CN110564365A - Preparation method of graphene foam composite material loaded with magnetic hollow nanospheres - Google Patents

Preparation method of graphene foam composite material loaded with magnetic hollow nanospheres Download PDF

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CN110564365A
CN110564365A CN201910826320.5A CN201910826320A CN110564365A CN 110564365 A CN110564365 A CN 110564365A CN 201910826320 A CN201910826320 A CN 201910826320A CN 110564365 A CN110564365 A CN 110564365A
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composite material
graphene
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graphene foam
metal salt
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CN110564365B (en
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陈平
刘佳良
徐东卫
于祺
陈博涵
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Dalian University of Technology
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    • C09K3/00Materials not provided for elsewhere
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0063Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use in a non-magnetic matrix, e.g. granular solids

Abstract

A preparation method of a graphene foam composite material loaded with magnetic hollow nanospheres belongs to the technical field of wave-absorbing composite materials. The method comprises the steps of preparing three-dimensional reticular graphene oxide foam loaded with glycerate metal salt by using graphene oxide, hexadecyl trimethyl ammonium bromide and metal salt as raw materials and adopting a solvothermal method; and after freeze drying, roasting and reducing in a protective atmosphere, and in situ obtaining the graphene foam composite material loaded with the magnetic hollow nanospheres. The prepared graphene foam composite material has the characteristics of small density, light weight and high specific surface area, and the method is simple to operate, low in cost and simple in preparation process, and is a novel technology for massively preparing the magnetic graphene foam composite material. By adjusting the proportion of the graphene and the metal salt, the magnetic property and the electrical property of the composite material can be adjusted. The graphene foam composite material loaded with the magnetic hollow nanospheres prepared by the invention has excellent electromagnetic performance and can be used as an electromagnetic wave absorption material.

Description

Preparation method of graphene foam composite material loaded with magnetic hollow nanospheres
Technical Field
The invention belongs to the technical field of wave-absorbing composite materials, and relates to a preparation technology of a graphene foam loaded magnetic hollow nanosphere composite material.
background
In recent decades, with the rapid development and wide application of electronic information technology, electromagnetic wave pollution exists in various aspects of life, which not only interferes with the normal operation of electronic instruments, but also creates potential safety hazards to the health of human beings. In addition, the electromagnetic wave absorbing material is the core of radar absorption technology and has important value in the fields of aerospace and national defense, so that the development of the electromagnetic wave absorbing material with strong absorption, thin thickness, light weight and wide frequency band has important significance.
the magnetic nano material is a hotspot of modern wave-absorbing material research because of the advantages of high saturation magnetization, large magnetic conductivity and the like, and the magnetic nano particles play a role in magnetic loss of electromagnetic waves and mainly show excellent wave-absorbing performance at high frequency. The defects of high density and easy agglomeration exist, the dispersion of the nano magnetic particles and the reduction of the filling amount are a technical difficulty, and the synthesis of the magnetic hollow nanospheres can well reduce the filling amount of materials.
The graphene is sp2The two-dimensional material which is formed by the hybrid tracks and has a hexagonal honeycomb lattice has a series of advantages of high conductivity, thermal stability, corrosion resistance, large specific surface area, light weight, high electron mobility and the like, and the characteristics enable the graphene to become an excellent dielectric loss type wave-absorbing material. However, the single magnetic material or graphene can reduce the impedance matching degree, cannot meet the comprehensive requirements of modern wave-absorbing materials, and has limited absorption and attenuation of electromagnetic waves. Therefore, how to combine graphene and magnetic particles to prepare graphene loaded with magnetic particles and coordinate dielectric loss and magnetic loss of the graphene and the magnetic particles becomes an important method for preparing the high-performance wave-absorbing material.
The graphene foam is a novel three-dimensional porous material, has the excellent properties of low specific density, high porosity, large specific surface, strong adsorbability and the like, and is widely applied to a plurality of fields. When the graphene foam material is combined with magnetic nanoparticles, the carrying capacity and the effective action area of the material can be greatly improved while the characteristics of graphene foam are maintained, and the possibility of agglomeration of the particles can be effectively reduced.
