CN113511649A - Preparation method and application of flexible block amine modified three-dimensional graphene mesoporous material - Google Patents
Preparation method and application of flexible block amine modified three-dimensional graphene mesoporous material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 150000001412 amines Chemical class 0.000 title claims abstract description 81
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000017 hydrogel Substances 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 28
- 238000004321 preservation Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- 239000003755 preservative agent Substances 0.000 claims description 5
- 230000002335 preservative effect Effects 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
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- 229960001124 trientine Drugs 0.000 description 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The invention discloses a preparation method of a flexible block amine modified three-dimensional graphene mesoporous material, which comprises the following steps: firstly, ultrasonically dispersing a graphene oxide aqueous solution, and then adjusting the pH value to obtain a graphene oxide dispersion liquid; secondly, uniformly mixing the high amine aqueous solution and the graphene oxide dispersion liquid, and performing ultrasonic treatment to obtain a mixture; thirdly, placing the mixture into a mold, and then keeping the temperature and standing to form hydrogel; fourthly, soaking and freeze-drying the stripped hydrogel to obtain a flexible block amine modified three-dimensional graphene mesoporous material; the invention also discloses application of the mesoporous material in the aspect of adsorbing carbon dioxide. According to the invention, the temperature and time of the action of the sheet layer of the graphene oxide and the high amine molecules are controlled, the regulation and control of the internal appearance and the pore structure of the mesoporous material are realized, the amine load capacity and the adsorption performance of the mesoporous material are improved, and meanwhile, the freeze-drying method is combined to maintain the complete high-resilience block structure; the mesoporous material is suitable for various carbon dioxide gas adsorption environments and has a wide application range.
Description
Technical Field
The invention belongs to the technical field of mesoporous adsorption materials, and particularly relates to a preparation method and application of a flexible block amine modified three-dimensional graphene mesoporous material.
Background
Carbon dioxide is a main combustion product of fossil fuel, and is a main cause of environmental changes such as an increase in atmospheric temperature, an increase in ocean acidity, and glacier thawing. Among them, the carbon dioxide gas generated by the human industrial activities accounts for the largest proportion of global greenhouse gases, and in order to slow down the global warming process, the ability to capture, convert and degrade the carbon dioxide present in the atmosphere and reduce the concentration thereof present in the atmosphere is a requirement of the current environmental situation for new materials.
Aerogel is a new material with three-dimensional porous nano structure, and has the characteristics of high porosity, high specific surface area, low density and the like, and also has special characteristics such as high temperature resistance, low thermal conductivity, low refractive index and the like. These advantages have promoted the wide application of aerogel in aspects of heat insulation, adsorption and desorption, photoelectrocatalysis, energy storage, sound absorption and the like. Among aerogels, a graphene mesoporous material is an aerogel which attracts attention in recent years, and inherits the dual advantages of the graphene characteristic and the aerogel structure. The graphene aerogel has a three-dimensional porous carbon structure, the internal network framework is composed of graphene nanosheets, and stacking between the sheets is avoided. From a large number of studies, it is not difficult to find that graphene aerogel is once considered as one of the most potential adsorbents for separating air pollutants due to its easily designed pore structure and high chemical stability, recyclability and reusability. However, the existing graphene adsorption material has the defects of low strength, high cost, harsh preparation environment and the like. In the preparation method of the graphene hybrid aerogel disclosed and reported in patent CN107117608B, the inventor indicates that the internal structure of the aerogel can be regulated and controlled by changing the concentrations of graphene oxide and polyethyleneimine; however, due to the disorder in the forming process of the aerogel material, the internal structure of the material cannot be completely regulated and controlled only by changing the dosage of the precursor, and the amine loading of the adsorption material cannot be effectively controlled. In the polyamine-functionalized three-dimensional graphene-based aerogel material disclosed in patent CN110540191A, the content of nitrogen is stable between 0-17%, the pore structure is clear, and effective adsorption and separation of thorium ions and rare earth elements are realized; however, the resulting material is not a block, lacks mechanical strength and has a low amine functionality loading. Therefore, designing and preparing a graphene aerogel adsorption material with low cost, complete and controllable structure, high amine loading capacity and relatively simple operation is the focus of current research.