises:
and mixing the organic fiber material with the carboxyl group, soluble metal salt and an organic ligand, and reacting for 1-3 h at room temperature.
In some embodiments, the step of growing a metal organic framework material in situ on the organic fiber-metal organic framework material intermediate comprises:
and mixing the organic fiber-metal organic framework material intermediate with soluble metal salt and an organic ligand, and reacting for 6-12 hours at room temperature.
In some of these embodiments, the soluble metal salt is selected from at least one of a metal chloride salt and a metal nitrate salt.
In some of these embodiments, the organic ligand is selected from at least one of terephthalic acid, sodium terephthalate, amino-substituted terephthalic acid, amino-substituted sodium terephthalate, trimesic acid, and sodium trimesate.
In some embodiments, annealing the metal-organic framework composite aerogel material to carbonize the organic fiber material in the metal-organic framework composite aerogel material.
According to the preparation method of the metal organic framework composite aerogel material, the organic fiber material is modified with carboxyl groups, so that the carboxyl groups can be coordinated with the metal center of the metal organic framework material, an organic fiber-metal organic framework material intermediate is generated in situ on the organic fiber with carboxyl groups, and then the metal organic framework material is continuously grown and extended to form a mesoporous structure. The organic fiber is combined with the metal organic material through a stable coordination bond, so that the prepared metal organic framework composite aerogel material is tightly combined and has good material integrity. The metal organic framework material is formed on the surface of the organic fiber in an in-situ growth and extension mode, the integrity of the metal organic framework composite aerogel material is further improved, the prepared metal organic framework composite aerogel material has few mesoporous structure defects, and the prepared metal organic framework composite aerogel material has good heat insulation and mechanical properties.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a metal organic framework composite aerogel material, which comprises a metal organic framework material and an organic fiber material with a carboxyl group, wherein the organic fiber material with the carboxyl group is connected with the metal organic framework material through a metal coordination bond formed by the carboxyl group, and the metal organic framework material grows and extends in situ on the surface of the organic fiber material with the carboxyl group to form a mesoporous structure.
In some of these embodiments, the mesoporous structure has a pore size of 20nm to 50 nm.
In some of these embodiments, the organic fibrous material having carboxyl groups is a carboxyl-modified wood fiber. The wood fiber has a two-dimensional fiber structure, has high strength and toughness, and is beneficial to improving the mechanical property of the metal organic framework composite aerosol material.
In some of these embodiments, the organic fibrous material having carboxyl groups has a diameter of 30nm to 100 nm.
In some of these embodiments, the metal-organic framework material is selected from one of an aluminum-based metal-organic framework material and an iron-based metal-organic framework material.
In some of these embodiments, the organic fiber material having carboxyl groups is a carboxyl-modified wood fiber and the metal-organic framework material is an aluminum-based metal-organic framework material.
In some of these embodiments, the metal organic framework material is an aluminum-based metal organic framework material. Preferably, the metal organic framework material is an Al-MIL-53 material.
In some of these embodiments, the organic fibrous material having carboxyl groups is carbonized into inorganic fibers.
The metal organic framework composite aerogel material comprises an organic fiber material and a metal organic framework material, wherein the organic fiber material is connected with the metal organic framework material through carboxyl. The organic fiber material is adopted as the matrix, so that the problem of insufficient forming toughness of the traditional inorganic material is solved. The metal organic framework material forms a mesoporous structure on the surface of the organic fiber, the hollow mesoporous structure effectively improves the overall heat resistance of the aerogel material, and the integrity of the material can be ensured even if the aerogel material bears high temperature of more than 350 ℃. The organic fiber and the metal organic framework material are connected through coordination of carboxyl and a metal center, and the organic fiber and the metal organic framework material are tightly combined in a chemical bonding mode, and the combination degree of the organic fiber and the metal organic framework material is far greater than that of a composite aerogel material combined in a conventional physical mode, so that the problems of powder falling, frangibility and the like are not easy to occur.
Because the organic fiber material is not resistant to high temperature, the organic fiber of the metal organic framework composite aerogel material is carbonized into inorganic fiber through annealing treatment, so that the metal organic framework composite aerogel material can keep the integrity of the material form at the high temperature of 1300 ℃, and can meet the heat insulation requirement at higher temperature.
