CN111013540A - Preparation method of graphene magnetic aerogel with high adsorption performance - Google Patents

Preparation method of graphene magnetic aerogel with high adsorption performance Download PDF

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CN111013540A
CN111013540A CN201911395737.7A CN201911395737A CN111013540A CN 111013540 A CN111013540 A CN 111013540A CN 201911395737 A CN201911395737 A CN 201911395737A CN 111013540 A CN111013540 A CN 111013540A
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graphene
preparation
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drying
aerogel
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党阿磊
王羽佳
李铁虎
赵廷凯
李�昊
艾艳玲
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Northwestern Polytechnical University
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Abstract

The invention relates to a preparation method of graphene magnetic aerogel with high adsorption performance, which is prepared from anhydrous sodium acetate, polyvinylpyrrolidone,Preparation of Fe by using ferric chloride hexahydrate and ethylene glycol as raw materials3O4Magnetic nanoparticles; pre-oxidizing the flake graphite by a pre-oxidation method, and then preparing a graphene oxide solution by an improved Hummers method; by solvothermal method of adding Fe3O4And combining with graphene, reducing to prepare the graphene magnetic hydrogel, and finally preparing the graphene magnetic aerogel material by adopting a freeze-drying method. Adsorption experiments show that the graphene magnetic aerogel prepared by the method has the advantages of high adsorption capacity, high surface area and the like, and greatly improves the adsorption performance on pollutants such as dyes, organic solvents, heavy metal particles and the like, so that the graphene magnetic aerogel has a good application prospect in the fields of sewage treatment and the like.

Description

Preparation method of graphene magnetic aerogel with high adsorption performance
Technical Field
The invention belongs to the field of non-metallic composite materials, also belongs to the fields of chemistry, chemical industry, agriculture and environmental engineering, and relates to a preparation method of graphene magnetic aerogel with high adsorption performance.
Background
With the deep industrialization process and the rapid economic development, the living standard of people is greatly improved, but pollutants (such as persistent organic pollutants, heavy metals, dyes, pesticides and the like) inevitably have great influence on the living environment, so that the effective treatment of the pollutants becomes a key problem to be solved urgently.
Three-dimensional foam materials, such as sponges, carbon foams, aerogels and the like, have important research and application values in the fields of heat insulation, sound insulation, energy storage, sensors, catalysis, adsorption, environment and the like due to the characteristics of ultralight weight, large specific surface area, excellent mechanical strength and the like, and the aerogels prepared by a sol-gel process become one of the important research fields in the field of material science due to the unique chemical and physical properties of the aerogels. Compared with other inorganic (such as silicon oxide, aluminum oxide, titanium oxide, etc.) and organic phase aerogels (carbon, cellulose, polyimide, etc.), graphene-based aerogels have the characteristics of light weight, strong adsorption capacity, good electrical conductivity, etc., and thus have received extensive attention from researchers in various countries. However, its application in the field of adsorption is greatly limited due to low mechanical strength, poor flexibility and low selective adsorption.
Magnetic aerogel, as a functional material combining a magnetic material and an aerogel matrix, has important functions in the fields of catalysis, adsorption, separation and the like since the discovery of the magnetic aerogel due to good magnetic functionality. For the preparation of graphene magnetic aerogel, ferrite magnetic nanoparticles (gamma-Fe) are generally selected2O3Manganese ferrite, zinc ferrite and Fe3O4And the like) are magnetic materials, and then are loaded on an aerogel matrix in a chemical grafting or physical dispersion mode to form the graphene magnetic aerogel with special functionalization.
At present, graphene/graphene oxide used for preparing graphene magnetic aerogel is mainly prepared by taking graphite powder as a raw material and adopting a Hummers method or an improved Hummers method. However, the number of layers of graphene/graphene oxide obtained by these methods is mostly 3 to 10, and the content of single-layer or few-layer (1 to 3 layers) graphene is low, so that when the graphene/graphene oxide is used as a raw material to prepare the graphene magnetic aerogel, the microstructure, specific surface area and adsorption performance of the graphene magnetic aerogel are greatly affected by relatively wide layer distribution.
In addition, during the preparation of graphene oxide, a large amount of unreacted or newly generated impurity ions (e.g., Na) contained in the graphene oxide solution+，NO4 -，K+，Mn2+，MnO4 -Etc.) can have great influence on the surface chemical properties of the graphene magnetic aerogel.
