CN110577818B - Preparation method of graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material - Google Patents
Preparation method of graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide composite material, which comprises the following steps of firstly, mixing a graphene oxide dispersion liquid, a ferric iron source and a ferrous iron source to obtain a precursor solution; then carrying out ultrasonic treatment on the precursor solution obtained in the step, and adding a pH value regulator for reaction to obtain black precipitate; and finally, mixing the black precipitate obtained in the step, a silicon source and an organic solvent again for reaction to obtain the graphene oxide/ferroferric oxide/silicon dioxide composite material. The preparation method has simple steps, reduces the time required by the reaction, improves the yield of the composite material, is beneficial to industrial mass production, achieves uniform distribution of ferroferric oxide, more effectively avoids the agglomeration of graphene oxide, does not use high-hazard reducing agents such as hydrazine hydrate and the like, and avoids environmental pollution. The composite wave-absorbing material prepared by the invention has excellent wave-absorbing performance and good application prospect.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, relates to a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide composite material, and particularly relates to a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material.
Background
Along with the rapid development of microwave and communication technologies, the threat of increasingly severe electromagnetic pollution to the environment and biological safety is increasingly emphasized by people. The harm caused by electromagnetic pollution is not underestimated, and in modern families, the electromagnetic wave directly or indirectly harms human health along with the action of 'electronic smoke' while bringing benefits to people, and becomes the fourth largest pollution following atmospheric pollution, water pollution and noise pollution. The protection and shielding of electromagnetic radiation are generally concerned by the whole society, so the research and development of the high-efficiency wave-absorbing material become a hotspot of the research in the industry. And the research of the high-efficiency wave-absorbing material also has important significance for improving the invisibility of weapon equipment and the viability of weapon systems. Therefore, research on wave-absorbing materials has been one of the focuses of attention in the field.
Ferroferric oxide is a typical magnetic loss material, and graphene is a novel carbon material formed by closely arranging single carbon atoms, and has a large specific surface area and good electric heat conduction performance. Meanwhile, graphene oxide has a high dielectric constant, and is easily polarized in an external electromagnetic field to generate dielectric loss. The single graphene sheet layer is easily penetrated by electromagnetic waves to lose the electromagnetic wave absorption capability, and meanwhile, the impedance matching is difficult due to the single high dielectric loss. And a large number of oxygen-containing groups (such as hydroxyl, carboxyl, epoxy and the like) exist on the surface of the graphene oxide, and the oxygen-containing groups on the surface of the graphene oxide are used as target points for combining with the nano material, so that the graphene oxide and the ferroferric oxide are chemically combined, electromagnetic waves can be prevented from directly transmitting by the barrier effect between quantum lattices and the steric hindrance effect after penetrating into the composite material, and the effect of reducing the frequency of the electromagnetic waves is achieved. Meanwhile, the ferroferric oxide nanoparticles loaded on the surface of the graphene can absorb electromagnetic waves through mechanisms such as magnetic hysteresis loss, eddy current loss, ferromagnetic resonance and the like. So that the composite material has excellent electromagnetic wave-absorbing performance. Therefore, the composite material composed of multiple materials such as graphene oxide/ferroferric oxide has received wide attention from scholars in the field.
In the prior art, a composite material composed of multiple materials such as graphene oxide/ferroferric oxide and the like is usually prepared by a conventional solvothermal method, the composite material composed of the multiple materials such as the graphene oxide/ferroferric oxide and the like needs to be subjected to a high-temperature and high-pressure reaction process, high-pressure-resistant equipment is necessarily needed for generating high pressure, the reaction equipment and conditions are quite harsh, the equipment cost is high, the energy consumption is high, high risk is caused during production, the problems of low yield, high price and the like of the composite material are further caused, the progress and development of the ferroferric oxide composite material in practical application are limited, and the popularization and application of industrialization are not facilitated.
However, when the ferroferric oxide nano particles are prepared by the existing solvothermal method, a high-temperature and high-pressure reaction process is needed, high-pressure resistant equipment is necessarily needed for generating high pressure, the equipment cost is high, the energy consumption is high, high danger is generated during use, and the problems of low yield, high price and the like of the composite material are caused,
therefore, how to find a more optimized preparation method of the triiron tetroxide-based composite material to solve the problems has mild process conditions, safety and environmental protection, and becomes an important problem to be solved urgently by a plurality of industrial manufacturers and a front-line research and development personnel.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a graphene oxide/ferroferric oxide/silicon dioxide composite material, and in particular, a method for preparing a graphene oxide/ferroferric oxide/silicon dioxide composite wave-absorbing material by coprecipitation under normal pressure.