At present, a method for preparing the graphene foam loaded magnetic nano hollow sphere composite material by a two-step method is not reported. Therefore, in order to further exert the respective advantages of the magnetic hollow nanospheres and the graphene foam, a technology which is environment-friendly, time-saving, efficient and suitable for large-scale preparation is invented, and the graphene foam composite material loaded with the magnetic hollow nanospheres and having excellent electromagnetic wave absorption performance is prepared.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a graphene foam loaded magnetic hollow nanosphere composite material, which is environment-friendly, time-saving and efficient. According to the method, graphene oxide, CTAB and metal salts of iron, cobalt, nickel and zinc are used as raw materials, an isopropanol and glycerol system is used as a solvent, and a solvothermal method is adopted to prepare the three-dimensional porous graphene foam loaded with the glycerate metal salts; carrying out freeze drying and roasting reduction in a protective atmosphere to obtain the graphene foam composite material loaded with the magnetic nanoparticles in situ; the prepared graphene foam loaded with the magnetic hollow nanospheres has the characteristics of high specific surface area and low density, the magnetic property and the dielectric property of the composite material are adjusted and controlled by adjusting the adding amount of the metal salt and the graphene oxide, and the wave-absorbing material with excellent performance is prepared. The method solves the problems that in the prior art, the binding force between graphene and magnetic particles is insufficient, the magnetic particles cannot be uniformly loaded on the graphene, the magnetic particles are easy to agglomerate, and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
A preparation method of a magnetic hollow nanosphere-loaded graphene foam composite material comprises the following steps:
(1) graphene oxides with different oxidation degrees are prepared according to a hummers method, and graphene oxide powder is obtained through freeze drying.
The hummers method specifically comprises the following steps: under the low-temperature environment of ice-water bath, adding the crystalline flake graphite and a strong oxidant into a strong acid solution, stirring and mixing uniformly, and keeping the system at a low temperature (0-10 ℃) for 30-240 min; then raising the temperature of the system to 35-40 ℃, continuously stirring for 2-4h, and then adding deionized water; raising the temperature of the system to 90-95 ℃ and keeping the temperature for 30-40 min; adding a proper amount of deionized water and H after the reaction is finished2O2stopping stirring, standing and layering, taking the lower-layer graphite oxide suspension, sequentially carrying out acid washing and water washing, finally carrying out ultrasonic treatment to obtain graphene oxide colloidal suspension, and carrying out freeze drying to obtain graphene oxide powder.
(2) Uniformly mixing the graphene oxide powder prepared in the step (1) with isopropanol, performing ultrasonic treatment for 1-2 hours, adding metal salt, CTAB, glycerol and water, and uniformly mixing to prepare a reaction solution; and injecting the reaction solution into a hydrothermal synthesis kettle to perform a solvothermal reaction, reacting at the reaction temperature of 160-220 ℃ for 6-24h, and after the reaction is finished, separating, washing with water, and freeze-drying to obtain the metal salt-loaded graphene foam precursor.
The reaction solution comprises the following substances in proportion: graphene oxide powder, isopropanol, glycerol, water, CTAB and a metal salt, wherein the amount of the metal salt is 100-400mg, the amount of the metal salt is 50-70mL, the amount of the metal salt is 7-10mL, the amount of the metal salt is 0-2mL, and the amount of the metal salt is 0-2000mg, and the metal salt is 500-3000 mg.
The metal salt is one of cobalt nitrate, ferric nitrate, nickel nitrate, zinc nitrate, ferric acetate, cobalt acetate, nickel acetate, zinc acetate and a combination thereof.
(3) And (4) calcining the metal salt loaded graphene foam precursor obtained in the step (3) at high temperature under the protection of inert gas, wherein the high-temperature calcination temperature is 350-1000 ℃, and the time is 30-300 min, so as to finally obtain the magnetic hollow nanosphere loaded graphene foam.
The inert gas is nitrogen, argon, helium, neon or a mixture of more than two gases; the flow of the protective gas is 40-100 mL/min; the heating rate is 1-10 ℃/min.
The graphene foam loaded hollow nanosphere composite material prepared by the invention has excellent electromagnetic performance and can be used as an electromagnetic wave-absorbing material.