Generally, most impurity ions in the solution can be removed by centrifugation, suction filtration, washing, and the like, but many graphene oxide materials are inevitably lost while the impurities are removed, and in addition, some impurity ions still exist in the graphene oxide solution after washing. Therefore, how to reduce the loss of graphene oxide in the purification process while completely removing impurity ions as much as possible still presents a great challenge to the preparation of graphene magnetic aerogel with high adsorption performance and good mechanical stability.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of a graphene magnetic aerogel with high adsorption performance, which can overcome the problems.
Technical scheme
A preparation method of graphene magnetic aerogel with high adsorption performance is characterized by comprising the following steps:
step 1, graphite pre-oxidation: respectively adding the graphite powder, the concentrated nitric acid, the concentrated sulfuric acid and the potassium permanganate into a reaction container according to the mass ratio of 0.5-2: 0.2-1.5, and stirring and mixing to obtain black brown viscous liquid; washing the viscous liquid with water until the pH value is 6.8-7.2, drying, then putting the dried substance into a crucible at the temperature of 800-1000 ℃, covering the crucible with a crucible cover, and cooling the crucible to room temperature to obtain expanded graphite; then taking expanded graphite, potassium persulfate and phosphorus pentoxide, stirring the expanded graphite, the potassium persulfate and the phosphorus pentoxide in a mass ratio of 1-5: 1-4 in concentrated sulfuric acid at 80 ℃ for 1-8 hours, then washing the solution with water to ensure that the pH value is 6.8-7.2, and drying the washed product to obtain pre-oxidized graphite;
step 2, preparation and purification of graphene oxide: fully mixing pre-oxidized graphite and sodium nitrate with concentrated sulfuric acid in a mass ratio of 0.1-1: 0.1-1, and then stirring for 10-60 min at the temperature of 0-8 ℃; after uniform mixing, adding potassium permanganate with the mass ratio of 1-6: 0.1-1 to pre-oxidized graphene to react for 20-100 min, then heating to 30-60 ℃, continuing to react for 10-100 min, and adding 50-150 mL of deionized water; then, continuously heating to 80-100 ℃, keeping the temperature and stirring for 10-40 min, and adding 150-300 mL of deionized water and 1-10 mL of 30% hydrogen peroxide solution when the reaction solution is cooled to room temperature to obtain a golden yellow graphene oxide solution; filtering the obtained graphene oxide solution, and washing the graphene oxide solution for 2-7 times by using deionized water and 5% -10% hydrochloric acid; finally, centrifuging the washed product for 2-7 times under the condition of 1000-3000 rpm, and then carrying out dialysis purification treatment for 3-7 days to obtain a required graphene oxide solution;
step 3, preparing Fe3O4Magnetic nanospheres: taking ferric chloride hexahydrate, polyvinylpyrrolidone and anhydrous sodium acetate, and mixing the raw materials in a mass ratio of 1-5: 1-3: 2-4, mixing and stirring for 30-90 min in a reaction vessel filled with glycol; then placing the mixed solution in a stainless steel hydrothermal reaction kettle, preserving heat for 5-15 hours at 170-250 ℃, and collecting the obtained product through an external magnet; centrifuging the product at room temperature of 3500-4000 rpm for 2-7 times, wherein each time lasts for 4-15 min, drying the centrifuged sample at 50-90 ℃ for 10-20 h, and obtaining the dried product which is magnetic Fe3O4Nanospheres;
step 4, preparing the graphene magnetic aerogel: mixing graphene oxide solution, reducing agent and magnetic Fe3O4Mixing the nanospheres at a mass ratio of 0.1-5: 0.01-0.1: 0.1-5, and performing a solvothermal reaction at 80-100 ℃ to further generate the magnetic graphene hydrogel; and then washing the hydrogel by using an ethanol solution with the volume ratio of 10-40%, and then freeze-drying to obtain the graphene magnetic aerogel.
The drying in the step 1 is drying for 10-20 hours at the temperature of 50-90 ℃.
The particle size diameter of the graphite powder is 50-150 mu m.
The graphite powder is 200-800 meshes and has a particle size of 12-74 mu m.
The reducing agent includes, but is not limited to: hydrogen peroxide, ethylenediamine, hydroiodic acid, oxalic acid, hydrazine hydrate, sodium bisulfite, or ascorbic acid.
The drying includes atmospheric drying, supercritical drying or freeze drying.
The freeze drying method comprises the following steps: the freezing temperature is-20 deg.C to 85 deg.C, the freeze-drying time is selected from 20 to 100h according to the volume of hydrogel, and the vacuum degree is 1 to 12 Pa.
