CN108774491B - Three-dimensional graphene sponge/Fe2O3Composite wave-absorbing material and preparation method thereof - Google Patents
Three-dimensional graphene sponge/Fe2O3Composite wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
Three-dimensional graphene sponge/Fe2O3A composite wave-absorbing material and a preparation method thereof belong to the technical field of wave-absorbing materials. Firstly, preparing three-dimensional graphene by a template method, adding the three-dimensional graphene into deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed three-dimensional graphene sponge suspension. Then adding Fe dropwise into the suspension3+Adjusting the pH value of the aqueous solution through ammonia water, and reacting at 70-95 ℃. By controlling FeCl3The structure and the wave-absorbing performance of the composite wave-absorbing material are adjusted by using the amount, the pH value, the reaction temperature and the reaction time. Magnetic nano Fe loaded on graphene sponge2O3The graphene matrix of the particle composite wave-absorbing material is in a mesoporous sponge structure, and Fe2O3The particles are uniformly anchored into the graphene sponge structure. The composite wave-absorbing material prepared by the invention has a series of characteristics of high wave-absorbing strength, wide effective absorption frequency band, low density, small thickness and the like, and has important application value in the aspect of developing high-efficiency and light-weight electromagnetic wave-absorbing materials.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and relates to three-dimensional graphene sponge/Fe2O3Composite wave-absorbing material and a preparation method thereof.
Background
In recent years, with the rapid development of electronic devices and communication facilities, severe electromagnetic radiation has become an important pollution source, and electromagnetic pollution has become a non-negligible problem. Electromagnetic radiation not only affects the normal operation of highly sensitive precise electronic equipment, but also has significant negative effects on human health, so that the development of an ideal wave-absorbing material with the characteristics of strong absorption, wide frequency band, low density, thin thickness and the like has important significance.
Graphene is an ultrathin two-dimensional carbon nanomaterial, has a series of advantages of small density, large specific surface area, excellent mechanical properties, good chemical stability and the like, and has attracted great interest of researchers as a dielectric loss type wave-absorbing material. Magnetic iron oxide (Fe)2O3) The nano particles are paid attention to due to the advantages of excellent magnetic property, low toxicity, good biocompatibility, rich raw material sources, excellent dispersibility, low cost and the like, and become a wave-absorbing material with great prospect. At present Fe2O3The preparation method mainly comprises a hydrothermal method (J.Mater.chem.A, 2013,1, 8547-8552), a solvothermal method (J.phys.chem.C, 2017, 117(38): 19701-19711), a thermal decomposition method (J.phys.chem.C, 2008(112): 19957-19962), but the methods have higher reaction temperature, or need to use non-environment-friendly organic solvents, surfactants and Fe2O3The defects of high density and poor chemical corrosion resistance limit the application of the material in the wave-absorbing material aspect. Graphene alone or magnetic Fe2O3The nano particles have a single wave absorbing mechanism, so that the absorption loss of electromagnetic waves is limited, and the comprehensive requirements of modern wave absorbing materials cannot be met. Therefore, how to combine graphene with Fe2O3The composite application combines the wave-absorbing mechanisms of the two and the respective advantages to generate good impedance matching property, thereby becoming an important method for preparing the high-performance wave-absorbing material.
At present, the research on the graphene composite wave-absorbing material is mainly carried out around two-dimensional (2D) lamellar structure graphene, the research on the wave-absorbing performance of the three-dimensional (3D) graphene-based composite material is less, and particularly, the research on the 3D graphene sponge loaded magnetic nanoparticle wave-absorbing material is not reported. Zeng, et al [ j. mater.chem.c,2016,4,10518 ] uses a self-assembly technique combining water-in-oil and a high temperature calcination two-step process to convert magnetic Fe3O4The nano particles are introduced into graphene microspheres with hollow structures to prepare Air @ rGO € Fe3O4A composite wave-absorbing material. CN 107418513A discloses graphene foam loaded magnetic Fe3O4A nano particle composite wave-absorbing material and a preparation method thereof. The magnetic nano particles related to the two composite wave-absorbing materials are Fe3O4Respectively generated by high-temperature calcination and hydrothermal reaction, and the adopted method has high temperature, time consumption and complex operation and is not suitable for large-scale preparation. The three-dimensional graphene material synthesis method mainly comprises a self-assembly method, a template method, a direct deposition method and the like, wherein the template method can well control the appearance of the three-dimensional graphene by designing a three-dimensional template in advance. Yu et al (adv. mater,2013,25,6692 and 6698) successfully synthesized 3D rGO-PU sponge by using polyurethane sponge (PU) as a template. D.D. Nguyen, et al [ Energy environ.Sci, 2012,5, 7908-7912 ] the 3D graphene sponge is prepared by using melamine as a template. The wave absorbing performance of the material is closely related to the shape and structure of the material. Therefore, it is necessary to bind magnetic Fe2O3The invention discloses a technology which is environment-friendly, time-saving, efficient and suitable for large-scale preparation, and provides respective advantages of nanoparticles and graphene to prepare three-dimensional graphene sponge/Fe with excellent wave absorption performance2O3A composite wave-absorbing material.
