CN112691645A - Carbon aerogel/metal organic framework composite material, preparation method thereof and application thereof in gas storage - Google Patents
Carbon aerogel/metal organic framework composite material, preparation method thereof and application thereof in gas storage Download PDFInfo
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Abstract
The invention provides a carbon aerogel/metal organic framework composite material, a preparation method thereof and application thereof in gas storage, and belongs to the technical field of high polymer materials and gas storage. The composite material consists of MOFs material with better adsorption capacity and carbon aerogel framework material, wherein the MOFs material is directly assembled into the framework of the aerogel as a guest material and is carbonized together to obtain a blocky composite adsorbent material without a binder, and the blocky composite adsorbent material can effectively adsorb methane gas and store the methane gas, so that the composite material has good practical application value.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and gas storage, and particularly relates to an aerogel/metal organic framework composite material, a preparation method thereof and application thereof in gas storage.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Metal Organic Frameworks (MOFs) are a novel porous material which develops very rapidly in the last two decades, have the characteristics of ultra-high specific surface area, adjustable pore size, ultra-large porosity and the like, and are widely applied to the fields of gas adsorption, catalysis, photoelectric materials and the like. Currently, a considerable number of MOFs have been used for gas adsorption and exhibit excellent adsorption properties, which are considered to be the most potential adsorption materials. Nevertheless, most of the MOFs are granules or powders, which are not favorable for recycling; and the material cost is high, and the mass production is difficult, which seriously hinders the practical application thereof.
Based on this, efforts are being made to incorporate MOFs into aerogel matrices to produce biomass aerogel composites. Therefore, the defects of the original material are overcome, the advantages of a single material are exerted, and the method is a strategy for obtaining an ideal material. Aerogel composites are a new class of nanostructured materials that have received increasing attention due to their advantageous properties. The combination of the microporosity and mesoporosity of MOFs and the mesoporosity and macroporosity of aerogels make aerogel composites a hierarchical porous material. And due to the combination of the excellent properties of the two materials, the aerogel composite material shows excellent properties in adsorption, catalysis, energy conversion and storage device applications. In view of the excellent adsorption performance of biomass aerogel and MOFs, the composite material gradually becomes a research hotspot in the field of gas adsorption, and the research and development of the novel efficient adsorbent have important practical significance and research value for adsorption application.
With the increasing concern of people on the living environment, natural gas is receiving increasing attention from all countries in the world as a clean novel energy source due to the characteristics of low pollution, low cost, easy processing and the like. Compared with the traditional storage mode of compressed natural gas and liquefied natural gas, the Adsorbed Natural Gas (ANG) has the advantages of light storage tank dead weight, good safety, low operation cost and the like, and is considered to be the safest and most economic storage method at present. ANG mainly uses a porous material with high specific surface area as a medium, and realizes efficient storage of methane under low pressure (35-65 bar). The high-performance adsorbent material is the core of the ANG technology, breaks through the limited storage capacity which is a key problem existing at present, and promotes the popularization and the application of the natural gas adsorption storage technology to a great extent.
However, as the MOFs are powder adsorbents and are filled in the storage tank, a plurality of gaps are left among particles, the density of natural gas in the gaps is actually the pure compressed natural gas density under the pressure of the storage tank (3-6MPa), and the MOFs do not contribute to increasing the storage density of ANG.
In order to overcome the disadvantages of compressed natural gas, research on natural gas adsorption technology is widely conducted in various countries. The natural gas adsorption technology adopts an adsorbent with a high specific surface area, realizes high-density storage of natural gas under low pressure through the adsorption effect of micropores, and achieves the storage capacity similar to that of compressed natural gas. Compared with compressed natural gas, the natural gas adsorption technology has the advantages of light storage tank dead weight, good safety, low operation cost and the like, and has remarkable economic advantages. Because the main component of natural gas is methane, designing and preparing high-efficiency storage materials for adsorbing methane is the key point of research on natural gas adsorption technology.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a carbon aerogel/metal organic framework composite material, a preparation method thereof and application thereof in gas storage. The composite material consists of MOFs material with better adsorption capacity and carbon aerogel framework material, wherein the MOFs material is directly assembled into the framework of the aerogel as a guest material and is carbonized together to obtain a blocky composite adsorbent material without a binder, and the blocky composite adsorbent material can effectively adsorb methane gas and store the methane gas, so that the composite material has good practical application value.