Advantageous effects
The invention provides a preparation method of graphene magnetic aerogel with high adsorption performance, which is used for preparing Fe by taking anhydrous sodium acetate, polyvinylpyrrolidone, ferric chloride hexahydrate and ethylene glycol as raw materials3O4Magnetic nanoparticles; pre-oxidizing the flake graphite by a pre-oxidation method, and then preparing a graphene oxide solution by an improved Hummers method; by solvothermal method of adding Fe3O4And combining with graphene, reducing to prepare the graphene magnetic hydrogel, and finally preparing the graphene magnetic aerogel material by adopting a freeze-drying method. Adsorption experiments show that the graphene magnetic aerogel prepared by the method has the advantages of high adsorption capacity, high surface area and the like, and greatly improves the adsorption performance on pollutants such as dyes, organic solvents, heavy metal particles and the like, so that the graphene magnetic aerogel has a good application prospect in the fields of sewage treatment and the like.
Compared with the prior art, the invention mainly has the advantages and effects that:
(1) the morphology, size and number of layers of the graphene oxide can greatly influence the microstructure and specific surface area of the graphene magnetic aerogel, so that the pre-oxidized graphite which is easy to perform redox intercalation reaction is prepared by performing high-temperature (800-1000 ℃) pre-oxidation treatment on a graphite raw material, the content of the prepared single-layer or few-layer (1-3 layers) graphene oxide is greatly increased, the microstructure and specific surface area of the graphene magnetic aerogel are optimized and improved respectively, and the application of the high specific surface area of the graphene in the field of adsorption is further exerted.
(2) Compared with the method for purifying the graphene oxide solution at the early stage, the method for removing the impurity ions from the graphene oxide solution by using the dialysis purification method greatly reduces the yield of the impurity ions in the graphene oxide solution under the condition of improving the yield of the graphite oxide. Meanwhile, on the premise of improving the mechanical stability of the aerogel, the selectivity and the adsorption capacity of the adsorption material can be increased, the reusability is realized, and the use cost of the adsorption material and the loss of energy are greatly reduced.
(3) Meanwhile, the adsorbed aerogel can be separated and utilized through the magnet, so that secondary pollution caused by other methods to an adsorption solution is reduced, and the method has a very strong application prospect in the fields of environmental protection, sewage treatment and the like.
(4) Through adsorption tests on different dyes, heavy metal ions and organic solutions, compared with other aerogels, the graphene magnetic aerogel prepared by the method has good mechanical properties, high adsorption capacity and capability of adsorbing various pollutants.
Drawings
Fig. 1 is a flow chart of a method for preparing a graphene magnetic aerogel;
fig. 2 is a transmission electron micrograph of graphene oxide prepared in example 1;
FIG. 3 is example 1Fe3O4Scanning electron microscope images of magnetic nanoparticles;
FIG. 4 is a scanning electron micrograph of the graphene magnetic aerogel of example 1;
FIG. 5 is a transmission electron micrograph of the graphene magnetic aerogel in example 1;
fig. 6 is a macroscopic compression performance test chart of the graphene magnetic aerogel of example 1;
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
in the embodiment of the invention, the adsorption performance of the graphene magnetic aerogel is researched through the adsorption capacity and the adsorption rate of dyes (methylene blue, methyl orange, congo red and rhodamine B), heavy metal ions (divalent Cu ions Cd ions) and organic solvents (tetrahydrofuran, n-hexane and xylene).
The method specifically comprises the following steps:
(1) pre-oxidizing graphite: respectively taking the graphite powder (the particle diameter is 50-150 mu m), concentrated nitric acid, concentrated sulfuric acid and potassium permanganate, adding the graphite powder, the concentrated nitric acid, the concentrated sulfuric acid and the potassium permanganate into a reaction container according to the mass ratio of (0.5-2) to (0.2-1.5) to stir and mix to obtain black brown viscous liquid. And then, washing the viscous liquid with water (until the pH value is 6.8-7.2) and drying (drying at the temperature of 50-90 ℃ for 10-20 h), immediately putting the dried sample into a crucible at the temperature of 800-1000 ℃, covering the crucible, and cooling the crucible to room temperature to obtain the expanded graphite sample. And then taking the expanded graphite, potassium persulfate and phosphorus pentoxide, stirring the expanded graphite, the potassium persulfate and the phosphorus pentoxide in a mass ratio of (1-5) to (1-4) in concentrated sulfuric acid at 80 ℃ for 1-8 hours, washing the solution with water until the pH value is 6.8-7.2, and drying the washed product at 50-90 ℃ for 10-20 hours to obtain pre-oxidized graphite.
