CN112892489A - MOFs/carbon aerogel adsorption filtering material and preparation method thereof - Google Patents

MOFs/carbon aerogel adsorption filtering material and preparation method thereof Download PDF

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CN112892489A
CN112892489A CN202011560593.9A CN202011560593A CN112892489A CN 112892489 A CN112892489 A CN 112892489A CN 202011560593 A CN202011560593 A CN 202011560593A CN 112892489 A CN112892489 A CN 112892489A
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protein
mofs
aerogel
carbon aerogel
carbon
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CN112892489B (en
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刘瑞娜
卢艳红
王树军
陈钰
魏磊
齐青
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Langfang Normal University
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Abstract

The invention relates to a high-performance MOFs/carbon aerogel adsorption filtration material and a preparation method thereof, wherein the preparation method comprises the following steps: dipping carbon aerogel in a solution of protein and organic micromolecule ligand, taking out the dipped aerogel and transferring the aerogel into a metal ion solution with moderate concentration, taking the protein as an inducer, carrying out biomimetic mineralization reaction on metal ions and the organic micromolecule ligand under the induction of the protein, taking out a product and placing the product in a vacuum drying oven, evaporating the solvent, and preparing the MOFs/carbon aerogel composite material loaded at one time; the MOFs is loaded at least once in the steps, and the obtained loaded MOFs/carbon aerogel composite material has excellent adsorption and filtration properties.

Description

MOFs/carbon aerogel adsorption filtering material and preparation method thereof
Technical Field
The invention belongs to high-performance functional materials, and particularly relates to an MOFs/carbon aerogel adsorption filtration material and a preparation method thereof.
Background
With the progress of global industry and economy, great convenience is brought to the society, but negative problems brought by the progress are gradually shown, a great amount of industrial emission brings great adverse effects on the environment, the problems of environmental pollution and the like are obvious, and the concept of green economy advocated by the country and the place is widely practiced, wherein the problems of adsorption, filtration and the like of pollutants or other impurities are widely concerned by all bodies, and the method becomes an important research hotspot at present.
The method for adsorption filtration at present mainly comprises a physical method, a chemical method and a biological method, wherein the specific methods comprise adsorption, ion exchange, chemical precipitation, chemical treatment, coagulation and flocculation, oxidation, electrochemical treatment, biological treatment, membrane filtration and the like, and aiming at an adsorption filtration material, various high-efficiency adsorption materials are reported at present, such as activated carbon, carbon nanotubes, graphene, minerals, siliceous materials, molecular sieves, metal organic frameworks and the like.
Metal-Organic Frameworks (MOFs) compounds are a class of porous materials formed by Metal ions or atom clusters and Organic ligands through coordination bonds, and have the advantages of high specific surface area, high porosity, adjustable pore size, variable framework structure and the like, so that the Metal-Organic Frameworks (MOFs) compounds are widely applied to the fields of catalyst synthesis, gas storage, liquid phase adsorption, luminescent materials and the like in recent years.
Aerogel is successfully prepared by Kistler in 1931 by adopting a supercritical drying method, and is the key point of research of researchers at present due to the characteristics of high porosity, high specific surface area, low density, low dielectric constant, high adsorption and the like. The carbon sponge has high elasticity, has ultra-fast and ultra-high adsorption force on organic solvents, and is the material with the highest oil absorption force reported so far. The existing oil absorption products can only absorb liquid with the mass about 10 times of the self mass, and the absorption capacity of the carbon sponge is about 250 times, and can reach 900 times at most.
In the prior art, the publication numbers are: the invention patent of CN111974459A discloses a tubular free radical catalyst and a preparation method thereof, wherein the preparation method comprises the steps of firstly preparing a cellulose dissolving solution, then adding nickel nitrate into the cellulose dissolving solution, adding a cross-linking agent for preliminary cross-linking, freezing and drying to prepare a composite aerogel, and then soaking in a 2-methylimidazole solution to prepare MOFS/cellulose composite aerogel; in the process, cellulose molecules form a three-dimensional porous structure with mutual communication under the action of a cross-linking agent, and MOFs crystals are uniformly attached to pore channels of the three-dimensional porous structure to form a multi-stage porous structure; and then, taking the self-made MOFS/cellulose composite aerogel as a framework, immersing the self-made MOFS/cellulose composite aerogel into titanium-containing sol, repeatedly dipping, forming a multilayer film on the surface of the framework by the titanium-containing sol, adding sodium hydroxide for reaction, and growing a sodium titanate nanotube array on the surface of the framework in situ.