The invention provides a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide composite material, which comprises the following steps:
A) mixing the graphene oxide dispersion liquid, a ferric iron source and a ferrous iron source to obtain a precursor solution;
B) performing ultrasonic treatment on the precursor solution obtained in the step, and adding a pH value regulator for reaction to obtain black precipitate;
C) and mixing the black precipitate obtained in the step, a silicon source and an organic solvent again for reaction to obtain the graphene oxide/ferroferric oxide/silicon dioxide composite material.
Preferably, the ferric iron source comprises one or more of ferric chloride, ferric sulfate and ferric nitrate;
the ferrous iron source comprises one or more of ferrous chloride, ferrous sulfate and ferrous nitrate;
the molar ratio of the ferric iron source to the ferrous iron source is (1-10): (10-1);
the mass ratio of the total mass of the ferric iron source and the ferrous iron source to the graphene oxide is (5-100): 1.
preferably, the mass fraction of the graphene oxide dispersion liquid is 0.1-1%;
the mixing is ultrasonic dispersion;
the mixing time is 10-120 min.
Preferably, the ultrasound is ultrasonic stirring;
the ultrasonic time is 10-120 min;
the pH value regulator comprises one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and urea.
Preferably, the pH value after the pH value regulator is added is 8-11;
the reaction time is 1-6 h;
the reaction also comprises a magnetic absorption step.
Preferably, the silicon source comprises one or more of ethyl orthosilicate, methyl orthosilicate, tetrabutyl silicate, tetrapropyl silicate and butyl orthosilicate;
the organic solvent comprises one or more of ethanol, methanol, benzyl alcohol, isopropanol and glycol;
the volume ratio of the silicon source to the organic solvent is 1: (20-200);
the mass ratio of the silicon source to the graphene oxide is (50-800): 1.
preferably, the time of the remixing reaction is 1-6 h;
the post-treatment step is also included after the secondary mixing reaction;
the post-treatment comprises one or more of magnetic separation, washing, drying and crushing.
Preferably, the black precipitate is a ferroferric oxide/silicon dioxide composite material;
the graphene oxide/ferroferric oxide/silicon dioxide composite material has the specific structure as follows:
the ferroferric oxide/silicon dioxide composite material is ferroferric oxide @ silicon dioxide nano particles;
the ferroferric oxide @ silicon dioxide nano-particles have a core-shell structure, wherein the ferroferric oxide nano-particles are used as cores, and the silicon dioxide is used as shells.
Preferably, the particle size of the ferroferric oxide nano particles is 15-50 nm;
the thickness of the silicon dioxide shell layer is 5-30 nm;
the ferroferric oxide @ silicon dioxide nanoparticles are uniformly distributed on the surface of graphene oxide;
the thickness of the graphene oxide sheet layer is 0.35-2.5 nm;
the sheet diameter of the graphene oxide is 5-20 mu m.
The invention also provides a wave-absorbing material which comprises the graphene oxide/ferroferric oxide/silicon dioxide composite material prepared by the preparation method in any one of the technical schemes.
The invention provides a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide composite material, which comprises the following steps of firstly, mixing a graphene oxide dispersion liquid, a ferric iron source and a ferrous iron source to obtain a precursor solution; then carrying out ultrasonic treatment on the precursor solution obtained in the step, and adding a pH value regulator for reaction to obtain black precipitate; and finally, mixing the black precipitate obtained in the step, a silicon source and an organic solvent again for reaction to obtain the graphene oxide/ferroferric oxide/silicon dioxide composite material. Compared with the prior art, the method provided by the invention has the advantages that the normal pressure coprecipitation method is particularly adopted to carry out chemical reaction at normal temperature and normal pressure, and the limitation of the solvothermal method on equipment and conditions is avoided, aiming at the problems that the existing solvothermal method for preparing the ferric oxide-based composite material is high in equipment cost, high in energy consumption, high in risk during production, low in yield of the composite material, high in price and the like.