(2) Preparing and purifying graphene oxide: and (2) fully mixing the pre-oxidized graphite obtained in the step (1) and sodium nitrate with concentrated sulfuric acid in a mass ratio of (0.1-1) to (0.1-1) in a reaction container, and then stirring for 10-60 min at the temperature of 0-8 ℃. After the mixture is uniformly mixed, adding potassium permanganate with the mass ratio of (1-6) to (0.1-1) to the pre-oxidized graphene to react for 20-100 min, then heating to 30-60 ℃, continuing to react for 10-100 min, and adding 50-150 mL of deionized water. And then continuously heating to 80-100 ℃, keeping the temperature and stirring for 10-40 min, and adding 150-300 mL of deionized water and 1-10 mL of 30% hydrogen peroxide solution when the reaction solution is cooled to room temperature to obtain a golden yellow graphene oxide solution. And filtering the obtained graphene oxide solution, and washing the graphene oxide solution for 2-7 times by using deionized water and 5% -10% hydrochloric acid. And finally, centrifuging the washed product for 2-7 times under the condition of 1000-3000 rpm, and then performing dialysis purification treatment (for about 3-7 days) to obtain the graphene oxide solution required by the experiment.
(3) Preparation of Fe3O4Magnetic nanospheres: taking ferric chloride hexahydrate, polyvinylpyrrolidone and anhydrous sodium acetate according to the mass ratio of (1-5): (1-3): (2-4) mixing and stirring (stirring for 30-90 min) in a reaction vessel filled with ethylene glycol. And then placing the mixed solution in a stainless steel hydrothermal reaction kettle, preserving heat for 5-15 hours at the temperature of 170-250 ℃, and collecting the obtained product through an external magnet. Centrifuging the product at room temperature of 3500-4000 rpm for 2-7 times, wherein each time lasts for 4-15 min, drying the centrifuged sample at 50-90 ℃ for 10-20 h, and obtaining the dried product which is magnetic Fe3O4Nanospheres.
(4) Preparing graphene magnetic aerogel: graphene oxide and ethylenediamine in step (2) and graphene oxide and ethylenediamine in step (3)Fe3O4The mass ratio of (0.1-5): (0.01-0.1): (0.1-5), and then carrying out solvothermal reaction for a certain time at 80-100 ℃ to further generate the magnetic graphene hydrogel. And then washing the hydrogel by using an ethanol solution with the volume ratio of 10-40%, and then freeze-drying to obtain the graphene magnetic aerogel.
In the step (1), graphite serving as a preferable raw material is 200 to 800 meshes and has a particle size of 74 to 12 μm.
In the step (2), the solution after centrifugation is washed by suction filtration, dialysis, standing and centrifugation. Preferably, a dialysis method is used. The dialysis time is 3 to 7 days.
In the step (4), the reducing agent includes any one of hydrogen peroxide, ethylenediamine, hydroiodic acid, oxalic acid, hydrazine hydrate, sodium bisulfite and ascorbic acid. Preferably, ethylenediamine is used as the reducing agent.
In the step (4), the mass ratio of the graphene oxide to the preferred reducing agent ethylenediamine is (0.1-5): (0.01-0.1).
In the step (4), the drying method comprises any one of normal pressure drying, supercritical drying and freeze drying, preferably, the freeze drying method is selected, the freezing temperature is-20-85 ℃,
the freeze-drying time is selected from 20 to 100 hours according to the volume of the hydrogel, and the vacuum degree is 1-12 Pa.
In the specific embodiment of the invention, pre-oxidized graphite oxide or non-pre-oxidized graphite is used as a raw material, graphene oxide is prepared by utilizing a method combining an improved Hummers method and liquid phase dialysis or an improved Hummers method, and then Fe is prepared by a hydrothermal method3O4And finally, combining the magnetic nanoparticles and the graphene oxide by a solvothermal method to prepare the graphene magnetic aerogel with uniformly dispersed magnetic nanoparticles, as shown in fig. 1. The invention is described in detail below with reference to the figures and the specific examples.
Example 1:
pre-oxidizing graphite powder and dialyzing and purifying the generated graphene oxide solution.