Specifically, the invention relates to the following technical scheme:
in a first aspect of the present invention, there is provided a carbon aerogel/metal organic framework composite material comprising:
a carbon aerogel framework material; and the number of the first and second groups,
a MOF material supported on an aerogel framework material.
In a second aspect of the present invention, there is provided a method for preparing the above carbon aerogel/metal-organic framework composite material, comprising:
1) preparing a precursor of the aerogel material, and adding a chemical cross-linking agent into the precursor to form a sol solution;
2) adding MOF material to a solvent to form a MOF suspension;
3) mixing the sol solution prepared in the step 1) with the MOF suspension prepared in the step 2), preparing an aerogel/metal organic framework through the following steps a) or b), and carbonizing in a protective atmosphere to obtain the composite material.
a) Hydro-thermal synthesis is carried out to form hydrogel, and after aging and solvent replacement, supercritical drying is carried out;
b) freezing for a period of time and then carrying out freeze-drying treatment.
In a third aspect of the invention, there is provided the use of the above carbon aerogel/metal organic framework composite material in gas storage.
The gas can be methane, hydrogen, nitrogen, carbon monoxide and the like; further preferred is methane.
The beneficial technical effects of one or more technical schemes are as follows:
(1) the carbon aerogel/metal organic framework composite material prepared by the technical scheme has a large specific surface area, meanwhile, the strong host-guest interaction in pores is provided by the synergistic effect of the MOF and the carbon aerogel, and the adsorption kinetics is faster due to the rapid mass transfer in the pores of the carbon aerogel framework, and meanwhile, the carbon aerogel/metal organic framework composite material has good mechanical properties.
(2) The carbon aerogel/metal organic framework composite material prepared by the technical scheme is an integral block material, and a binder is not required to be added in the preparation and forming process, so that the phenomenon of hole plugging caused by the addition of the binder is avoided; and the carbon aerogel framework material has good thermal conductivity, can accelerate the adsorption and desorption rates, is favorable for reducing the cost and prolonging the service life of the adsorbent.
(3) The technical scheme reports that the material with the methane and other gas adsorption and storage functions is prepared based on the metal organic framework and the carbon aerogel in a compounding mode for the first time, tests prove that the material has excellent methane adsorption and storage performance, meanwhile, the selected raw material resources are wide, the cost is low, the green chemical production concept is met, and the actual industrialization and industrialization development of the material are facilitated.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an SEM image of a Cu-MOF/konjac glucomannan carbon aerogel composite adsorbent prepared in example 1 of the invention.
FIG. 2 is an SEM image of a ZIF-8/gelatin carbon aerogel composite adsorbent prepared in example 2 of the present invention.
FIG. 3 is an SEM image of a ZIF-67/cellulosic carbon aerogel composite adsorbent prepared in example 3 of the present invention.
FIG. 4 is a nitrogen adsorption and desorption curve and a pore distribution curve chart of the Cu-MOF/konjac glucomannan carbon aerogel composite adsorbent prepared in example 1 of the present invention.
FIG. 5 is a contour diagram of the adsorption and desorption isotherms of methane gas of the Cu-MOF/konjac glucomannan carbon aerogel composite adsorbent prepared in example 1 of the present invention.
FIG. 6 is a graph showing the mechanical properties of the Cu-MOF/konjac glucomannan carbon aerogel composite adsorbent prepared in example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The present invention is further illustrated by reference to specific examples, which are intended to be illustrative only and not limiting. If the experimental conditions not specified in the examples are specified, they are generally according to the conventional conditions, or according to the conditions recommended by the sales companies; materials, reagents and the like used in examples were commercially available unless otherwise specified.
In an exemplary embodiment of the invention, there is provided a carbon aerogel/metal organic framework composite material, comprising:
a carbon aerogel framework material; and the number of the first and second groups,
a MOF material supported on a carbon aerogel framework material.
The structure of the finally prepared carbon aerogel framework material is regulated and controlled by regulating and controlling the type and the components of the precursor.