The invention patent with the publication number of CN112023891A discloses a Ni-MOF/carbon aerogel adsorbent for extracting iodine and a preparation method thereof, specifically, hexamethylenetetramine is dissolved in absolute ethyl alcohol, and CaCO is added in sequence3Reacting resorcinol with alpha-furaldehyde, standing in acetone, drying, carbonizing in tubular furnace, and removing CaCO in hydrochloric acid3And drying to obtain carbon aerogel; and then adding the carbon aerogel, nickel nitrate hexahydrate and trimesic acid into dimethylformamide for reaction and washing to obtain the Ni-MOF/carbon aerogel adsorbent. The Ni-MOF/carbon aerogel adsorbent can effectively separate iodine nuclide and other substances in waste gas, and has strong adsorption capacity and good analysis effect.
The invention aims to provide a high-performance adsorption material and a preparation method of the adsorption material, the material has excellent adsorption performance, the preparation method is simple, and the aerogel material can be well improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-performance MOFs/carbon aerogel adsorption filtration material which can effectively prevent the collapse problem of carbon aerogel and is combined with the adsorption performance of the MOFs material and the carbon aerogel to prepare a composite material with excellent adsorption filtration material.
The raw materials of the high-performance MOFs/carbon aerogel adsorption filter material provided by the invention comprise carbon aerogel, metal ion solution, organic micromolecular ligand and protein;
furthermore, the high-performance MOFs/carbon aerogel adsorption filter material provided by the method is characterized in that the carbon aerogel is one or more of carbon nanotube aerogel, carbon fiber aerogel or graphene aerogel;
furthermore, the content of the MOFs accounts for 5-30%, preferably 10-30%, and more preferably 20-30% of the material.
Furthermore, the MOFs (metal organic framework) material is prepared by carrying out biomimetic mineralization reaction on metal ions and organic small molecular ligands under the induction of protein;
specifically, the metal ions are one or more of alkali metal ions, alkaline earth metal ions, transition metal ions or rare earth metal ions;
further, the metal ion is Na+、K+、Zn2+、Mg2+、Fe2+/3+、Cu2+、Mn2+、Co2+/3+、Ni2+、La3+、Eu3+、Sm3+、Tb3+、Dy3+、Gd3+、Ho3+、Er3+One or more of (a).
Specifically, the organic small molecular ligand is one or more of imidazoles, pyrimidines, carboxylic acids or hydroxycarboxylic acids;
specifically, the organic small molecule ligand is one or more of 2-methylimidazole, phenanthroline, mannose, nicotinic acid, isonicotinic acid, oxalic acid, fumaric acid, citric acid, terephthalic acid, trimesic acid, pyromellitic acid, 2, 5-dihydroxyterephthalic acid and modified ligands.
Specifically, the protein is one or more of silk fibroin, down feather protein, wool protein, cashmere protein, bovine serum albumin, egg white protein, casein, corn protein or soybean protein;
further, the porosity of the high-performance MOFs/carbon aerogel adsorption filter material is more than 90%, preferably more than 92%, and more preferably more than 95%;
furthermore, the pore size of the high-performance MOFs/carbon aerogel adsorption filtering material is less than 10 microns; more preferably less than 5 microns; preferably less than 1000 nm; preferably less than 500 nm; more preferably less than 100 nm;
further, the mass ratio of the carbon aerogel to the protein liquid to the organic micromolecule ligand in the raw materials is 1-10: 1: 1-5;
further, the molar ratio of the metal ions to the organic small molecular ligands in the raw materials is 1: 1-10;
the idea of the adsorption filter material prepared by the invention is that MOFs material is loaded in the structure of carbon aerogel through a synthesis step, so that the technical problem that the carbon aerogel material is easy to collapse is solved, further, in order to increase the load of the MOFs material, protein is used as induction, small molecular organic ligands, metal ions and protein are biomimetically mineralized to form the MOFs nano crystalline material, and protein macromolecules are used as macromolecular organic ligands of the MOFs, and are partially present in an MOFs porous frame through weak action. In addition, the obtained MOFs material is subjected to in-situ reaction on the carbon aerogel, can penetrate into the framework of the carbon aerogel, and improves the mechanical properties of the carbon aerogel.