(1) Respectively taking the graphite powder (the particle diameter is 50-150 mu m), concentrated nitric acid, concentrated sulfuric acid and potassium permanganate, adding the graphite powder, the concentrated nitric acid, the concentrated sulfuric acid and the potassium permanganate into a reaction container according to the mass ratio of (0.5-2) to (0.2-1.5) to stir and mix to obtain black brown viscous liquid. And then, washing the viscous liquid with water (until the pH value is 6.8-7.2) and drying (drying at the temperature of 50-90 ℃ for 10-20 h), immediately putting the dried sample into a crucible at the temperature of 800-1000 ℃, covering the crucible, and cooling the crucible to room temperature to obtain the expanded graphite sample. And then taking the expanded graphite, potassium persulfate and phosphorus pentoxide, stirring the expanded graphite, the potassium persulfate and the phosphorus pentoxide in a mass ratio of (1-5) to (1-4) in concentrated sulfuric acid at 80 ℃ for 1-8 hours, washing the solution with water until the pH value is 6.8-7.2, and drying the washed product at 50-90 ℃ for 10-20 hours to obtain pre-oxidized graphite. Fully mixing pre-oxidized graphite and sodium nitrate with concentrated sulfuric acid in a mass ratio of (0.1-1) to (0.1-1) in a reaction vessel, and then stirring for 10-60 min at the temperature of 0-8 ℃. After the mixture is uniformly mixed, adding potassium permanganate with the mass ratio of (1-6) to (0.1-1) to the pre-oxidized graphene to react for 20-100 min, then heating to 30-60 ℃, continuing to react for 10-100 min, and adding 50-150 mL of deionized water. And then continuously heating to 80-100 ℃, keeping the temperature and stirring for 10-40 min, and adding 150-300 mL of deionized water and 1-10 mL of 30% hydrogen peroxide solution when the reaction solution is cooled to room temperature to obtain a golden yellow graphene oxide solution. And filtering the obtained graphene oxide solution, and washing the graphene oxide solution for 2-7 times by using deionized water and 5% -10% hydrochloric acid. And finally, centrifuging the washed product for 2-7 times under the condition of 1000-3000 rpm, and then performing dialysis purification treatment (for about 3-7 days) to obtain the graphene oxide solution required by the experiment.
2) Taking ferric chloride hexahydrate, polyvinylpyrrolidone and anhydrous sodium acetate according to the mass ratio of (1-5): (1-3): (2-4) mixing and stirring (stirring for 30-90 min) in a reaction vessel filled with ethylene glycol. And then placing the mixed solution in a stainless steel hydrothermal reaction kettle, preserving heat for 5-15 hours at the temperature of 170-250 ℃, and collecting the obtained product through an external magnet. Then, the product is processed at 3500-4 DEGCentrifuging at the room temperature of 000rpm for 2-7 times, each time for 4-15 min, drying the centrifuged sample at the temperature of 50-90 ℃ for 10-20 h, and obtaining the dried product which is magnetic Fe3O4Nanospheres.
(3) Mixing the graphene oxide prepared in the step (1), ethylenediamine and Fe in the step (2)3O4The mass ratio of (0.1-5): (0.01-0.1): (0.1-5), and then carrying out solvothermal reaction for a certain time at 80-100 ℃ to further generate the magnetic graphene hydrogel. And then washing the hydrogel by using an ethanol solution with the volume ratio of 10-40%, and then freeze-drying to obtain the graphene magnetic aerogel.
The graphene oxide and Fe in the step (3)3O4The mass ratio of the nanospheres is (0.1-5) to (0.1-5).
The mass ratio of the graphene oxide to the preferable reducing agent ethylenediamine in the step (3) is (0.1-5): (0.01 to 0.1);
the thickness of the graphene prepared in the step (3) is 1.062nm, which indicates that the prepared graphene has 1-3 layers, and is shown in fig. 2;
magnetic Fe produced in step (2)3O4The average size of the nanospheres is about 200-250 nm, see figure 3;
in the magnetic graphene aerogel obtained in the step (3), Fe3O4The nanospheres are uniformly dispersed in the aerogel matrix, see fig. 4 and 5;
the magnetic aerogel prepared in the step (3) has good flexibility, and under the pressure condition of 100g weight, the recovery rate of the aerogel reaches 98% after 50 times of repeated compression, which indicates that the prepared magnetic aerogel has good mechanical stability and flexibility, and is shown in fig. 6.