Wherein the MOF material is a metal organic framework material with good methane adsorption and storage capacity, and metal ions of the metal organic framework material comprise Cu2+、Zn2+、Cd2+、Co2+、Ni2+、Zr2+、Mg2+、Fe2+、La2+And Mn2+(ii) a More specifically, the metal organic framework material is ZIF-67, ZIF-8, HKUST-1, MIL101 and UiO-66.
In yet another embodiment of the present invention, the specific surface area of the MOF material is controlled to be 1000-3000m2Per g, its pore volume is 0.8-2.0cm3/g。
In another embodiment of the present invention, a method for preparing the carbon aerogel/metal-organic framework composite material comprises:
1) preparing a precursor of the aerogel material, and adding a chemical cross-linking agent into the precursor to form a sol solution;
2) adding MOF material to a solvent to form a MOF suspension;
3) mixing the sol solution prepared in the step 1) with the MOF suspension prepared in the step 2), preparing an aerogel/metal organic framework through the following steps a) or b), and carbonizing in a protective atmosphere to obtain the composite material.
a) Hydro-thermal synthesis is carried out to form hydrogel, and after aging and solvent replacement, supercritical drying is carried out;
b) freezing for a period of time and then carrying out freeze-drying treatment.
In another embodiment of the present invention, in step 1), the precursor comprises resorcinol and formaldehyde, and natural polysaccharide; the concentration of the precursor is controlled to be 1-30%;
in yet another embodiment of the present invention, the natural polysaccharide comprises chitosan, konjac glucomannan, sodium alginate, gelatin, agarose, starch, chitin, lignocellulose, hemicellulose, polyvinyl alcohol, hydroxymethyl cellulose, and the like;
in yet another embodiment of the present invention, the chemical crosslinking agent comprises N, N-methylenebis (acrylamide) (MBA), ethylenediamine, polyacrylic acid, formaldehyde, polyacrylamide, polyethylene glycol, and the like; controlling the concentration to be 0.1-5%;
in still another embodiment of the present invention, in the step 2),
solvents include, but are not limited to, water, methanol, ethanol, DMF, ethylene glycol, glycerol, pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane, and dimethylsulfoxide.
In still another embodiment of the present invention, in the step 3),
the carbonization treatment specifically comprises the following conditions: heating to 800-class 1000 ℃ at 3-8 ℃/min under the atmosphere of nitrogen or argon, and preserving heat for 2-4 h. The adsorption performance of the carbon aerogel/metal organic framework composite material is improved by maintaining proper carbonization treatment conditions.
In still another embodiment of the present invention, in the step a),
controlling the hydrothermal synthesis temperature to be 60-90 ℃ and the synthesis time to be 6-12 h;
the supercritical drying can be ethanol supercritical drying or carbon dioxide supercritical drying;
in still another embodiment of the present invention, in the step b),
freezing for 24-72h, wherein the freezing mode comprises a non-directional freezing mode, a directional freezing mode and a bidirectional freezing mode;
the freeze-drying treatment time is controlled to be 1-7 days;
in the preparation method, the mass ratio of the MOF material to the carbon aerogel framework material is 0.5-3: 1.
the carbon aerogel/metal organic framework composite material prepared by the preparation method is of an integral block structure, and a binder is not needed, so that methane gas is conveniently adsorbed and stored.
In yet another embodiment of the present invention, there is provided a use of the above carbon aerogel/metal organic framework composite material in gas storage.
In yet another embodiment of the present invention, the gas may be methane, ethane, hydrogen, nitrogen, carbon monoxide, carbon dioxide, or the like; further preferred is methane. Tests prove that the adsorption capacity of the aerogel/metal organic framework composite material prepared by the invention to methane is between 60 and 120V/V at low pressure of 35 to 65bar and room temperature of 25 ℃.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1 (Cu-MOF/Konjac glucomannan-based carbon aerogel)
Second twoThe amine was dissolved in 100mL of ultra pure water, and the prepared HKUST-1 powder of 10% wt (relative to the mass fraction of ethylenediamine) was dispersed in the above solution and ultrasonically dispersed for 30 min. Dissolving 1.5g konjac glucomannan powder in the above mixed suspension solution, stirring for 10min, water-bathing at 90 deg.C for 1h, transferring into container, cooling to 25 deg.C, transferring into freezer at-40 deg.C for 24h, transferring into freeze-drying machine, freeze-drying for 1d until all water is removed, and freeze-drying in N2Under protection, heating the composite material to 800 ℃ in a tube furnace at the speed of 5 ℃/min, preserving heat for 2h, cooling and taking out to obtain the Cu-MOF/konjac glucomannan-based carbon aerogel.