Disclosure of Invention
Aiming at the existing Fe2O3The invention provides efficient, environment-friendly and expandable three-dimensional graphene sponge/Fe, and provides defects of a preparation method and a blank of research of 3D graphene sponge in the field of electromagnetic wave absorption2O3A method for preparing a composite wave-absorbing material. The method takes three-dimensional graphene sponge as a matrix, iron ions as a unique iron source and deionized water as a solvent, and Fe is obtained under the conditions of an alkaline environment and a lower temperature2O3The synthesis of the magnetic nanoparticles and the compounding of the magnetic nanoparticles and the three-dimensional graphene sponge are completed in one step. The method overcomes the defects of high temperature, time consumption and complex operation of preparing magnetic nanoparticles in the prior art, and uses Fe2O3The graphene is uniformly loaded into a 3D graphene sponge structure, and the two are tightly combined. Three-dimensional graphene sponge/Fe prepared by the invention2O3The wave-absorbing material has the advantages of low density and large specific surface area, and can adjust Fe2O3The mass ratio of the three-dimensional graphene sponge to the three-dimensional graphene sponge is up toThe electromagnetic parameter of the composite material is regulated and controlled, so that the requirements of impedance matching and absorption characteristics are met, and the wave-absorbing material with excellent performance is prepared.
In order to achieve the purpose, the technical scheme of the invention is as follows:
three-dimensional graphene sponge/Fe2O3The composite wave-absorbing material takes three-dimensional graphene with a mesoporous sponge structure as a matrix, iron ions as a unique iron source, deionized water as a solvent, and spherical popcorn-shaped Fe with the particle size of 150-250 nm is prepared in an alkaline environment at a lower temperature2O3The nano particles are uniformly anchored in the three-dimensional graphene sponge structure; fe2O3The synthesis of the magnetic nanoparticles and the compounding of the magnetic nanoparticles and the three-dimensional graphene sponge are completed in one step.
Three-dimensional graphene sponge/Fe2O3The preparation method of the composite wave-absorbing material comprises the following steps:
(1) adding black nickel powder into a polyol solution containing a small amount of sodium hydroxide solution, pouring into a polyphenylene (PPL) lining stainless steel reaction kettle, putting into an oven, heating to 250-280 ℃, reacting for 12-15 h, naturally cooling to room temperature, washing the product for multiple times with deionized water and absolute ethyl alcohol, and vacuum drying to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 500-800 ℃ under the protection of inert atmosphere, preserving heat for 1-3 h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using acid liquor, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponge, adding a small amount of the three-dimensional graphene sponge into the deionized water, and performing ultrasonic treatment for 1-3 hours to obtain 2-5 mg/ml of uniformly dispersed suspension. 1-3 g of nickel powder is correspondingly added into every 20-90 ml of polyhydric alcohol.
(2) And (2) adding the three-dimensional graphene sponge suspension obtained in the step (1) into a three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, the iron salt is dissolved in deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring to obtain a mixed solution. After the dripping is finished, the mixture is added,heating the system to 70-95 ℃, dropwise adding an alkaline solution, adjusting the pH value to 9-13, and reacting for 3-5 h. The solution was washed with water and alcohol by magnet adsorption until the pH was 7. And finally, placing the sample in a vacuum oven, and carrying out vacuum drying to obtain a product. 0.06-0.15 g of three-dimensional graphene sponge is correspondingly added into every 0.375-0.625 g of iron salt in the mixed solution.