The saturated adsorption amounts of the magnetic aerogel prepared in the step (3) on dyes of methylene blue, methyl orange, rhodamine B and Congo red reach 545mg/g, 373mg/g, 552mg/g and 312.5mg/g respectively, the saturated adsorption amounts on heavy metal divalent Cu ions and Cd ions reach 116mg/g and 244mg/g respectively, and the saturated adsorption amounts on organic solvents of tetrahydrofuran, n-hexane and xylene reach 9300mg/g, 5300mg/g and 9750mg/g respectively, which indicates that the prepared magnetic aerogel has good adsorption performance, and refer to the following table.
Name (R) Methylene blue Methyl orange Rhodamine B Congo red Cu(Ⅱ) Cd(Ⅱ) Tetrahydrofuran (THF) N-hexane Xylene
Adsorption amount/(mg/g) 545 373 552 312.5 116 244 9300 5300 9750
Adsorption rate/%) 90.9 62.2 91.9 52.1 72.45 78.1 - - -
Example 2:
the graphite powder is pre-oxidized, and the generated graphene oxide solution is not dialyzed and purified.
(1) Respectively taking the graphite powder (the particle diameter is 50-150 mu m), concentrated nitric acid, concentrated sulfuric acid and potassium permanganate, adding the graphite powder, the concentrated nitric acid, the concentrated sulfuric acid and the potassium permanganate into a reaction container according to the mass ratio of (0.5-2) to (0.2-1.5) to stir and mix to obtain black brown viscous liquid. And then, washing the viscous liquid with water (until the pH value is 6.8-7.2) and drying (drying at the temperature of 50-90 ℃ for 10-20 h), immediately putting the dried sample into a crucible at the temperature of 800-1000 ℃, covering the crucible, and cooling the crucible to room temperature to obtain the expanded graphite sample. And then taking the expanded graphite, potassium persulfate and phosphorus pentoxide, stirring the expanded graphite, the potassium persulfate and the phosphorus pentoxide in a mass ratio of (1-5) to (1-4) in concentrated sulfuric acid at 80 ℃ for 1-8 hours, washing the solution with water until the pH value is 6.8-7.2, and drying the washed product at 50-90 ℃ for 10-20 hours to obtain pre-oxidized graphite. Fully mixing pre-oxidized graphite and sodium nitrate with concentrated sulfuric acid in a mass ratio of (0.1-1) to (0.1-1) in a reaction vessel, and then stirring for 10-60 min at the temperature of 0-8 ℃. After the mixture is uniformly mixed, adding potassium permanganate with the mass ratio of (1-6) to (0.1-1) to the pre-oxidized graphene to react for 20-100 min, then heating to 30-60 ℃, continuing to react for 10-100 min, and adding 50-150 mL of deionized water. And then continuously heating to 80-100 ℃, keeping the temperature and stirring for 10-40 min, and adding 150-300 mL of deionized water and 1-10 mL of 30% hydrogen peroxide solution when the reaction solution is cooled to room temperature to obtain a golden yellow graphene oxide solution. And filtering the obtained graphene oxide solution, and washing the graphene oxide solution for 2-7 times by using deionized water and 5% -10% hydrochloric acid. And finally, centrifuging the washed product for 2-7 times under the condition of 1000-3000 rpm to obtain the graphene oxide solution required by the experiment.
(2) Taking ferric chloride hexahydrate, polyvinylpyrrolidone and anhydrous sodium acetate according to the mass ratio of (1-5): (1-3): (2-4) mixing and stirring (stirring for 30-90 min) in a reaction vessel filled with ethylene glycol. And then placing the mixed solution in a stainless steel hydrothermal reaction kettle, preserving heat for 5-15 hours at the temperature of 170-250 ℃, and collecting the obtained product through an external magnet. Centrifuging the product at room temperature of 3500-4000 rpm for 2-7 times, wherein each time lasts for 4-15 min, drying the centrifuged sample at 50-90 ℃ for 10-20 h, and obtaining the dried product which is magnetic Fe3O4Nanospheres.
(3) Mixing the graphene oxide prepared in the step (1), ethylenediamine and Fe in the step (2)3O4The mass ratio of (0.1-5): (0.01-0.1): (0.1-5), and then carrying out solvothermal reaction for a certain time at 80-100 ℃ to further generate the magnetic graphene hydrogel. And then washing the hydrogel by using an ethanol solution with the volume ratio of 10-40%, and then freeze-drying to obtain the graphene magnetic aerogel.