The composite adsorbent shows micropore characteristics with the aperture of 1.2nm-1.8nm and the pore volume of 1.1cm through nitrogen adsorption and desorption tests3More than g, the gas molecular diffusion and adsorption-desorption performance is excellent. The BET specific surface area value can reach 1939m2(ii) in terms of/g. The adsorption capacity of the adsorbent at low pressure of 35bar and room temperature of 25 ℃ is 80V/V, and the desorption rate is more than 95%.
The konjac glucomannan-based carbon aerogel material has better mechanical toughness. When the pressure reached the maximum, no significant crushing of the sample occurred and the strain and stress of the carbon aerogel sample were 72% and 0.534Mpa, respectively. After 3000 times of cyclic processes of gas adsorption and desorption are carried out on the performance of the adsorbent, the adsorption volume of the natural gas is reduced by less than 10%.
Example 2 (ZIF-8/gelatin-based carbon aerogel)
Dissolving 0.5g of gelatin in 100ml of water, stirring for 1 hour, standing for 60 ℃ until the gelatin is completely dissolved, then adding 0.7ml of 37-40 wt% formaldehyde solution, stirring for 5 hours at 50 ℃, transferring to a refrigerator for overnight, dispersing prepared 10 wt% (relative to the mass fraction of the gelatin) ZIF-8 powder in the solution the next day, ultrasonically dispersing the mixed solution for 2 hours, rapidly cooling in liquid nitrogen, and freeze-drying. And then transferring the composite material to a freeze dryer for freeze drying for 2d until all water is removed, heating the composite material to 900 ℃ in a tube furnace at the speed of 5 ℃ per minute under the protection of Ar, preserving the temperature for 3h, cooling and taking out to obtain the gelatin-based carbon aerogel/ZIF-8 derived carbon.
Through nitrogen adsorption and desorption test, composite adsorption is carried outThe agent exhibits a micropore characteristic with a pore diameter of 1.5nm to 1.8nm and a pore volume of 1.5cm3More than g, the gas molecular diffusion and adsorption-desorption performance is excellent. The BET specific surface area value can reach 1200m2(ii) in terms of/g. The adsorption capacity of the adsorbent at low pressure of 35bar and room temperature of 25 ℃ is 60V/V, and the desorption rate is more than 95%.
The gelatin-based carbon aerogel material has better mechanical toughness. When the pressure reached the maximum, no significant fracture of the sample occurred (see fig. 4), and the strain and stress of the carbon aerogel sample were 75% and 0.561Mpa, respectively. After 3000 times of cyclic processes of gas adsorption and desorption are carried out on the performance of the adsorbent, the adsorption volume of the natural gas is reduced by less than 10%.
Example 3 (ZIF-67/cellulose-based carbon aerogel)
3.5g of Co (NO)3)2·6H2O and 3.94g of 2-methylimidazole are respectively dissolved in 40mL of methanol and 40mL of ethanol mixed solution, after the two solutions are uniformly stirred, the two solutions are mixed and stirred for 2min, and then 10g of cellulose hydrogel is immersed in the solution and is kept stand at room temperature for 24 h. Then passing through CO2And (4) performing supercritical drying to obtain the ZIF-67/cellulose aerogel. Then at N2Under protection, heating the composite material to 1000 ℃ in a tubular furnace at the speed of 5 ℃/min, preserving heat for 4h, cooling and taking out to obtain the ZIF-67 derived carbon/cellulose-based carbon aerogel.