The invention has the beneficial effects that:
(1) The prepared magnetic particles are nano-level hollow spheres, so that the filling quality is reduced, and the loss of electromagnetic waves in the material is increased.
(2) The prepared graphene foam is of a porous structure, can increase the specific surface area of the composite material and reduce the density of the composite material, and has the characteristics of high specific surface area and light weight, and magnetic hollow nanospheres are loaded on the inner surface and the outer surface of the graphene sheet layer.
(3) The magnetic hollow nanospheres are loaded between the graphene sheet layers, so that the problem of agglomeration of magnetic nanoparticles is solved, and the problem of agglomeration of graphene is also solved.
(4) By adjusting the ratio of the graphene to the metal salt, the electromagnetic performance of the composite material is adjusted, and the effective bandwidth of the material as a wave-absorbing stealth and electromagnetic shielding material is greatly widened. The graphene foam composite material loaded with the magnetic nanoparticles prepared by the invention has excellent electromagnetic performance and can be used as an electromagnetic wave absorption material.
(5) The prepared graphene foam loaded magnetic nanoparticle composite material has the advantages of high wave-absorbing strength, wide wave-absorbing frequency band, light weight, thin thickness and the like, and is more favorable than single graphene or magnetic Fe3O4Has more excellent wave-absorbing performance.
Drawings
FIG. 1 shows Fe-supported catalyst prepared in example 13O4Scanning electron microscope images of the nanoparticle graphene foams.
FIG. 2 is an X-ray diffraction pattern of example 1.
FIG. 3 is a graph showing the reflection loss curves of examples 1 to 5 of the present invention at a thickness of 2.5mm in the range of 1 to 18 GHz.
FIG. 4 is a graph showing reflection loss curves of example 1 of the present invention at various thicknesses in the range of 1 to 18 GHz.
Detailed Description
the present invention is further illustrated by the following specific examples.
example 1:
Step 1: 2.0g of scaleFlake graphite, 50mL concentrated H2SO4The mixture was placed in a 500m three-necked flask and stirred well in an ice-water mixture at 0 ℃. 6.0g of potassium permanganate is weighed and slowly added in batches, and the temperature of the reaction system is controlled at 0 ℃ for reaction for 1 hour. Then the system was transferred to a 35 ℃ water bath and reacted for 3 hours. After the reaction, 100mL of distilled water was slowly added dropwise and the reaction was carried out at 90 ℃ for 40 min. Finally, 100mL of distilled water and 15mLH were added2O2. The product was washed with 5% HCl and distilled water to pH 6-7. And carrying out ultrasonic treatment on the obtained graphite oxide to obtain a graphene oxide solution, and carrying out freeze drying for 24h to obtain graphene oxide powder.
Step 2: ultrasonically stirring and dissolving 200mg of graphene oxide powder in the step 1 and 70ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking as solution A; 10ml of glycerol and 1.212g of ferric nitrate were added to the above solution, sonicated for 1 hour, and 2ml of H was added2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 12 hours at the reaction temperature of 190 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
and step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 40mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 500 ℃, the calcining time is 2 hours, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
FIG. 1 shows Fe-supported catalyst prepared in example 13O4According to the scanning electron microscope image of the nano particle graphene foam, metal particles are uniformly loaded on graphene, and the graphene is in a three-dimensional network structure. FIG. 2 is an X-ray diffraction chart of example 1, in which it can be seen that diffraction peaks appeared corresponding to Fe, respectively3O4The (220), (311), (400), (511) and (440) crystal planes of (A) and (B), and the face-centered cubic system Fe3O4The standard XRD card (JCPDS No.19-0629) is completely consistent. FIG. 4 is a graph showing reflection loss curves of example 1 of the present invention at various thicknesses in the range of 1 to 18GHz, from which it can be seen that when the thickness is 3.1mmThe minimum reflectance value may reach-62 dB, and the minimum reflectance peak is shifted to a high frequency direction as the thickness is gradually decreased.
Example 2:
Step 1: the same as example 1.