The graphene oxide and Fe in the step (3)3O4The mass ratio of the nanospheres is (0.1-5): (0.1-5).
The mechanical stability of the magnetic aerogel prepared in step (3) is significantly deteriorated.
The saturated adsorption capacity of the magnetic aerogel prepared in the step (3) on dyes of methylene blue, methyl orange, rhodamine B and Congo red is respectively reduced by 60%, 45%, 72% and 57%, the saturated adsorption capacity on heavy metal divalent Cu ions and Cd ions is respectively reduced by 32% and 43%, and the saturated adsorption capacity on organic solvents of tetrahydrofuran, n-hexane and xylene is respectively reduced by 44%, 51% and 39%.
Example 3:
the graphite powder is not pre-oxidized, and the generated graphene oxide solution is not dialyzed and purified.
(1) The graphite powder and sodium nitrate are fully mixed with concentrated sulfuric acid in a reaction container according to the mass ratio of (0.1-1) to (0.1-1), and then the mixture is stirred for 10-60 min under the condition of heat preservation at 0-8 ℃. After the mixture is uniformly mixed, adding potassium permanganate with the mass ratio of (1-6) to (0.1-1) to the graphite powder to react for 20-100 min, then heating to 30-60 ℃, continuing to react for 10-100 min, and adding 50-150 mL of deionized water. And then continuously heating to 80-100 ℃, keeping the temperature and stirring for 10-40 min, and adding 150-300 mL of deionized water and 1-10 mL of 30% hydrogen peroxide solution when the reaction solution is cooled to room temperature to obtain a golden yellow graphene oxide solution. And filtering the obtained graphene oxide solution, and washing the graphene oxide solution for 2-7 times by using deionized water and 5% -10% hydrochloric acid. And finally, centrifuging the washed product for 2-7 times under the condition of 1000-3000 rpm to obtain the graphene oxide solution required by the experiment.
(2) Taking ferric chloride hexahydrate, polyvinylpyrrolidone and anhydrous sodium acetate according to the mass ratio of (1-5): (1-3): (2-4) mixing and stirring (stirring for 30-90 min) in a reaction vessel filled with ethylene glycol. And then placing the mixed solution in a stainless steel hydrothermal reaction kettle, preserving heat for 5-15 hours at the temperature of 170-250 ℃, and collecting the obtained product through an external magnet. Centrifuging the product at room temperature of 3500-4000 rpm for 2-7 times, wherein each time lasts for 4-15 min, drying the centrifuged sample at 50-90 ℃ for 10-20 h, and obtaining the dried product which is magnetic Fe3O4Nanospheres.
(3) Mixing the graphene oxide prepared in the step (1), ethylenediamine and Fe in the step (2)3O4The mass ratio of (0.1-5): (0.01-0.1): (0.1-5), and then carrying out solvothermal reaction for a certain time at 80-100 ℃ to further generate the magnetic graphene hydrogel. And then washing the hydrogel by using an ethanol solution with the volume ratio of 10-40%, and then freeze-drying to obtain the graphene magnetic aerogel.
In the step (3)The graphene oxide and Fe3O4The mass ratio of the nanospheres is (0.1-5): (0.1-5).
The mechanical stability of the magnetic aerogel prepared in step (3) is significantly deteriorated.
The saturated adsorption capacity of the magnetic aerogel prepared in the step (3) on dyes of methylene blue, methyl orange, rhodamine B and Congo red is respectively reduced by 43%, 36%, 40% and 47%, the saturated adsorption capacity on heavy metal divalent Cu ions and Cd ions is respectively reduced by 27% and 21%, and the saturated adsorption capacity on organic solvents of tetrahydrofuran, n-hexane and xylene is respectively reduced by 32%, 29% and 41%.