Further, the invention also provides a preparation method of the high-performance MOFs/carbon aerogel adsorption filter material, which specifically comprises the following steps:
step (1), loading a reaction precursor by carbon aerogel;
specifically, the precursor comprises a solution of a protein and an organic small molecule ligand;
specifically, the carbon aerogel is soaked in a precursor solution, so that the protein and the small molecule ligand can enter the aerogel.
And (2) reacting the aerogel loaded with the protein and the organic small molecular ligand in the step (1) with a metal ion solution.
Specifically, the aerogel loaded with the protein and the organic small molecule ligand is added into a metal ion solution, or the metal ion solution is added into an aerogel container loaded with the protein and the organic small molecule ligand.
Further, the step (2) also comprises a drying operation;
the drying operation is mainly to remove the solvent from the material, that is, a drying step is possible as long as the solvent can be removed in the present invention.
The drying is vacuum drying.
Specifically, the temperature of vacuum drying is 60-100 ℃;
the idea of the invention is that protein is used as an inducer to induce metal ions and organic micromolecular ligands to perform biomimetic mineralization reaction to obtain the biomimetic mineralized MOFs nano crystal material, because the protein and the micromolecular organic ligands are adsorbed on carbon aerogel, when the MOFs material is obtained through biomimetic mineralization, the MOFs material is adsorbed in the carbon aerogel, and the combination of the MOFs material and the carbon aerogel is more stable due to the adsorption mode, and meanwhile, due to the in-situ synthesis of the MOFs material, the loading of the particles can further improve the void condition of the carbon aerogel, so that the porosity is more uniform, and the void size is more stable. In the mechanical structure, the introduction of the MOFs material strengthens the skeleton of the carbon fiber, so that the obtained adsorption filtering material can effectively prevent the collapse of carbon aerogel in the compression process, and the service durability of the adsorption filtering material is longer.
Further, according to the preparation method of the invention, the steps (1) and (2) can be repeated according to the porosity, the size of the gap and the requirement of the filtering effect required by the adsorption filtering material, so that the content of the MOFs in the adsorption filtering material can be controlled.
Furthermore, the invention provides a preparation method of the specific high-performance MOFs/carbon aerogel adsorption filter material, which specifically comprises the following steps:
step (1), loading a reaction precursor by carbon aerogel;
firstly, dipping carbon aerogel in a solution of protein and organic micromolecule ligand for 20-40 min, fully filling the precursor solution with the carbon aerogel,
reacting the aerogel loaded with the protein and the organic micromolecular ligand in the step (1) with a metal ion solution;
taking out the aerogel loaded with the proteins and the organic micromolecule ligand in the step (1), transferring the aerogel into a metal ion solution with moderate concentration, taking the proteins as an inducer, carrying out biomimetic mineralization reaction on the metal ions and the organic micromolecule ligand under the induction of the proteins, taking out the sample after 1 second to 10 minutes, placing the sample in a vacuum drying oven, treating for 12 hours at the temperature of 60-100 ℃, evaporating the solvent, and preparing to obtain the MOFs/carbon aerogel composite material loaded for one time;
further, the primary-load MOFs/carbon aerogel composite material obtained in the step (1) is immersed in the precursor solution, the steps (1) and (2) are repeated, and the steps of dipping, mineralizing, evaporating and curing are repeated for 2-3 times, so that the sample MOFs/carbon aerogel composite material is obtained.
Further, the carbon aerogel is one or more of carbon nanotube aerogel, carbon fiber aerogel or graphene aerogel;
further, the metal ion is Na+、K+、Zn2+、Mg2+、Fe2+/3+、Cu2+、Mn2+、Co2+/3+、Ni2+、La3+、Eu3+、Sm3+、Tb3+、Dy3+、Gd3+、Ho3+、Er3+One or more of (a).