In addition, graphene oxide and ferroferric oxide are compounded more creatively, a divalent iron source and a third-order iron source are adopted at the same time, graphene oxide can be directly compounded with ferroferric oxide primary particles, then silicon dioxide is coated, the steps are simple, the time required by reaction is greatly reduced, the yield of the composite material is improved, industrial large-scale production is facilitated, the preparation scheme achieves uniform distribution of ferroferric oxide, graphene oxide agglomeration is effectively avoided, high-harm reducing agents such as hydrazine hydrate are not used, and environmental pollution is avoided. The graphene oxide/ferroferric oxide/silicon dioxide composite wave-absorbing material prepared by the invention has excellent wave-absorbing performance and has good application prospect in the field of electromagnetic wave absorption.
Experimental results show that the preparation method provided by the invention can effectively improve the electromagnetic absorption strength and the electromagnetic absorption width of the magnetic graphene material, the maximum absorption strength reaches-28.2 dB, the effective absorption width is 4.0GHz, and the temperature resistance and the oxidation resistance are also obviously improved.
Drawings
FIG. 1 is a simplified process flow diagram of a manufacturing process according to an embodiment of the present invention;
fig. 2 is a scanning electron microscope photograph of the graphene oxide/ferroferric oxide @ silica composite material prepared in example 1 of the present invention;
FIG. 3 is a TEM photograph of the graphene oxide/ferroferric oxide @ silica composite prepared in example 1 of the present invention;
fig. 4 is an electromagnetic reflectance curve of the graphene oxide/ferroferric oxide @ silica composite material prepared in the embodiment of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the conventional purity used in the field of analytical purification or ferroferric oxide composite materials.
The invention provides a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide composite material, which is characterized by comprising the following steps of:
A) mixing the graphene oxide dispersion liquid, a ferric iron source and a ferrous iron source to obtain a precursor solution;
B) performing ultrasonic treatment on the precursor solution obtained in the step, and adding a pH value regulator for reaction to obtain black precipitate;
C) and mixing the black precipitate obtained in the step, a silicon source and an organic solvent again for reaction to obtain the graphene oxide/ferroferric oxide/silicon dioxide composite material.
Firstly, mixing graphene oxide dispersion liquid, a ferric iron source and a ferrous iron source to obtain a precursor solution.
The parameters of the graphene oxide dispersion liquid are not particularly limited in the present invention, and may be conventional parameters of graphene oxide aqueous dispersion liquid known to those skilled in the art, and those skilled in the art may select and adjust the parameters according to actual production conditions, product requirements and quality requirements, and the mass concentration of the graphene oxide dispersion liquid in the present invention is preferably 0.1% to 1%, more preferably 0.3% to 0.8%, and still more preferably 0.5% to 0.6%.
The selection of the ferric iron source is not particularly limited in the present invention, and the ferric iron source for preparing ferroferric oxide, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the ferric iron source in the present invention preferably comprises one or more of ferric chloride, ferric sulfate and ferric nitrate, more preferably ferric chloride, ferric sulfate or ferric nitrate, and most preferably ferric chloride.
The selection of the ferrous iron source is not particularly limited in the present invention, and the ferrous iron source for preparing ferroferric oxide, which is well known to those skilled in the art, may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the ferrous iron source in the present invention preferably includes one or more of ferrous chloride, ferrous sulfate and ferrous nitrate, more preferably ferrous chloride, ferrous sulfate or ferrous nitrate, and most preferably ferrous chloride.
The adding amount of the ferric iron source and the ferrous iron source is not particularly limited, and can be selected and adjusted according to the actual production condition, the product requirement and the quality requirement by the technical personnel in the field according to the conventional using amount for preparing ferroferric oxide well known by the technical personnel in the field, and in order to improve the performance of the final product, the mass ratio of the total mass of the ferric iron source and the ferrous iron source to the graphene oxide is preferably (5-100): 1, more preferably (15 to 90): 1, more preferably (25 to 80): 1, more preferably (45-60): 1.
the proportion of the ferric iron source and the ferrous iron source is not particularly limited, and a person skilled in the art can select and adjust the proportion according to the actual production condition, the product requirement and the quality requirement, in order to improve the performance of the final product, the molar ratio of the ferric iron source to the ferrous iron source is preferably (1-10): (10-1), more preferably (3-8): (10-1), more preferably (5-6): (10-1), which may be (1-10): (8-3), or (1-10): (5-6).