Name (R) Methylene blue Methyl orange Rhodamine B Congo red Cu(Ⅱ) Cd(Ⅱ) Tetrahydrofuran (THF) N-hexane Xylene
Adsorption amount/(mg/g) 545 373 552 312.5 116 244 9300 5300 9750
Adsorption rate/%) 90.9 62.2 91.9 52.1 72.45 78.1 - - -

Claims (7)

1. A preparation method of graphene magnetic aerogel with high adsorption performance is characterized by comprising the following steps:
step 1, graphite pre-oxidation: respectively taking lithopone powder, concentrated nitric acid, concentrated sulfuric acid and potassium permanganate, adding the lithopone powder, the concentrated nitric acid, the concentrated sulfuric acid and the potassium permanganate into a reaction container according to the mass ratio of 0.5-2: 0.2-1.5, and stirring and mixing to obtain dark brown viscous liquid; washing the viscous liquid with water until the pH value is 6.8-7.2, drying, then putting the dried substance into a crucible at the temperature of 800-1000 ℃, covering the crucible with a crucible cover, and cooling the crucible to room temperature to obtain expanded graphite; taking expanded graphite, potassium persulfate and phosphorus pentoxide, stirring at a mass ratio of 1-5: 1-4 in concentrated sulfuric acid at 80 ℃ for 1-8 h, washing the solution with water to ensure that the pH value is 6.8-7.2, and drying the product after washing to obtain pre-oxidized graphite;
step 2, preparation and purification of graphene oxide: fully mixing pre-oxidized graphite and sodium nitrate with concentrated sulfuric acid in a mass ratio of 0.1-1: 0.1-1, and then stirring for 10-60 min at the temperature of 0-8 ℃; after uniform mixing, adding potassium permanganate with the mass ratio of 1-6: 0.1-1 to pre-oxidized graphene to react for 20-100 min, then heating to 30-60 ℃, continuing to react for 10-100 min, and adding 50-150 mL of deionized water; then, continuously heating to 80-100 ℃, keeping the temperature and stirring for 10-40 min, and adding 150-300 mL of deionized water and 1-10 mL of 30% hydrogen peroxide solution when the reaction solution is cooled to room temperature to obtain a golden yellow graphene oxide solution; filtering the obtained graphene oxide solution, and washing the graphene oxide solution for 2-7 times by using deionized water and 5% -10% hydrochloric acid; finally, centrifuging the washed product for 2-7 times under the condition of 1000-3000 rpm, and then carrying out dialysis purification treatment for 3-7 days to obtain a required graphene oxide solution;
step 3, preparing Fe3O4Magnetic nanospheres: mixing ferric chloride hexahydrate, polyvinylpyrrolidone and anhydrous sodium acetate in a reaction vessel filled with glycol according to the mass ratio of 1-5: 1-3: 2-4 for 30-90 min; then placing the mixed solution in a stainless steel hydrothermal reaction kettle, preserving heat for 5-15 hours at 170-250 ℃, and collecting the obtained product through an external magnet; centrifuging the product at room temperature of 3500-4000 rpm for 2-7 times, wherein each time lasts for 4-15 min, drying the centrifuged sample at 50-90 ℃ for 10-20 h, and obtaining the dried product which is magnetic Fe3O4Nanospheres;
step 4, preparing the graphene magnetic aerogel: mixing graphene oxide solution, reducing agent and magnetic Fe3O4Mixing the nanospheres at a mass ratio of 0.1-5: 0.01-0.1: 0.1-5, and performing a solvothermal reaction at 80-100 ℃ to further generate the magnetic graphene hydrogel; and then washing the hydrogel by using an ethanol solution with the volume ratio of 10-40%, and then freeze-drying to obtain the graphene magnetic aerogel.
2. The preparation method of the graphene magnetic aerogel with high adsorption performance according to claim 1, wherein the preparation method comprises the following steps: the drying in the step 1 is drying for 10-20 hours at the temperature of 50-90 ℃.
3. The preparation method of the graphene magnetic aerogel with high adsorption performance according to claim 1, wherein the preparation method comprises the following steps: the particle size diameter of the graphite powder is 50-150 mu m.
4. The preparation method of the graphene magnetic aerogel with high adsorption performance according to claim 3, wherein the preparation method comprises the following steps: the graphite powder is 200-800 meshes and has a particle size of 12-74 mu m.
5. The preparation method of the graphene magnetic aerogel with high adsorption performance according to claim 1, wherein the preparation method comprises the following steps: the reducing agent includes, but is not limited to: hydrogen peroxide, ethylenediamine, hydroiodic acid, oxalic acid, hydrazine hydrate, sodium bisulfite, or ascorbic acid.
6. The preparation method of the graphene magnetic aerogel with high adsorption performance according to claim 1, wherein the preparation method comprises the following steps: the drying includes atmospheric drying, supercritical drying or freeze drying.
7. The preparation method of the graphene magnetic aerogel with high adsorption performance according to claim 6, wherein the preparation method comprises the following steps: the freeze drying method comprises the following steps: the freezing temperature is-20 deg.C to 85 deg.C, the freeze-drying time is selected from 20 to 100h according to the volume of hydrogel, and the vacuum degree is 1 to 12 Pa.
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