The polyhydric alcohol in the step (1) is triethylene glycol or diethylene glycol; the volume ratio of the polyalcohol solution to the sodium hydroxide solution is 20: 1-30: 1, wherein the concentration of the sodium hydroxide solution is 1 mol/L.
The inert gas in the step (1) is one or a mixture of more than two of nitrogen, argon, helium and neon.
The acid solution in the step (1) is one or more of dilute hydrochloric acid, sulfuric acid solution and nitric acid solution.
And (3) the ferric salt in the step (2) is one or more of ferric chloride, ferric sulfate and ferric nitrate.
The alkaline solution in the step (2) is NH3·H2O、NaOH、Na2CO3、NaHCO3One or more of them.
The invention has the beneficial effects that:
(1) the method takes three-dimensional graphene sponge as a matrix and iron ions as a unique iron source, and completes Fe in one step under the conditions of alkaline environment and proper temperature2O3The synthesis of the magnetic nanoparticles and the composition of the magnetic nanoparticles and the three-dimensional graphene sponge have the technical characteristics of simple and convenient operation conditions, time saving and high efficiency, and the obtained three-dimensional graphene sponge/Fe2O3The composite wave-absorbing material has excellent wave-absorbing performance.
(2) Mixing Fe2O3The magnetic nanoparticles are loaded in the three-dimensional graphene sponge structure, so that the functionalization of the three-dimensional graphene sponge is realized, and the application range of the three-dimensional graphene sponge is widened.
(3) The preparation process is green and environment-friendly, has strong repeatability, and the size of magnetic particles and the three-dimensional graphene sponge/Fe can be adjusted by adjusting the quality, the pH value, the reaction time and the reaction temperature of ferric salt2O3CompoundingWave absorbing property of the wave absorbing material.
(4) Prepared three-dimensional graphene sponge/Fe2O3The composite wave-absorbing material has a series of advantages of high absorption strength, wide effective frequency band, low density and good heat resistance, and embodies three-dimensional graphene sponge and Fe2O3The two are combined for application.
Drawings
Fig. 1 is a scanning electron microscope image of the three-dimensional graphene sponge prepared in example 1.
FIG. 2 shows three-dimensional graphene sponge/Fe prepared in example 12O3Scanning electron microscope images of the composite wave-absorbing material.
FIG. 3 shows three-dimensional graphene sponge/Fe prepared in example 12O3And an X-ray diffraction pattern of the composite wave-absorbing material.
FIG. 4 shows three-dimensional graphene sponge/Fe prepared in example 12O3And the reflection loss curve of the composite wave-absorbing material in the range of 2-18 GHz.
FIG. 5 shows three-dimensional graphene sponge/Fe prepared in example 22O3Scanning electron microscope images of the composite wave-absorbing material.
FIG. 6 shows three-dimensional graphene sponge/Fe prepared in example 22O3X-ray diffraction pattern of the composite wave-absorbing material.
FIG. 7 shows three-dimensional graphene sponge/Fe prepared in example 22O3And the reflection loss curve of the composite wave-absorbing material in the range of 2-18 GHz.
Detailed Description
The invention will now be further illustrated by reference to specific examples.
Example 1:
step 1: adding 1g of black nickel powder into 20ml of triethylene glycol solvent, dropwise adding 1ml of 1mol/L sodium hydroxide solution into the mixture, pouring the mixture into a polyphenylene (PPL) lining stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 250 ℃, and reacting for 12 hours. After the reaction, naturally cooling to room temperature, washing the product for many times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 500 ℃ at the speed of 5 ℃/min under the protection of inert atmosphere, preserving heat for 1h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using dilute hydrochloric acid, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponges, adding a small amount of the three-dimensional graphene sponges into the deionized water, and performing ultrasonic treatment for 1 hour to obtain 2mg/ml uniformly dispersed suspension.