Step 2: ultrasonically stirring and dissolving 200mg of graphene oxide powder in the step 1 and 70ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking as solution A; 10ml of glycerol and 0.808g of ferric nitrate were added to the above solution, sonicated for 1 hour, and 2ml of H was added2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 12 hours at the reaction temperature of 190 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
And step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 40mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 500 ℃, the calcining time is 2 hours, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
Example 3:
Step 1: the same as example 1.
Step 2: ultrasonically stirring and dissolving 200mg of graphene oxide powder in the step 1 and 70ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking as solution A; 10ml of glycerol and 1.616g of ferric nitrate were added to the above solution, sonicated for 1 hour, and 2ml of H was added2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 12 hours at the reaction temperature of 190 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
And step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 40mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 500 ℃, the calcining time is 2 hours, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
Example 4:
Step 1: the same as example 1.
Step 2: ultrasonically stirring and dissolving 200mg of graphene oxide powder in the step 1 and 70ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking as solution A; 10ml of glycerol, 0.808g of ferric nitrate and 0.388g of cobalt nitrate were added to the above solution, sonicated for 1 hour, and 2ml of H was added2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 12 hours at the reaction temperature of 190 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
And step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 40mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 500 ℃, the calcining time is 2 hours, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
Example 5:
step 1: the same as example 1.
Step 2: ultrasonically stirring and dissolving 200mg of graphene oxide powder in the step 1 and 70ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking as solution A; 10ml of glycerol, 1.212g of ferric nitrate and 0.97g of cobalt nitrate were added to the above solution, sonicated for 1 hour, and 2ml of H was added2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 12 hours at the reaction temperature of 190 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
And step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 40mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 500 ℃, the calcining time is 2 hours, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
FIG. 3 is a graph showing the reflection loss curves of examples 1 to 5 of the present invention at a thickness of 2.5mm in the range of 1 to 18GHz, and it can be seen that the peak reflectivity of example 1 at this thickness is the smallest, which is-59 dB.
Example 6:
Step 1: 2.0g of flake graphite, 50mL of concentrated H2SO4The mixture was placed in a 500m three-necked flask and stirred well in an ice-water mixture at 0 ℃. 6.0g of potassium permanganate is weighed and slowly added in batches, and the temperature of the reaction system is controlled to be 10 ℃ for reaction for 30 min. Then the system is moved into a water bath at 40 ℃ and reacted for 2 h. After the reaction, 100mL of distilled water was slowly added dropwise and the reaction was carried out at 95 ℃ for 30 min. Finally, 100mL of distilled water and 15mLH were added2O2. The product was washed with 5% HCl and distilled water to pH 6-7. And carrying out ultrasonic treatment on the obtained graphite oxide to obtain a graphene oxide solution, and carrying out freeze drying for 24h to obtain graphene oxide powder.
Step 2: ultrasonically stirring and dissolving 100mg of graphene oxide powder obtained in the step 1 and 70ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking the mixture as solution A; adding 7ml glycerol and 3g ferric nitrate into the solution, performing ultrasonic treatment for 2 hours, and adding 2ml H2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 24 hours at the reaction temperature of 160 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
And step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 100mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 350 ℃, the calcining time is 5 hours, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
Example 7:
Step 1: 2.0g of flake graphite, 50mL of concentrated H2SO4the mixture was placed in a 500m three-necked flask and stirred well in an ice-water mixture at 0 ℃. 6.0g of potassium permanganate is weighed and slowly added in batches, and the temperature of the reaction system is controlled to be 0 ℃ for reaction for 200 min. However, the device is not suitable for use in a kitchenthen the system is moved into a water bath with the temperature of 40 ℃ for reaction for 2 hours. After the reaction, 100mL of distilled water was slowly added dropwise and the reaction was carried out at 95 ℃ for 30 min. Finally, 100mL of distilled water and 15mLH were added2O2. The product was washed with 5% HCl and distilled water to pH 6-7. And carrying out ultrasonic treatment on the obtained graphite oxide to obtain a graphene oxide solution, and carrying out freeze drying for 24h to obtain graphene oxide powder.