Specifically, the organic small molecule ligand is one or more of 2-methylimidazole, phenanthroline, mannose, nicotinic acid, isonicotinic acid, oxalic acid, fumaric acid, citric acid, terephthalic acid, trimesic acid, pyromellitic acid, 2, 5-dihydroxyterephthalic acid and modified ligands.
Specifically, the protein is one or more of silk fibroin, down feather protein, wool protein, cashmere protein, bovine serum albumin, egg white protein, casein, corn protein or soybean protein.
More specifically, the invention aims to carry out biomimetic mineralization reaction on a raw material capable of forming a metal organic framework and protein, and load the raw material on a carbon aerogel tissue, thereby improving the performance of the carbon aerogel and improving the adsorption performance of the whole composite material. Therefore, the coordination of the specific metal ion and the organic ligand is not particularly limited in terms of the present invention.
Preferably, the preferred small molecule ligand of the present invention is pyromellitic acid, and the metal particle of reagent C is Eu3+；
Preferably, the small molecular ligand is 2-methylimidazole, and the metal ion is Zn2+。
Preferably, the small molecule ligand is 2, 5-dihydroxyterephthalic acid, and the metal ion is Mg2+；
Preferably, the small molecular ligand is terephthalic acid, and the metal ion is Fe3+；
Preferably, the small molecular ligand is 2, 5-dihydroxyterephthalic acid, and the metal ion is Eu3+；
Preferably, the small molecular ligand is trimesic acid, and the metal ion is Cu2+；
Preferably, the small molecular ligand is mannose, and the metal ion is Sm3+。
Furthermore, the invention provides an application of the high-performance MOFs/carbon aerogel adsorption filter material, and particularly can be used for adsorbing harmful substances in air, water and soil.
Compared with the prior art, the invention provides a novel adsorption filtering material, which is characterized in that carbon aerogel is soaked in a solution of protein and organic micromolecule ligand, the soaked aerogel is taken out and transferred into a metal ion solution with moderate concentration, the protein is taken as an inducer, the metal ion and the organic micromolecule ligand are subjected to biomimetic mineralization reaction under the induction of the protein, a product is taken out and placed in a vacuum drying oven, the solvent is evaporated, and the MOFs/carbon aerogel composite material loaded for one time is prepared; the MOFs material is introduced into the carbon aerogel, so that the void ratio and the void size of the carbon aerogel are effectively improved, and meanwhile, the mechanical property of the carbon aerogel is optimized and improved, so that the aerogel is not easy to collapse after being compressed, and the recycling frequency of the material can be improved.
Drawings
FIG. 1: SEM picture of carbon fiber aerogel;
FIG. 2: SEM image of the MOFs/carbon fiber aerogel adsorption filter material prepared in example 1;
FIG. 3: example 6 adsorption effect of carbon aerogel composite materials loaded with different MOFs contents on harmful substances.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in further detail with reference to examples, but those skilled in the art will appreciate that these examples are intended to more specifically explain the concept of the present invention and should not be used to limit the scope of the present invention.
Example 1
A preparation method of a specific high-performance MOFs/carbon aerogel adsorption filter material,
step (1): loading a reaction precursor on carbon aerogel;
and (3) soaking the carbon aerogel in a solution of the protein and the organic micromolecule ligand for 20min, and fully filling the precursor solution into the carbon aerogel.
The carbon aerogel is carbon fiber aerogel;
wherein the organic micromolecule is 2-methylimidazole, and the protein is silk fibroin.
Step (2): and (2) reacting the aerogel loaded with the protein and the organic small molecule ligand in the step (1) with a metal ion solution. Preparing a primary-loaded MOFs/carbon aerogel composite material;
adding the material of the step (1) into a metal ion solution.
The metal ion solution is Zn2+(ii) a The reaction time isFor 3 minutes.
Putting the obtained product into a vacuum drier, setting the temperature at 80 ℃, and drying for 12 hours to completely volatilize the solvent.