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a flexible block amine modified three-dimensional graphene mesoporous material aiming at the defects of the prior art. According to the method, graphene oxide is used as a matrix, high amine molecules in a high amine aqueous solution are used as a cross-linking agent, the internal appearance and the pore structure of the mesoporous material are regulated and controlled by controlling the temperature and time of the action of the lamellar layer of the graphene and the high amine molecules, the amine loading capacity and the adsorption performance of the mesoporous material are improved, and the mesoporous material is enabled to keep a complete and high-resilience block structure by combining a freeze-drying method, so that the problems of low amine loading capacity, poor mechanical strength and a non-block structure of a polyamine functional three-dimensional graphene-based aerogel material are solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized by comprising the following steps:
step one, carrying out ultrasonic dispersion on a graphene oxide aqueous solution, and then adjusting the pH value by using a sodium hydroxide aqueous solution to obtain a graphene oxide dispersion liquid;
step two, mixing the high amine aqueous solution and the graphene oxide dispersion liquid obtained in the step one, stirring uniformly, and performing ultrasonic treatment to obtain a mixture;
step three, placing the mixture obtained in the step two into a mold, and then placing the mold in a heat preservation box for heat preservation and standing to form hydrogel;
and step four, removing the film from the hydrogel formed in the step three, soaking the hydrogel in deionized water, and then freeze-drying the hydrogel to obtain the flexible block amine modified three-dimensional graphene mesoporous material.
The method comprises the steps of uniformly mixing a high amine aqueous solution and a graphene oxide dispersion liquid, carrying out ultrasonic treatment, carrying out heat preservation and standing, and carrying out freeze drying to obtain a flexible block amine modified three-dimensional graphene mesoporous material, namely, taking graphene oxide as a matrix, taking high amine molecules in the high amine aqueous solution as a cross-linking agent, mixing the graphene oxide and the cross-linking agent, carrying out heat preservation and standing, modifying the three-dimensional graphene mesoporous material by utilizing the interaction of hydrogen bonds and static electricity between sheets of the graphene oxide and the cross-linking agent with high amine density through a one-step sol-gel process, controlling the temperature and time of heat preservation and standing, realizing regulation and control of the internal appearance and pore structure of the mesoporous material, promoting the communication of pores, forming a fluffy and unstacked three-dimensional porous structure, improving the amine loading capacity of the mesoporous material, and further enhancing the adsorption performance of gases such as carbon dioxide gas; meanwhile, the hydrogel is dried by adopting a freeze drying method, so that the mesoporous material keeps a complete block structure and has high resilience, and finally the mesoporous material with the complete structure, excellent adsorption performance and high resilience block is obtained.
The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized in that in the first step, the concentration of the graphene oxide aqueous solution is 2 mg/mL-10 mg/mL, the concentration of the sodium hydroxide aqueous solution is 4mg/mL, and the adjusted pH value is 8.0. The optimized adjusted pH effectively prevents the subsequent graphene oxide dispersion liquid from forming flocculated substances after being mixed with the high amine aqueous solution, and ensures the smooth proceeding of the modification process.
The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized in that in the second step, the amine in the high amine aqueous solution is one or more than two of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and polyethylene imine. The amine in the high amine aqueous solution has wide sources, and the feasibility of the preparation method is improved.
The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized in that in the second step, the high amine aqueous solution is a polyethyleneimine aqueous solution, the concentration of the polyethyleneimine aqueous solution is 10 mg/mL-30 mg/mL, and the mass ratio of the polyethyleneimine in the polyethyleneimine aqueous solution to the graphene oxide in the graphene oxide dispersion liquid is 6: 1-1: 6. Aqueous solutions of the preferred class of high amines are relatively easy to obtain and the preparation conditions are simpler and milder.