step 2: ultrasonically stirring and dissolving 400mg of graphene oxide powder in the step 1 and 50ml of isopropanol until the graphene oxide powder and the isopropanol are uniformly mixed, and marking as solution A; 10ml of glycerol and 0.5g of ferric nitrate were added to the above solution, sonicated for 1 hour, and 2ml of H was added2Stirring for 20 minutes to obtain a mixed reaction solution, injecting the mixed reaction solution into a 150mL hydrothermal synthesis kettle, reacting for 6 hours at the reaction temperature of 220 ℃, and after the reaction is finished, carrying out solid-liquid separation, water washing and freeze drying.
and step 3: and (3) putting the graphene oxide foam loaded with the glycerate salt obtained in the step (2) into a crucible, putting the crucible into a quartz tube of a tube furnace, introducing argon into the quartz tube, wherein the air flow is 80mL/min, after introducing the argon for 20 minutes, the temperature rise rate of the furnace is 5 ℃/min, the calcining temperature is set to be 1000 ℃, the calcining time is 30min, then cooling to the room temperature along with the furnace, and closing the protective gas to obtain the graphene foam loaded with the magnetic hollow nanospheres.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.

Claims (5)

1. a preparation method of a magnetic hollow nanosphere-loaded graphene foam composite material is characterized by comprising the following steps:
(1) Preparing graphene oxide with different oxidation degrees according to a hummers method, and freeze-drying to obtain graphene oxide powder;
(2) Uniformly mixing the graphene oxide powder prepared in the step (1) with isopropanol, performing ultrasonic treatment for 1-2 hours, adding metal salt, CTAB, glycerol and water, and uniformly mixing to prepare a reaction solution; injecting the reaction solution into a hydrothermal synthesis kettle to perform a solvothermal reaction, reacting at the reaction temperature of 160-220 ℃ for 6-24h, and after the reaction is finished, separating, washing with water, and freeze-drying to obtain a metal salt-loaded graphene foam precursor;
The reaction solution comprises the following substances in proportion: graphene oxide powder, isopropanol, glycerol, water, CTAB and a metal salt, wherein the metal salt is 100-400mg, 50-70mL, 7-10mL, 0-2mL, 0-2000mg and 500-3000 mg;
(3) And (4) calcining the metal salt loaded graphene foam precursor obtained in the step (3) at high temperature under the protection of inert gas, wherein the high-temperature calcination temperature is 350-1000 ℃, and the time is 30-300 min, so as to obtain the magnetic hollow nanosphere loaded graphene foam.
2. The method for preparing the magnetic hollow nanosphere-loaded graphene foam composite material according to claim 1, wherein the hummers method in step (1) is as follows: under the ice-water bath low-temperature environment, adding the crystalline flake graphite and a strong oxidant into a strong acid solution, stirring and mixing uniformly, and keeping the system at a low temperature for 30-240 min; then raising the temperature of the system to 35-40 ℃, continuously stirring for 2-4h, and then adding deionized water; raising the temperature of the system to 90-95 ℃ and keeping the temperature for 30-40 min; adding a proper amount of deionized water and H after the reaction is finished2O2Stopping stirring, standing and layering, taking the lower-layer graphite oxide suspension, sequentially carrying out acid washing and water washing, finally carrying out ultrasonic treatment to obtain graphene oxide colloidal suspension, and carrying out freeze drying to obtain graphene oxide powder.
3. The method for preparing the magnetic hollow nanosphere-loaded graphene foam composite material according to claim 1 or 2, wherein the metal salt in step (2) is one of cobalt nitrate, iron nitrate, nickel nitrate, zinc nitrate, iron acetate, cobalt acetate, nickel acetate, zinc acetate, and combinations thereof.
4. The method for preparing the magnetic hollow nanosphere-loaded graphene foam composite material according to claim 1 or 2, wherein the inert gas in step (3) is nitrogen, argon, helium, neon or a mixture of two or more gases; the protective gas flow is 40-100 mL/min.
5. The method for preparing the magnetic hollow nanosphere-loaded graphene foam composite material according to claim 3, wherein the inert gas in step (3) is nitrogen, argon, helium, neon or a mixture of two or more gases; the protective gas flow is 40-100 mL/min.
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