And (3) repeating the steps (1) to (2) for three times to obtain the MOFs/carbon aerogel adsorption filtering material.
The mass ratio of the carbon aerogel to the protein liquid to the organic micromolecular ligand is 1: 1: 1;
the molar ratio of the metal ions to the organic micromolecular ligand in the raw materials is 1: 5
Example 2
A preparation method of a specific high-performance MOFs/carbon aerogel adsorption filter material,
step (1): loading a reaction precursor on carbon aerogel;
and (3) soaking the carbon aerogel in a solution of the protein and the organic micromolecule ligand for 20-40 min, and fully filling the precursor solution into the carbon aerogel.
The carbon aerogel is carbon fiber aerogel;
wherein the organic micromolecule ligand 2, 5-dihydroxy terephthalic acid and the protein are silk fibroin.
Step (2): and (2) reacting the aerogel loaded with the protein and the organic small molecule ligand in the step (1) with a metal ion solution. Preparing a primary-loaded MOFs/carbon aerogel composite material;
adding the material of the step (1) into a metal ion solution.
The metal ion solution is Mg2+(ii) a The reaction time was 2 minutes.
Putting the obtained product into a vacuum drier, setting the temperature at 80 ℃, and drying for 12 hours to completely volatilize the solvent.
And (3) repeating the steps (1) to (2) for three times to obtain the MOFs/carbon aerogel adsorption filtering material.
The mass ratio of the carbon aerogel to the protein liquid to the organic micromolecular ligand is 2: 1: 1;
the molar ratio of the metal ions to the organic micromolecular ligand in the raw materials is 1: 5
Example 3
A preparation method of a specific high-performance MOFs/carbon aerogel adsorption filter material,
step (1): loading a reaction precursor on carbon aerogel;
and (3) soaking the carbon aerogel in a solution of the protein and the organic micromolecule ligand for 20-40 min, and fully filling the precursor solution into the carbon aerogel.
The carbon aerogel is carbon fiber aerogel;
wherein the organic micromolecules are terephthalic acid, and the protein is soybean protein.
Step (2): and (2) reacting the aerogel loaded with the protein and the organic small molecule ligand in the step (1) with a metal ion solution. Preparing a primary-loaded MOFs/carbon aerogel composite material;
adding the material of the step (1) into a metal ion solution.
The metal ion solution is Fe3+(ii) a The reaction time was 3 minutes.
Putting the obtained product into a vacuum drier, setting the temperature at 80 ℃, and drying for 12 hours to completely volatilize the solvent.
And (3) repeating the steps (1) to (2) for three times to obtain the MOFs/carbon aerogel adsorption filtering material.
The mass ratio of the carbon aerogel to the protein liquid to the organic micromolecular ligand is 2: 1: 1;
the molar ratio of the metal ions to the organic micromolecular ligand in the raw materials is 1: 4.
example 4
A preparation method of a specific high-performance MOFs/carbon aerogel adsorption filter material,
step (1): loading a reaction precursor on carbon aerogel;
and (3) soaking the carbon aerogel in a solution of the protein and the organic micromolecule ligand for 20-40 min, and fully filling the precursor solution into the carbon aerogel.
The carbon aerogel is carbon fiber aerogel;
wherein the organic micromolecule is trimesic acid, and the protein is soybean protein.
Step (2): and (2) reacting the aerogel loaded with the protein and the organic small molecule ligand in the step (1) with a metal ion solution. Preparing a primary-loaded MOFs/carbon aerogel composite material;
adding the material of the step (1) into a metal ion solution.
The metal ion solution is Cu2+(ii) a The reaction time was 3 minutes.
Putting the obtained product into a vacuum drier, setting the temperature at 80 ℃, and drying for 12 hours to completely volatilize the solvent.
And (3) repeating the steps (1) to (2) for three times to obtain the MOFs/carbon aerogel adsorption filtering material.
The mass ratio of the carbon aerogel to the protein liquid to the organic micromolecular ligand is 2: 1: 1;
the molar ratio of the metal ions to the organic micromolecular ligand in the raw materials is 1: 4.
example 5
A preparation method of a specific high-performance MOFs/carbon aerogel adsorption filter material,
step (1): loading a reaction precursor on carbon aerogel;
and (3) soaking the carbon aerogel in a solution of the protein and the organic micromolecule ligand for 20-40 min, and fully filling the precursor solution into the carbon aerogel.