Step 2: and (3) adding 30ml of the three-dimensional graphene sponge suspension obtained in the step (1) into a 100ml three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, 0.375g FeCl was added3·6H2O is dissolved in 10ml of deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring. After the addition, the temperature of the system was raised to 90 ℃ by heating, 25% ammonia was added dropwise to adjust the pH to 11, and the reaction was carried out for 4 hours. The solution was washed with magnet-adsorbed water and alcohol until the pH was 7. And finally, placing the sample in a vacuum oven at 60 ℃ and carrying out vacuum drying for 12h to obtain the product.
FIG. 2 shows that three-dimensional graphene sponge/Fe is prepared2O3Scanning electron microscope image of the composite wave-absorbing material, and FIG. 3 is three-dimensional graphene sponge/Fe2O3The X-ray diffraction pattern of the composite wave-absorbing material can show Fe from figure 22O3Uniformly loaded into a three-dimensional graphene sponge structure, and tightly combined, wherein each diffraction peak and Fe in figure 32O3The peak positions of the standard cards of the crystal are consistent, which shows that Fe2O3The successful synthesis of the compound.
FIG. 4 is a three-dimensional graphene sponge/Fe2O3The reflection loss curve of the composite wave-absorbing material in the range of 2-18 GHz shows that the composite wave-absorbing material has the maximum reflection loss of-55.7 dB when d is 1.4mm, and has the widest effective absorption bandwidth of 4.42GHz when d is 1.7 mm.
Example 2:
step 1: adding 2g of black nickel powder into 40ml of triethylene glycol solvent, dropwise adding 2ml of 1mol/L sodium hydroxide solution into the mixture, pouring the mixture into a polyphenylene (PPL) lining stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 250 ℃, and reacting for 12 hours. After the reaction, naturally cooling to room temperature, washing the product for many times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 500 ℃ at the speed of 8 ℃/min under the protection of inert atmosphere, preserving heat for 1h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using dilute hydrochloric acid, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponges, adding a small amount of the three-dimensional graphene sponges into the deionized water, and performing ultrasonic treatment for 2 hours to obtain 2.5mg/ml of uniformly dispersed suspension.
Step 2: and (3) adding 30ml of the three-dimensional graphene sponge suspension obtained in the step (1) into a 100ml three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, 0.5g FeCl was added3·6H2O is dissolved in 10ml of deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring. After the completion of the dropwise addition, the system was heated to 90 ℃ and an alkaline solution was added dropwise to adjust the pH to 11, followed by reaction for 4 hours. The solution was washed with magnet-adsorbed water and alcohol until the pH was 7. And finally, placing the sample in a vacuum oven at 70 ℃ and carrying out vacuum drying for 16h to obtain the product.
FIG. 5 shows the prepared three-dimensional graphene sponge/Fe2O3Scanning electron microscope image of the composite wave-absorbing material, and FIG. 6 shows the prepared three-dimensional graphene sponge/Fe2O3The X-ray diffraction pattern of the composite wave-absorbing material can show that Fe is contained in figure 52O3Uniformly loaded into a three-dimensional graphene sponge structure, and tightly combined with the three-dimensional graphene sponge structure, wherein each diffraction peak and Fe appearing in figure 62O3The peak positions of the standard cards of the crystal are consistent, which shows that Fe2O3The successful synthesis of the compound.
FIG. 7 is a three-dimensional graphene sponge/Fe2O3The reflection loss curve of the composite wave-absorbing material in the range of 2-18 GHz shows that the composite wave-absorbing material has the maximum reflection loss and the widest effective absorption bandwidth of-29.8 dB and 4.33GHz respectively when d is 1.5 mm.
Example 3:
step 1: adding 3g of black nickel powder into 60ml of triethylene glycol solvent, dropwise adding 3ml of 1mol/L sodium hydroxide solution into the mixture, pouring the mixture into a polyphenylene (PPL) lining stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 250 ℃, and reacting for 12 hours. After the reaction, naturally cooling to room temperature, washing the product for many times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 500 ℃ at the speed of 10 ℃/min under the protection of inert atmosphere, preserving heat for 1h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using dilute hydrochloric acid, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponges, adding a small amount of the three-dimensional graphene sponges into the deionized water, and performing ultrasonic treatment for 3 hours to obtain 3mg/ml uniformly dispersed suspension.