The invention also provides a preparation method of the metal-organic framework composite aerogel material, which is characterized by comprising the following steps of S1-S3.
Step S1: modifying the organic fiber material with carboxyl groups;
step S2: growing a metal organic framework material on an organic fiber material with a carboxyl group in situ to obtain an organic fiber-metal organic framework material intermediate, wherein the organic fiber material with the carboxyl group is connected with the metal organic framework material through a metal coordination bond formed by the carboxyl group;
step S3: and growing the metal organic framework material on the organic fiber-metal organic framework material intermediate in situ to extend the organic metal framework material to form a mesoporous structure.
In some of these embodiments, the agent used to modify the carboxyl groups of the organic fibrous material is an oxidizing agent.
In some of these embodiments, the step of growing the metal-organic framework material in situ on the organic fibrous material having carboxyl groups comprises:
mixing an organic fiber material with carboxyl groups, soluble metal salt and an organic ligand, and reacting for 1-3 hours at room temperature.
In some of these embodiments, the step of growing the metal organic framework material in situ on the organic fiber-metal organic framework material intermediate comprises:
and mixing the organic fiber-metal organic framework material intermediate with soluble metal salt and organic ligand, and reacting for 6-12 h at room temperature.
Specifically, room temperature as used herein means a temperature of 25 ℃. + -. 5 ℃.
In some of these embodiments, the soluble metal salt is selected from at least one of a metal chloride salt and a metal nitrate salt.
In some of these embodiments, the organic ligand is selected from at least one of terephthalic acid, sodium terephthalate, amino-substituted terephthalic acid, amino-substituted sodium terephthalate, trimesic acid, and sodium trimesate.
Specifically, the preparation method of the metal organic framework composite aerogel material comprises the following steps:
in step S1, the surface of the wood fiber is oxidized with an oxidizing agent to modify carboxyl groups.
In step S2, the organic fibrous material having carboxyl groups is mixed with a soluble aluminum salt and an organic ligand for reaction. The organic ligand is at least one selected from terephthalic acid, sodium terephthalate, amino-substituted terephthalic acid, amino-substituted sodium terephthalate, trimesic acid and sodium trimesate. Specifically, the molar ratio of the soluble aluminum salt to the organic ligand is (1-3): 1. The molar ratio of soluble aluminum salt to organic ligand can be determined based on the structure of the target metal organic framework material being prepared.
In step S3, the molar ratio of soluble aluminum salt to organic ligand is consistent with step S2.
In some embodiments, annealing the metal-organic framework composite aerogel material to carbonize the organic fiber material in the metal-organic framework composite aerogel material.
According to the preparation method of the metal organic framework composite aerogel material, the organic fiber material is modified with carboxyl groups, so that the carboxyl groups can be coordinated with the metal center of the metal organic framework material, an organic fiber-metal organic framework material intermediate is generated in situ on the organic fiber with carboxyl groups, and then the metal organic framework material is continuously grown and extended to form a mesoporous structure. The organic fiber is combined with the metal organic material through a stable coordination bond, so that the prepared metal organic framework composite aerogel material is tightly combined and has good material integrity. The metal organic framework material is formed on the surface of the organic fiber in an in-situ growth and extension mode, the integrity of the metal organic framework composite aerogel material is further improved, the prepared metal organic framework composite aerogel material has few mesoporous structure defects, and the prepared metal organic framework composite aerogel material has good heat insulation and mechanical properties.
The invention also provides application of the metal organic framework composite aerogel material in preparation of a heat insulation material.
The preparation method of the metal organic framework composite aerogel material of the present invention is further described in detail with reference to the following specific examples.
The following examples are mainly made for the metal-organic framework material being Al-MIL-53 material, and it is understood that in other embodiments, the preparation method of the metal-organic framework composite aerogel material of the present invention is not limited to the case of only using Al-MIL-53 material as the metal-organic framework material, and can be other metal-organic framework materials. Example 1
The method comprises the following steps: 10g of wood fibre powder were dispersedly stirred in an aqueous NaOH solution (2 wt%) at room temperature at 300rpm for 72 hours. The solution was filtered through a PVDF membrane filter (pore size: 0.1 μm) and washed several times with deionized water. The washed wood fibres are then collected. 500mL of the fiber suspension had a concentration of 2mg/mL with ultrasonic agitation for 10 minutes. 10mL of tetramethylpiperidine (mg/mL) and 150mg of sodium bromide were added to 500mL of the fiber suspension with stirring at 800 rpm. Surface oxidation was then started by the addition of 0.7mL (1.5mmol) of 13% NaClO solution. During the oxidation, the pH of the mixture was adjusted and maintained at 10.5 by dropwise addition of 0.5M NaOH aqueous solution. After 2 hours of reaction, 30mL of ethanol was added to cool the reaction.