Wherein the organic micromolecule is 2-methylimidazole.
Step (2): and (2) reacting the aerogel loaded with the protein and the organic small molecule ligand in the step (1) with a metal ion solution. Preparing a primary-loaded MOFs/carbon aerogel composite material;
adding the material of the step (1) into a metal ion solution.
The carbon aerogel is carbon fiber aerogel;
the metal ion solution is Zn2+(ii) a The reaction time was 3 minutes;
putting the obtained product into a vacuum drier, setting the temperature at 80 ℃, and drying for 12 hours to completely volatilize the solvent.
And (3) repeating the steps (1) to (2) for three times to obtain the MOFs/carbon aerogel adsorption filtering material.
The mass ratio of the carbon aerogel to the small-molecule organic ligand is 2: 1: 1;
further, the molar ratio of the metal ions to the organic small molecular ligands in the raw materials is 1: 5.
example 6
Based on example 1, step (3) in example 1 was controlled, so as to control the MOFs content in the carbon aerogel, and the material was tested for adsorption performance. As can be seen from the test results shown in the attached FIG. 3, the adsorption capacity of the adsorbent is gradually enhanced with the increase of the content of the MOFs, and the adsorbent is strongest when the content of the MOFs is about 20%.
The examples in the embodiments of the present invention are only for the purpose of comprehensive and concrete explanation of the present invention, and do not represent all the technical ideas of the present invention, nor do they represent the scope of the present invention.

Claims (8)

1. The MOFs/carbon aerogel adsorption filtration material is characterized in that raw materials of the MOFs/carbon aerogel adsorption filtration material comprise carbon aerogel, metal ion solution, organic micromolecular ligand and protein;
the carbon aerogel is one or more of carbon nanotube aerogel, carbon fiber aerogel or graphene aerogel.
2. The MOFs/carbon aerogel adsorption and filtration material of claim 1, wherein the MOFs material is obtained by biomimetic mineralization reaction of metal ions and organic small molecular ligands under protein induction;
the metal ions are one or more of alkali metal ions, alkaline earth metal ions, transition metal ions or rare earth metal ions;
the organic micromolecular ligand is one or more of imidazoles, pyrimidines, carboxylic acids or hydroxycarboxylic acids;
the protein is one or more of silk fibroin, down feather protein, wool protein, cashmere protein, bovine serum albumin, egg white protein, casein, zein or soybean protein.
3. A MOFs/carbon aerogel adsorption filter material according to claim 2,
the metal ion is Na+、K+、Zn2+、Mg2+、Fe2+/3+、Cu2+、Mn2+、Co2+/3+、Ni2+、La3+、Eu3+、Sm3+、Tb3+、Dy3+、Gd3+、Ho3+、Er3+One or more of;
the organic micromolecule ligand is one or more of 2-methylimidazole, phenanthroline, mannose, nicotinic acid, isonicotinic acid, oxalic acid, fumaric acid, citric acid, terephthalic acid, trimesic acid, pyromellitic acid, 2, 5-dihydroxyterephthalic acid and modified ligand.
4. A MOFs/carbon aerogel adsorption filter material according to any of claims 1 to 3, wherein the adsorption filter material has a porosity of more than 90%, preferably more than 92%, more preferably more than 95%; the material pore size is less than 10 microns; more preferably less than 5 microns; preferably less than 1000 nm; preferably less than 500 nm; more preferably less than 100 nm.
5. The MOFs/carbon aerogel adsorption filtration material according to any one of claims 1 to 3, wherein the mass ratio of the carbon aerogel to the protein liquid to the organic small molecule ligand is 1-10: 1: 1-5; the molar ratio of the metal ions to the organic micromolecular ligand is 1: 1 to 10.