The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized by pouring the mixture into a mold, covering the mold with a preservative film, pricking small holes on the preservative film, and then placing the mold in a heat preservation box to preserve heat at 20-90 ℃ and standing for 12-24 hours. The preferable temperature and time range of the heat preservation and standing is wide, and the temperature and time range can be conveniently adjusted according to actual conditions, wherein the higher temperature is favorable for accelerating the forming of the internal structure of the hydrogel and shortening the gelation time; meanwhile, the molds with different shapes can be selected according to application requirements to obtain hydrogels with different shapes, so that the application requirements of mesoporous materials with different shapes can be met.
The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized in that the deionized water is soaked for 1 hour in the fourth step; the temperature of the freeze drying is not more than-4 ℃, the pressure is not more than 20Pa, and the time is 48 h. The adverse effect of unreacted residual high amine aqueous solution on the surface of the hydrogel on the mesoporous material is effectively removed through the optimal soaking time; the optimized freeze drying process parameters ensure that water in the pores of the hydrogel is fully frozen and sublimated, so that the mesoporous material is effectively ensured to keep a complete block structure and has high resilience.
In addition, the invention also provides application of the flexible block amine modified three-dimensional graphene mesoporous material prepared by the method in the aspect of adsorbing carbon dioxide.
The flexible block amine modified three-dimensional graphene mesoporous material prepared by the method has the advantages that the connectivity of the pore channel is good, the specific surface area of the pore channel is high, the amine loading capacity of the mesoporous material is greatly improved, the specific adsorption is realized after the amine functional group and carbon dioxide molecules are bonded, the adsorption performance of the mesoporous material to carbon dioxide is greatly improved and enhanced, and the emission of carbon dioxide gas is reduced; meanwhile, the mesoporous material has the advantages of complete structure, high resilience and good mechanical strength, thereby having good application performance, being suitable for various adsorption environments and expanding the application range of the mesoporous material.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, graphene oxide is used as a matrix, high amine molecules in a high amine aqueous solution are used as a cross-linking agent, the internal appearance and the pore structure of the mesoporous material are regulated and controlled by controlling the temperature and time of the action of the sheet layer of the graphene and the high amine molecules, the amine loading capacity of the mesoporous material is improved, the adsorption performance of carbon dioxide gas is further enhanced, and meanwhile, the mesoporous material is enabled to keep a complete and high-resilience block structure by combining a freeze-drying method, so that the mesoporous material has high mechanical strength and is convenient to apply.
2. The method realizes the regulation and control of the amine loading capacity and the carbon dioxide gas adsorption performance of the mesoporous material by controlling the temperature and the time of heat preservation and standing, meets various use requirements, and enlarges the application range of the method.
3. The content of nitrogen element in the flexible block amine modified three-dimensional graphene mesoporous material prepared by the invention is up to 30%.
4. According to the invention, the structure-function integrated flexible block amine modified three-dimensional graphene mesoporous material with complete structure and excellent adsorption performance can be obtained by a one-step sol-gel process, and the preparation process is simple and easy to implement, pollution-free and easy for industrial application.
5. The flexible block amine modified three-dimensional graphene mesoporous material prepared by the invention has the advantages of good adsorption performance on carbon dioxide gas, complete structure, high resilience, good mechanical strength, suitability for various adsorption environments and wide application range.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is an external topography of a flexible block amine modified three-dimensional graphene mesoporous material prepared in embodiment 1 of the present invention.
Fig. 2 is a surface micro-topography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in example 1 of the present invention.
Fig. 3 is a carbon dioxide adsorption curve diagram of the flexible block amine modified three-dimensional graphene mesoporous material prepared in embodiment 1 of the present invention.
Fig. 4 is a surface micro-topography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in example 2 of the present invention.
Fig. 5 is a surface micro-topography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in example 3 of the present invention.