Step two: the modified wood fiber is thoroughly filtered and washed by deionized water, and 10mL of Al (NO) is added 3 ) 3 ·9H 2 O (2mmol) and 50mL (73% wt) of an aqueous solution of PVP were stirred at 500 rpm. 10mL of sodium terephthalate (1mmol) solution was then added titrated over 5 minutes and the mixture stirred at 500rpm/min for 2 hours at room temperature, followed by lyophilization to afford the lignocellulosic-Al-MIL-53 intermediate.
Step three: immersing the dried wood fiber-Al-MIL-53 intermediate into sodium terephthalate solution (2mmol), and dropwise adding Al (NO) 3 ) 3 ·9H 2 O (4mmol) solution. The mixture was gently shaken for 10 hours to prolong the growth of Al-MIL-53. And washing the treated aerogel with deionized water for 5 times, and then freeze-drying to obtain the metal-organic framework composite aerogel material.
Example 2
The method comprises the following steps: 10g of wood fibre powder were dispersedly stirred in an aqueous NaOH solution (8 wt%) at room temperature at 500rpm for 48 hours. The solution was filtered through a PVDF membrane filter (pore size: 0.1 μm) and washed several times with deionized water. The washed wood fibres are then collected. 500mL of the fiber suspension with a concentration of 2mg/mL was sonicated for 10 minutes. 10mL of tetramethylpiperidine (mg/mL) and 150mg of sodium bromide were added to 500mL of the fiber suspension with stirring at 800 rpm. Surface oxidation was then started by the addition of 0.7mL (1.5mmol) of 13% NaClO solution. During the oxidation, the pH of the mixture was adjusted and maintained at 10.5 by dropwise addition of 0.5M NaOH aqueous solution. After 2 hours of reaction, 30mL of ethanol was added to cool the reaction.
Step two: the modified wood fiber is thoroughly filtered and washed by deionized water, and 10mL of Al (NO) is added 3 ) 3 ·9H 2 O (2.5mmol) and 50mL (73% wt) of aqueous PVP solution were stirred at 500 rpm. 10mL of sodium terephthalate (1mmol) solution was then added titrated over 5 minutes and the mixture stirred at 500rpm/min for 2 hours at room temperature, followed by lyophilization to afford the lignocellulosic-Al-MIL-53 intermediate.
Step three: immersing the dried wood fiber-Al-MIL-53 intermediate into sodium terephthalate solution (2mmol), and dropwise adding Al (NO) 3 ) 3 ·9H 2 O (5mmol) solution. The mixture was gently shaken for 10 hours to prolong the growth of Al-MIL-53. And washing the treated aerogel with deionized water for 5 times, and then freeze-drying to obtain the metal-organic framework composite aerogel material.
Example 3
Steps one to three are the same as in embodiment 1, except that step four is further included.
Step four: and (4) heating the metal organic frame composite material obtained in the step three to 600 ℃, and preserving heat for 4h to finish annealing treatment, thereby obtaining the metal organic frame aerogel composite material carbonized by organic fibers.
Comparative example 1
The second step and the third step are the same as in example 1, except that the treatment of modifying carboxyl groups with wood fibers in the second step and the treatment of the third step are performed using wood fibers without modification of carboxyl groups.
Comparative example 2
The first step and the second step are the same as the embodiment 1, except that the third step of in-situ growing the extended metal organic framework material is omitted.