6. A method for preparing the MOFs/carbon aerogel adsorption and filtration material according to any one of claims 1 to 5, which comprises the following steps:
step (1), loading a reaction precursor by carbon aerogel;
the precursor comprises a solution of protein and organic small molecule ligand;
the carbon aerogel is soaked in a precursor solution, so that protein and micromolecular ligands can enter the aerogel;
reacting the aerogel loaded with the protein and the organic micromolecular ligand in the step (1) with a metal ion solution;
adding the aerogel loaded with the protein and the organic small molecule ligand in the step (1) into a metal ion solution, or adding the metal ion solution into an aerogel container loaded with the protein and the organic small molecule ligand.
7. A method for preparing the MOFs/carbon aerogel adsorption filtration material according to claim 6, wherein the step (2) further comprises a drying operation;
the drying is vacuum drying; the temperature of vacuum drying is 60-100 ℃.
8. A process for the preparation of the MOFs/carbon aerogel adsorption filtration material according to any one of claims 6 to 7,
and (3) repeating the step (1) and the step (2).
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113559797A (en) * 2021-08-09 2021-10-29 云南大学 Biochar aerogel material and preparation method and application thereof
CN113944053A (en) * 2021-11-19 2022-01-18 廊坊师范学院 Preparation method of MOFs material with detection application in extreme environment
CN115368582A (en) * 2022-09-01 2022-11-22 湖北工业大学 Preparation method of isonicotinic acid functionalized Eu-MOFs fluorescent probe and metronidazole recoverability detection method thereof
CN115920790A (en) * 2023-01-06 2023-04-07 南昌航空大学 Preparation method of multifunctional nitrogen-doped carbon aerogel
CN116237013A (en) * 2023-01-16 2023-06-09 廊坊师范学院 Carbon material based on biomass and eutectic solvent and wastewater adsorption treatment method
CN116532096A (en) * 2023-04-27 2023-08-04 浙江大学 Supported MOFs material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103483360A (en) * 2013-09-09 2014-01-01 太原理工大学 Preparation method for metal complex functionalized ZIF-8 (zinc 2-methylimidazolate) material
CN104087572A (en) * 2014-07-01 2014-10-08 清华大学 Protein and metal organic skeleton compound composite material and preparation method thereof
CN107871617A (en) * 2016-09-28 2018-04-03 中国人民解放军国防科学技术大学 Graphene metal organic frame composite and its preparation method and application
CN107913674A (en) * 2017-10-27 2018-04-17 苏州大学 Load 3D rutheniums/graphene aerogel composite material of MOF and preparation method thereof and the application in lasting processing CO

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103483360A (en) * 2013-09-09 2014-01-01 太原理工大学 Preparation method for metal complex functionalized ZIF-8 (zinc 2-methylimidazolate) material
CN104087572A (en) * 2014-07-01 2014-10-08 清华大学 Protein and metal organic skeleton compound composite material and preparation method thereof
CN107871617A (en) * 2016-09-28 2018-04-03 中国人民解放军国防科学技术大学 Graphene metal organic frame composite and its preparation method and application
CN107913674A (en) * 2017-10-27 2018-04-17 苏州大学 Load 3D rutheniums/graphene aerogel composite material of MOF and preparation method thereof and the application in lasting processing CO

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113559797A (en) * 2021-08-09 2021-10-29 云南大学 Biochar aerogel material and preparation method and application thereof
CN113944053A (en) * 2021-11-19 2022-01-18 廊坊师范学院 Preparation method of MOFs material with detection application in extreme environment
CN113944053B (en) * 2021-11-19 2024-03-01 廊坊师范学院 Preparation method of MOFs material with detection application in extreme environment
CN115368582A (en) * 2022-09-01 2022-11-22 湖北工业大学 Preparation method of isonicotinic acid functionalized Eu-MOFs fluorescent probe and metronidazole recoverability detection method thereof
CN115920790A (en) * 2023-01-06 2023-04-07 南昌航空大学 Preparation method of multifunctional nitrogen-doped carbon aerogel
CN116237013A (en) * 2023-01-16 2023-06-09 廊坊师范学院 Carbon material based on biomass and eutectic solvent and wastewater adsorption treatment method
CN116532096A (en) * 2023-04-27 2023-08-04 浙江大学 Supported MOFs material and preparation method and application thereof

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