The composite adsorbent shows micropore characteristics with the aperture of 1.4nm-1.7nm and the pore volume of 1.3cm through nitrogen adsorption and desorption tests3More than g, the gas molecular diffusion and adsorption-desorption performance is excellent. The BET specific surface area value can reach 1400m2(ii) in terms of/g. The adsorption capacity of the adsorbent at low pressure of 35bar and room temperature of 25 ℃ is 80V/V, and the desorption rate is more than 95%.
The cellulose-based carbon aerogel material has better mechanical toughness. When the pressure reached the maximum, no significant crushing of the sample occurred and the strain and stress of the carbon aerogel sample were 78% and 0.582Mpa, respectively. After 3000 times of cyclic processes of gas adsorption and desorption are carried out on the performance of the adsorbent, the adsorption volume of the natural gas is reduced by less than 10%.
Comparative example 1
Dissolving ethylenediamine inThe prepared HKUST-1 powder of 10% wt (relative to the mass fraction of ethylenediamine) was dispersed in 100mL of ultrapure water in the above solution and ultrasonically dispersed for 30 min. Dissolving 1.5g konjac glucomannan powder in the above mixed suspension solution, stirring for 10min, water-bathing at 90 deg.C for 1h, transferring into container, cooling to 25 deg.C, transferring into freezer at-40 deg.C for 24h, transferring into freeze-drying machine, freeze-drying for 1d until all water is removed, and freeze-drying in N2Under protection, heating the composite material to 900 ℃ in a tube furnace at the speed of 5 ℃/min, preserving heat for 2h, cooling and taking out to obtain the Cu-MOF/konjac glucomannan-based carbon aerogel.
The BET specific surface area value reaches 1532m2(ii) in terms of/g. The adsorbent has methane adsorbing amount of 50V/V and desorption rate of about 88% at low pressure of 35bar and room temperature of 25 deg.c.
When the pressure reaches the maximum value, the sample is broken, and the strain and the stress of the carbon aerogel sample are 80 percent and 0.596MPa respectively. The performance of the adsorbent is reduced by about 20% after 3000 times of gas adsorption and desorption cycle.
Comparative example 2
Ethylenediamine was dissolved in 100mL of ultrapure water, and the prepared Cu-MOF-74 powder of 10% wt (relative to the mass fraction of ethylenediamine) was dispersed in the above solution and ultrasonically dispersed for 30 min. Dissolving 1.5g konjac glucomannan powder in the above mixed suspension solution, stirring for 10min, water-bathing at 90 deg.C for 1h, transferring into container, cooling to 25 deg.C, transferring into freezer at-40 deg.C for 24h, transferring into freeze-drying machine, freeze-drying for 1d until all water is removed, and freeze-drying in N2Under protection, heating the composite material to 800 ℃ in a tube furnace at the speed of 5 ℃/min, preserving heat for 2h, cooling and taking out to obtain the Cu-MOF/konjac glucomannan-based carbon aerogel.
The composite adsorbent shows micropore characteristics with the aperture of 5.5nm-7.5nm and the pore volume of 1.4cm through nitrogen adsorption and desorption tests3More than g, the gas molecular diffusion and adsorption-desorption performance is excellent. The BET specific surface area value can reach 2032m2(ii) in terms of/g. The methane adsorption amount of the adsorbent is 85V/V at low pressure of 35bar and room temperature of 25 ℃, and the desorption rate is about 92%.
When the pressure reached the maximum, the sample broke up, and the strain and stress of the carbon aerogel sample were 83% and 0.615Mpa, respectively. The performance of the adsorbent is reduced by about 22% after 3000 times of gas adsorption and desorption cycles.
Comparative example 3
Ethylenediamine was dissolved in 100mL of ultrapure water, and the prepared HKUST-1 powder of 10% wt (relative to the mass fraction of ethylenediamine) was dispersed in the above solution and ultrasonically dispersed for 30 min. Dissolving 1.5g konjac glucomannan powder in the above mixed suspension solution, stirring for 10min, water-bathing at 90 deg.C for 1h, transferring into container, cooling to 25 deg.C, transferring into freezer at-40 deg.C for 24h, transferring into freeze-drying machine, freeze-drying for 1d until all water is removed, and freeze-drying in N2Under protection, heating the composite material to 800 ℃ in a tube furnace at the speed of 10 ℃/min, preserving heat for 2h, cooling and taking out to obtain the Cu-MOF/konjac glucomannan-based carbon aerogel.