Comparative example 3
The method comprises the following steps: 10g of wood fibre powder were dispersedly stirred in an aqueous NaOH solution (2 wt%) at room temperature at 300rpm for 72 hours. The solution was filtered through a PVDF membrane filter (pore size: 0.1 μm) and washed several times with deionized water. The washed wood fibres are then collected. 500mL of the fiber suspension with a concentration of 2mg/mL was sonicated for 10 minutes. 10mL of tetramethylpiperidine (mg/mL) and 150mg of sodium bromide were added to 500mL of the fiber suspension with stirring at 800 rpm. Surface oxidation was then started by the addition of 0.7mL (1.5mmol) of 13% NaClO solution. During the oxidation, the pH of the mixture was adjusted and maintained at 10.5 by dropwise addition of 0.5M NaOH aqueous solution. After 2 hours of reaction, 30mL of ethanol was added to cool the reaction.
Step two: and thoroughly filtering and washing the modified wood fiber by using deionized water, adding 20mL of Al-MIL-53 solution prepared in advance, mixing (Al is 4mmol), stirring the mixture at the room temperature at the rotating speed of 500rpm/min for 2 hours, and then freeze-drying to obtain the metal organic framework aerogel composite material.
The metal organic framework aerogel composite material prepared in the embodiments 1 to 3 has a metal organic framework aerogel material forming a mesoporous structure, and has good heat resistance. The metal organic framework aerogel composite material has a stable structure, and is not easy to collapse and fall off during use.
In the metal organic framework aerogel composite material formed in the comparative example 1, the metal organic framework material is not fixed on the fibers by chemical bonds, and the acting force between the metal organic framework material and the fibers is weak, so that the metal organic framework material is easy to collapse into powder crystal particles, and the heat resistance is greatly reduced.
Comparative example 2 the metal organic framework material was grown in situ on the carboxyl-modified wood fiber in one step, resulting in more crystal grains, not favorable for forming a mesoporous structure with a pore diameter of 20-50nm, inferior in heat insulation performance compared to example 1, and difficult to form a stable block structure for application in heat insulation materials.
Comparative example 3 the metal organic framework material prepared in advance was mixed with the wood fiber modified with carboxyl, and during the mixing process, the original metal organic framework structure was easily damaged, and the re-compounded metal organic framework material had increased defects, non-uniform mesoporous size, and poor stability as the metal organic framework composite aerosol material of example 1.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (14)

1. The metal-organic framework composite aerogel material is characterized by comprising a metal-organic framework material and an organic fiber material with a carboxyl group, wherein the organic fiber material with the carboxyl group is connected with the metal-organic framework material through a metal coordination bond formed by the carboxyl group, and the metal-organic framework material grows and extends in situ on the surface of the organic fiber material with the carboxyl group to form a mesoporous structure;
the preparation method of the metal-organic framework composite aerogel material comprises the following steps:
modifying carboxyl groups on an organic fiber material to prepare the organic fiber material with the carboxyl groups;
growing a metal organic framework material on the organic fiber material with the carboxyl group in situ to obtain an organic fiber-metal organic framework material intermediate, wherein the organic fiber material with the carboxyl group forms a metal coordination bond with the metal organic framework material through the carboxyl group;
and growing a metal organic framework material on the organic fiber-metal organic framework material intermediate in situ, and extending the organic metal organic framework material to form a mesoporous structure.
2. The metal-organic framework composite aerogel material of claim 1, wherein the pore size of the mesoporous structure is 20nm to 50 nm.
3. The metal-organic framework composite aerogel material of claim 1, wherein the organic fibrous material having carboxyl groups is a carboxyl-modified wood fiber.
4. The metal-organic framework composite aerogel material of claim 1, wherein the organic fiber material having carboxyl groups has a diameter of 30nm to 100 nm.
5. The metal-organic framework composite aerogel material of claim 1, wherein the metal-organic framework material is selected from one of an aluminum-based metal-organic framework material and an iron-based metal-organic framework material.
6. The metal-organic framework composite aerogel material of claim 1, wherein the organic fiber material having carboxyl groups is a carboxyl-modified wood fiber, and the metal-organic framework material is an aluminum-based metal-organic framework material.
7. The metal-organic framework composite aerogel material of any of claims 1 to 6, wherein the organic fiber material having carboxyl groups is carbonized into inorganic fibers.
8. The preparation method of the metal-organic framework composite aerogel material is characterized by comprising the following steps of:
modifying the organic fiber material with carboxyl groups;
growing a metal organic framework material on an organic fiber material with a carboxyl group in situ to obtain an organic fiber-metal organic framework material intermediate, wherein the organic fiber material with the carboxyl group is connected with the metal organic framework material through a metal coordination bond formed by the carboxyl group;
and growing a metal organic framework material on the organic fiber-metal organic framework material intermediate in situ, and extending the organic metal organic framework material to form a mesoporous structure.