Fig. 6 is a surface micro-topography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in example 6 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, placing a graphene oxide aqueous solution with the concentration of 10mg/mL into an ultrasonic water bath for ultrasonic dispersion twice, wherein the ultrasonic time is 0.5h each time, and then adjusting the pH value to 8.0 by adopting a sodium hydroxide aqueous solution with the concentration of 4mg/mL to obtain a graphene oxide dispersion liquid;
step two, mixing a 30mg/mL polyethyleneimine water solution with the graphene oxide dispersion liquid obtained in the step one, uniformly stirring, and performing ultrasonic treatment for 1min to obtain a mixture; the mass ratio of the polyethyleneimine in the polyethyleneimine water solution to the graphene oxide in the graphene oxide dispersion liquid is 1: 1;
step three, pouring the mixture obtained in the step two into a cylindrical mold, covering the cylindrical mold with a preservative film, pricking small holes on the preservative film, and then placing the cylindrical mold in a heat preservation box to keep the cylindrical mold at 90 ℃ and standing the cylindrical mold for 24 hours to form hydrogel;
step four, removing the film from the hydrogel formed in the step three, soaking the hydrogel in deionized water for 1 hour, and then carrying out freeze drying to obtain a flexible block amine modified three-dimensional graphene mesoporous material with the diameter of 2.5cm and the height of 1 cm; the temperature of the freeze drying is not more than-80 ℃, the pressure is 0.1Pa, and the time is 48 h.
Fig. 1 is an external topography of the flexible block amine modified three-dimensional graphene mesoporous material prepared in this embodiment, and fig. 2 is a surface microscopic topography SEM image of the flexible block amine modified three-dimensional graphene mesoporous material prepared in this embodiment, and as can be seen from fig. 1 and fig. 2, the flexible block amine modified three-dimensional graphene mesoporous material has a complete structure and has a clearly visible 3D pore structure in a random orientation.
Fig. 3 is a carbon dioxide adsorption curve diagram of the flexible bulk amine-modified three-dimensional graphene mesoporous material prepared in this embodiment, and it can be seen from fig. 3 that the adsorption amount of the flexible bulk amine-modified three-dimensional graphene mesoporous material to carbon dioxide gas increases with the increase of pressure, but does not show saturation, which is a typical characteristic of a porous material.
The amine in the high amine aqueous solution of this embodiment may also be one or more than two of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine other than polyethyleneimine.
Example 2
The present embodiment is different from embodiment 1 in that: in the third step, the temperature for heat preservation and standing is 25 ℃, and the time is 12 hours.
Fig. 4 is a surface micro-topography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in this embodiment, and as can be seen from fig. 4, the flexible bulk amine modified three-dimensional graphene mesoporous material does not form a clearly visible 3D pore channel structure, but forms a pore channel structure formed by stacking multiple graphene oxide sheets.
Example 3
The present embodiment is different from embodiment 1 in that: in the first step, the concentration of the graphene oxide aqueous solution is 5 mg/mL; in the second step, the concentration of the polyethyleneimine aqueous solution is 20mg/mL, and the mass ratio of the polyethyleneimine in the polyethyleneimine aqueous solution to the graphene oxide in the graphene oxide dispersion liquid is 6: 1; in the third step, the temperature for heat preservation and standing is 50 ℃ and the time is 18 h.
Fig. 5 is a surface micro-topography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in this embodiment, and as can be seen from fig. 5, the flexible bulk amine modified three-dimensional graphene mesoporous material does not form a clearly visible 3D pore channel structure, but forms a pore channel structure formed by stacking multiple graphene oxide sheets.
Example 4
The present embodiment is different from embodiment 1 in that: in the first step, the concentration of the graphene oxide aqueous solution is 5 mg/mL; in the second step, the concentration of the polyethyleneimine aqueous solution is 20mg/mL, and the mass ratio of the polyethyleneimine in the polyethyleneimine aqueous solution to the graphene oxide in the graphene oxide dispersion liquid is 1: 6; in the third step, the temperature for heat preservation and standing is 50 ℃ and the time is 18 h.
Example 5
The present embodiment is different from embodiment 1 in that: in the first step, the concentration of the graphene oxide aqueous solution is 2 mg/mL; in the second step, the concentration of the polyethyleneimine aqueous solution is 10mg/mL, and the mass ratio of the polyethyleneimine in the polyethyleneimine aqueous solution to the graphene oxide in the graphene oxide dispersion liquid is 1: 1; in the third step, the temperature for heat preservation and standing is 90 ℃, and the time is 24 hours.