The composite adsorbent shows micropore characteristics with the aperture of 0.8-1.4 nm and the pore volume of 0.9cm through nitrogen adsorption and desorption tests3More than g, the BET specific surface area value can reach 1528m2(ii) in terms of/g. The methane adsorption amount of the adsorbent is 45V/V at low pressure of 35bar and room temperature of 25 ℃, and the desorption rate is about 70%.
When the pressure reached the maximum, no significant crushing of the sample occurred and the strain and stress of the carbon aerogel sample were 74% and 0.552Mpa, respectively. The performance of the adsorbent is reduced by about 18% after 3000 times of gas adsorption and desorption cycles.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A carbon aerogel/metal organic framework composite material, comprising:
a carbon aerogel framework material; and the number of the first and second groups,
a MOF material supported on a carbon aerogel framework material.
2. The carbon aerogel/metal-organic framework composite material of claim 1, wherein the MOF material is specifically a metal-organic framework material having good adsorption and storage capacity for methane, and the metal ions thereof comprise Cu2+、Zn2 +、Cd2+、Co2+、Ni2+、Zr2+、Mg2+、Fe2+、La2+And Mn2+；
Preferably, the metal organic framework material is ZIF-67, ZIF-8, HKUST-1, MIL101 and UiO-66;
preferably, the specific surface area of the MOF material is 1000-3000m2Per g, its pore volume is 0.8-2.0cm3/g。
3. The process for preparing the carbon aerogel/metal-organic framework composite material of claim 1 or 2, comprising:
1) preparing a precursor of the aerogel material, and adding a chemical cross-linking agent into the precursor to form a sol solution;
2) adding MOF material to a solvent to form a MOF suspension;
3) mixing the sol solution prepared in the step 1) with the MOF suspension prepared in the step 2), preparing an aerogel/metal organic framework through the following steps of a) or b), and carbonizing in a protective atmosphere to obtain the composite material;
a) hydro-thermal synthesis is carried out to form hydrogel, and after aging and solvent replacement, supercritical drying is carried out;
b) freezing for a period of time and then carrying out freeze-drying treatment.
4. The preparation method according to claim 3, wherein in the step 1), the precursor comprises resorcinol and formaldehyde, natural polysaccharide; the concentration of the precursor is controlled to be 1-30%.
5. The method of claim 4, wherein the natural polysaccharide comprises chitosan, konjac glucomannan, sodium alginate, gelatin, agarose, starch, chitin, lignocellulose, hemicellulose, polyvinyl alcohol, and hydroxymethyl cellulose;
the chemical cross-linking agent comprises N, N-methylene-bis (acrylamide), ethylenediamine, polyacrylic acid, formaldehyde, polyacrylamide and polyethylene glycol; the concentration is controlled to be 0.1-5%.
6. The method according to claim 3, wherein in the step 2),
the solvent includes water, methanol, ethanol, DMF, ethylene glycol, glycerol, pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane, and dimethylsulfoxide.
7. The method according to claim 3, wherein in the step 3),
the carbonization treatment specifically comprises the following conditions: heating to 800-class 1000 ℃ at 3-8 ℃/min under the atmosphere of nitrogen or argon, and preserving heat for 2-4 h.
8. The method according to claim 3, wherein in step a),
controlling the hydrothermal synthesis temperature to be 60-90 ℃ and the synthesis time to be 6-12 h;
supercritical drying specifically adopts ethanol supercritical drying or carbon dioxide supercritical drying;
in the step b), the step (c),
freezing for 24-72h, wherein the freezing mode comprises a non-directional freezing mode, a directional freezing mode and a bidirectional freezing mode;
the freeze-drying time is controlled to be 1-7 days.
9. The method of claim 4, wherein the mass ratio of MOF material to aerogel framework material is from 0.5 to 3: 1.
10. use of the carbon aerogel/metal-organic framework composite of any of claims 1-3 in gas storage;
preferably, the gas is methane, ethane, hydrogen, nitrogen, carbon monoxide, carbon dioxide, or the like; further preferred is methane.
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