Step 2: and (3) adding 30ml of the three-dimensional graphene sponge suspension obtained in the step (1) into a 100ml three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, 0.625g FeCl3·6H2O is dissolved in 10ml of deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring. After the completion of the dropwise addition, the system was heated to 90 ℃ and an alkaline solution was added dropwise to adjust the pH to 11, followed by reaction for 4 hours. The solution was washed with magnet-adsorbed water and alcohol until the pH was 7. Finally, the sample is placed in a vacuum oven at 80 ℃ and dried for 18h in vacuum to obtain the product.
Example 4:
step 1: adding 1g of black nickel powder into 30ml of triethylene glycol solvent, dropwise adding 1ml of 1mol/L sodium hydroxide solution into the mixture, pouring the mixture into a polyphenylene (PPL) lining stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 260 ℃, and reacting for 12 hours. After the reaction, naturally cooling to room temperature, washing the product for many times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 500 ℃ at the speed of 8 ℃/min under the protection of inert atmosphere, preserving heat for 1h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using dilute hydrochloric acid, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponges, adding a small amount of the three-dimensional graphene sponges into the deionized water, and performing ultrasonic treatment for 1 hour to obtain 4mg/ml uniformly dispersed suspension.
Step 2: and (3) adding 30ml of the three-dimensional graphene sponge suspension obtained in the step (1) into a 100ml three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, 0.375g FeCl was added3·6H2O is dissolved in 10ml of deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring. After the completion of the dropwise addition, the system was heated to 70 ℃ and an alkaline solution was added dropwise to adjust the pH to 9, followed by reaction for 3 hours. The solution was washed with magnet-adsorbed water and alcohol until the pH was 7. And finally, placing the sample in a vacuum oven at 60 ℃ and carrying out vacuum drying for 20h to obtain the product.
Example 5:
step 1: adding 2g of black nickel powder into 60ml of triethylene glycol solvent, dropwise adding 2ml of 1mol/L sodium hydroxide solution into the mixture, pouring the mixture into a polyphenylene (PPL) lining stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 270 ℃, and reacting for 13 hours. After the reaction, naturally cooling to room temperature, washing the product for many times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 600 ℃ at the speed of 10 ℃/min under the protection of inert atmosphere, preserving heat for 2h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using dilute hydrochloric acid, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponges, adding a small amount of the three-dimensional graphene sponges into the deionized water, and performing ultrasonic treatment for 2 hours to obtain 5mg/ml uniformly dispersed suspension.
Step 2: and (3) adding 30ml of the three-dimensional graphene sponge suspension obtained in the step (1) into a 100ml three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, 0.5g FeCl was added3·6H2O is dissolved in 10ml of deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring. After the dropwise addition, the mixture is heated to raise the temperature of the system to 80 ℃, and the mixture is added dropwiseAlkaline solution, adjusting pH to 11, and reacting for 4 h. The solution was washed with magnet-adsorbed water and alcohol until the pH was 7. And finally, placing the sample in a vacuum oven at 80 ℃, and performing vacuum drying for 20 hours to obtain a product.
Example 6:
step 1: adding 3g of black nickel powder into 90ml of triethylene glycol solvent, dropwise adding 3ml of 1mol/L sodium hydroxide solution into the mixture, pouring the mixture into a polyphenylene (PPL) lining stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 280 ℃, and reacting for 15 hours. After the reaction, naturally cooling to room temperature, washing the product for many times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder. And then putting the black powder into a ceramic square boat, sending the ceramic square boat into a tube furnace, introducing inert gas, heating to 800 ℃ at the speed of 10 ℃/min under the protection of inert atmosphere, preserving heat for 3h, and naturally cooling to room temperature. And finally, dissolving the nickel nanoparticle cores by using dilute hydrochloric acid, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponges, adding a small amount of the three-dimensional graphene sponges into the deionized water, and performing ultrasonic treatment for 3 hours to obtain 5mg/ml uniformly dispersed suspension.
Step 2: and (3) adding 30ml of the three-dimensional graphene sponge suspension obtained in the step (1) into a 100ml three-neck flask, and mechanically stirring in a water bath kettle. Subsequently, 0.625g FeCl3·6H2O is dissolved in 10ml of deionized water to form a solution containing Fe3+And slowly dripping the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring. After the completion of the dropwise addition, the system was heated to 95 ℃ and an alkaline solution was added dropwise to adjust the pH to 13, followed by reaction for 5 hours. The solution was washed with magnet-adsorbed water and alcohol until the pH was 7. And finally, placing the sample in a vacuum oven at 80 ℃ and carrying out vacuum drying for 24h to obtain the product.