Example 6
The present embodiment is different from embodiment 1 in that: in the first step, the concentration of the graphene oxide aqueous solution is 2 mg/mL; in the second step, the concentration of the polyethyleneimine aqueous solution is 10mg/mL, and the mass ratio of the polyethyleneimine in the polyethyleneimine aqueous solution to the graphene oxide in the graphene oxide dispersion liquid is 1: 1; in the third step, the temperature for heat preservation and standing is 20 ℃, and the time is 24 hours.
Fig. 6 is a surface microtopography SEM image of the flexible bulk amine modified three-dimensional graphene mesoporous material prepared in this embodiment, and as can be seen from fig. 6, the flexible bulk amine modified three-dimensional graphene mesoporous material does not form a clearly visible 3D pore channel structure, but forms a pore channel structure formed by stacking multiple graphene oxide sheets, and the sheets are larger.
As can be seen from comparison between fig. 2 and fig. 4 to 6, in example 1, a 3D pore structure is more easily formed inside the prepared dielectric material by adopting a higher heat-preservation standing temperature and a longer heat-preservation standing time; compared with example 1, when the temperature and time of the heat preservation and standing are both reduced, the hydrogen bond and electrostatic interaction capacity between the graphene oxide sheets and the cross-linking agent with high amine density is weakened in examples 2 to 4, and a 3D pore structure cannot be formed, but the pore structure is formed by stacking multiple graphene oxide sheets. In conclusion, the invention realizes the regulation and control of the internal structure and the pore canal shape of the medium material by regulating the temperature and the time of heat preservation and standing in the preparation process.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material is characterized by comprising the following steps:
step one, carrying out ultrasonic dispersion on a graphene oxide aqueous solution, and then adjusting the pH value by using a sodium hydroxide aqueous solution to obtain a graphene oxide dispersion liquid;
step two, mixing the high amine aqueous solution and the graphene oxide dispersion liquid obtained in the step one, stirring uniformly, and performing ultrasonic treatment to obtain a mixture;
step three, placing the mixture obtained in the step two into a mold, and then placing the mold in a heat preservation box for heat preservation and standing to form hydrogel;
and step four, removing the film from the hydrogel formed in the step three, soaking the hydrogel in deionized water, and then freeze-drying the hydrogel to obtain the flexible block amine modified three-dimensional graphene mesoporous material.
2. The method for preparing the flexible bulk amine modified three-dimensional graphene mesoporous material according to claim 1, wherein in the first step, the concentration of the graphene oxide aqueous solution is 2 mg/mL-10 mg/mL, the concentration of the sodium hydroxide aqueous solution is 4mg/mL, and the adjusted pH value is 8.0.
3. The method for preparing the flexible block amine modified three-dimensional graphene mesoporous material according to claim 1, wherein in the second step, the amine in the high amine aqueous solution is one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine.
4. The method for preparing the flexible block amine modified three-dimensional graphene mesoporous material according to claim 3, wherein in the second step, the high amine aqueous solution is a polyethyleneimine aqueous solution, the concentration of the polyethyleneimine aqueous solution is 10 mg/mL-30 mg/mL, and the mass ratio of the polyethyleneimine in the polyethyleneimine aqueous solution to the graphene oxide in the graphene oxide dispersion is 6: 1-1: 6.
5. The preparation method of the flexible block amine modified three-dimensional graphene mesoporous material according to claim 1, wherein the third step is that the mixture is poured into a mold, covered with a preservative film, perforated with small holes, and then placed in a thermal insulation box to be kept at 20-90 ℃ for 12-24 h.
6. The method for preparing the flexible block amine modified three-dimensional graphene mesoporous material according to claim 1, wherein the soaking time of the deionized water in the fourth step is 1 h; the temperature of the freeze drying is not more than-4 ℃, the pressure is not more than 20Pa, and the time is 48 h.
7. The application of the flexible block amine modified three-dimensional graphene mesoporous material prepared by the method according to any one of claims 1-6 in adsorbing carbon dioxide.
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