9. The method for preparing the metal-organic framework composite aerogel material according to claim 8, wherein the agent used for modifying carboxyl groups with the organic fiber material is an oxidizing agent.
10. The method of preparing a metal organic framework composite aerogel material according to claim 8, wherein the step of growing a metal organic framework material in situ on the organic fiber material having carboxyl groups comprises:
and mixing the organic fiber material with the carboxyl group, soluble metal salt and an organic ligand, and reacting for 1-3 hours at room temperature.
11. The method of claim 8, wherein the step of growing a metal organic framework material in situ on the organic fiber-metal organic framework material intermediate comprises:
and mixing the organic fiber-metal organic framework material intermediate with soluble metal salt and an organic ligand, and reacting for 6-12 hours at room temperature.
12. The method for preparing a metal-organic framework composite aerogel material according to claim 10 or 11, wherein the soluble metal salt is selected from at least one of metal chloride salt and metal nitrate salt.
13. The method of claim 10 or 11, wherein the organic ligand is at least one selected from the group consisting of terephthalic acid, sodium terephthalate, amino-substituted terephthalic acid, amino-substituted sodium terephthalate, trimesic acid, and sodium trimesate.
14. The method for preparing the metal-organic framework composite aerogel material according to any one of claims 8 to 11, further comprising annealing the metal-organic framework composite aerogel material to carbonize the organic fiber material in the metal-organic framework composite aerogel material.
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
CN114031366A (en) * 2021-12-20 2022-02-11 湖南荣岚智能科技有限公司 Composite material prepared by aerogel-filled metal frame structure and preparation method thereof
CN114592344B (en) * 2022-03-29 2024-04-16 武汉纺织大学 Preparation method of high-strength high-toughness fiber material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629080A (en) * 2015-03-06 2015-05-20 武汉理工大学 Method for synthesizing ZIF-8 aerogel on basis of cellulose hard template
CN106669554A (en) * 2016-11-18 2017-05-17 江苏大学 Atmospheric pressure preparation method of iron-containing organic framework silicon-based composite aerogel
CN106995531A (en) * 2017-03-01 2017-08-01 浙江大学 The synthesizing preparation method in situ of cellulose/metal organic frame compound and its application
CN107142538A (en) * 2017-06-27 2017-09-08 陕西科技大学 A kind of preparation method of metal organic frame composite antibacterial fibre cellulose fiber filler
CN110433775A (en) * 2019-09-10 2019-11-12 福州大学 A kind of solid-phase micro-extraction fibre and preparation method of in-situ chemical bond wire organic framework material
CN111282522A (en) * 2020-02-10 2020-06-16 四川大学 Metal organic framework composite aerogel material and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2579132B1 (en) * 2016-04-27 2017-05-19 Universidad Del País Vasco / Euskal Herriko Unibertsitatea METAL-ORGANIC GELS AND METAL-ORGANIC AEROGELS BUILT FROM COORDINATION POLYMER NANOFIBERS

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629080A (en) * 2015-03-06 2015-05-20 武汉理工大学 Method for synthesizing ZIF-8 aerogel on basis of cellulose hard template
CN106669554A (en) * 2016-11-18 2017-05-17 江苏大学 Atmospheric pressure preparation method of iron-containing organic framework silicon-based composite aerogel
CN106995531A (en) * 2017-03-01 2017-08-01 浙江大学 The synthesizing preparation method in situ of cellulose/metal organic frame compound and its application
CN107142538A (en) * 2017-06-27 2017-09-08 陕西科技大学 A kind of preparation method of metal organic frame composite antibacterial fibre cellulose fiber filler
CN110433775A (en) * 2019-09-10 2019-11-12 福州大学 A kind of solid-phase micro-extraction fibre and preparation method of in-situ chemical bond wire organic framework material
CN111282522A (en) * 2020-02-10 2020-06-16 四川大学 Metal organic framework composite aerogel material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis and characterization of Cu-BTC metal–organic;Zhiqiang Li 等;《Cellulose》;20191127;第1733–1744页 *

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