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 (9)
1. Three-dimensional graphene sponge/Fe2O3The preparation method of the composite wave-absorbing material is characterized in that the material takes three-dimensional graphene with a mesoporous sponge structure as a matrix, iron ions as a unique iron source, deionized water as a solvent, and spherical popcorn-shaped Fe with the particle size of 150-250 nm is prepared under the alkaline environment condition2O3The method for uniformly anchoring the nano particles in the three-dimensional graphene sponge structure comprises the following steps:
(1) adding nickel powder into a mixed solution of a sodium hydroxide solution and polyhydric alcohol, pouring into a reaction kettle, putting into an oven, heating to 250-280 ℃, reacting for 12-15 h, naturally cooling to room temperature, washing the product for multiple times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain black powder; feeding the black powder into a tube furnace, heating to 500-800 ℃ under the protection of inert atmosphere, preserving heat for 1-3 h, and naturally cooling to room temperature; finally, dissolving the nickel nanoparticle cores by using acid liquor, washing the nickel nanoparticle cores for multiple times by using deionized water until the pH value is 7, then performing freeze-drying to obtain three-dimensional graphene sponge, and adding the three-dimensional graphene sponge into the deionized water to perform ultrasonic treatment to obtain 2-5 mg/ml uniformly dispersed suspension; wherein, 1-3 g nickel powder is correspondingly added into every 20-90 ml of polyhydric alcohol;
(2) adding the three-dimensional graphene sponge suspension obtained in the step (1) into a three-neck flask, and mechanically stirring; dissolving iron salt in deionized water to form Fe-containing solution3+Dropwise adding the yellow solution into a three-neck flask containing the three-dimensional graphene sponge suspension, and mechanically stirring to obtain a mixed solution; after the dropwise addition, heating to raise the temperature of the system to 70-95 ℃, dropwise adding an alkaline solution, adjusting the pH to 9-13, and reacting for 3-5 hours; performing magnetic adsorption water washing and alcohol washing until the pH value is 7; finally, placing the sample in a vacuum oven, and carrying out vacuum drying to obtain a product; 0.06-0.15 g of three-dimensional graphene sponge is correspondingly added into every 0.375-0.625 g of iron salt in the mixed solution.
2. The method according to claim 1, wherein the polyhydric alcohol in the step (1) is triethylene glycol or diethylene glycol; the volume ratio of the polyalcohol solution to the sodium hydroxide solution is 20: 1-30: 1, wherein the concentration of the sodium hydroxide solution is 1 mol/L.
3. The preparation method of claim 1 or 2, wherein the three-dimensional graphene sponge in the step (1) is added into deionized water for ultrasonic treatment for 1-3 hours.
4. The method according to claim 1 or 2, wherein the acid solution in step (1) is one or more of dilute hydrochloric acid, a sulfuric acid solution, and a nitric acid solution.
5. The method according to claim 3, wherein the acid solution in step (1) is one or more of dilute hydrochloric acid, a sulfuric acid solution, and a nitric acid solution.
6. The method of claim 1, 2 or 5, wherein the iron salt in step (2) is one or more of ferric chloride, ferric sulfate and ferric nitrate.
7. The method according to claim 3, wherein the iron salt in step (2) is one or more of ferric chloride, ferric sulfate and ferric nitrate.
8. The method according to claim 1, 2,5 or 7, wherein the alkaline solution in the step (2) is NH3·H2O、NaOH、Na2CO3、NaHCO3One or more of them.
9. The method according to claim 6, wherein the alkaline solution in the step (2) is NH3·H2O、NaOH、Na2CO3、NaHCO3One or more of them.
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| CN111817020B (en) * | 2020-06-30 | 2021-10-15 | 太原科技大学 | Preparation method of magnetic alloy loaded porous ceramic composite wave-absorbing material |
| CN113104903B (en) * | 2021-03-01 | 2023-09-22 | 西安理工大学 | Preparation method of biomass-based wave-absorbing material |
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