The mixing method and parameters are not particularly limited, and can be selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality requirement, the mixing method is preferably ultrasonic dispersion, and the mixing time is preferably 10-120 min, more preferably 30-90 min, and more preferably 50-70 min.
The precursor solution obtained in the step is subjected to ultrasonic treatment, and then a pH value regulator is added for reaction to obtain black precipitate.
The ultrasonic mode and parameters are not particularly limited, and the ultrasonic mode and parameters known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality requirement, the ultrasonic is preferably ultrasonic stirring, and the ultrasonic time is preferably 10-120 min, more preferably 30-90 min, and more preferably 50-70 min.
The selection of the pH regulator is not particularly limited in the present invention, and may be a conventional pH regulator well known to those skilled in the art, and those skilled in the art can select and adjust the pH regulator according to actual production conditions, product requirements and quality requirements, and the pH regulator in the present invention preferably includes one or more of ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate and urea, and more preferably, ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate or urea.
The addition amount of the pH regulator is not particularly limited, and the conventional alkaline pH value known by the skilled in the art can be used, and the skilled in the art can select and adjust the pH value according to the actual production condition, the product requirement and the quality requirement, and the pH value after the pH regulator is added is preferably 8-11, more preferably 8.5-10.5, and more preferably 9-10.
The reaction time is not particularly limited in the present invention, and the reaction time known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, product requirements and quality requirements, and the reaction time is preferably 1 to 6 hours, more preferably 2 to 5 hours, and more preferably 3 to 4 hours.
In order to further improve the performance of the product and ensure the reaction effect, the method preferably further comprises a step of removing liquid after the reaction, more preferably adopts magnetic attraction, and specifically comprises the following steps:
and magnetically attracting the black precipitate solution obtained after the reaction, and then pouring out the clear liquid to obtain the black precipitate.
Finally, mixing the black precipitate obtained in the step, a silicon source and an organic solvent again for reaction to obtain the graphene oxide/ferroferric oxide/silicon dioxide composite material.
The selection of the silicon source is not particularly limited by the present invention, and the silicon source used for preparing silicon dioxide, which is well known to those skilled in the art, may be selected and adjusted by those skilled in the art according to the actual production situation, product requirements and quality requirements, and the silicon source of the present invention preferably comprises one or more of tetraethoxysilane, tetrabutylsilicate, tetrapropyl silicate and tetrabutyl silicate, and more preferably tetraethoxysilane, tetrabutyl silicate, tetrapropyl silicate or tetrabutyl silicate.
The addition amount of the silicon source is not particularly limited, and the silicon source can be used for preparing conventional dosage which is well known to those skilled in the art, and those skilled in the art can select and adjust the dosage according to the actual production condition, the product requirement and the quality requirement, and in order to improve the performance of the final product, the mass ratio of the silicon source to the graphene oxide is preferably (50-800): 1, more preferably (100 to 700): 1, more preferably (200 to 600): 1, more preferably (300 to 500): 1.
the selection of the organic solvent is not particularly limited in the present invention, and the organic solvent is known to those skilled in the art, and those skilled in the art can select and adjust the organic solvent according to the actual production situation, the product requirement and the quality requirement, and the organic solvent of the present invention preferably includes one or more of ethanol, methanol, benzyl alcohol, isopropanol and ethylene glycol, and more preferably ethanol, methanol, benzyl alcohol, isopropanol or ethylene glycol.
The amount of the organic solvent added in the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to the actual production situation, product requirement and quality requirement, and the volume ratio of the silicon source to the organic solvent is preferably 1: (20-200), more preferably 1: (50 to 180), more preferably 1: (80-150), more preferably 1: (100-120).
The time for the remixing reaction is not particularly limited in the present invention, and the time for such reaction known to those skilled in the art may be used, and those skilled in the art may select and adjust the time according to the actual production situation, the product requirement and the quality requirement, and the time for the remixing reaction in the present invention is preferably 1 to 6 hours, more preferably 2 to 5 hours, and more preferably 3 to 4 hours.
In order to further improve the performance of the product and ensure the effect of the reaction, the post-treatment step is preferably included after the remixing reaction, the specific process and parameters of the post-treatment step are not particularly limited, and the post-treatment step and parameters of the reaction well known to those skilled in the art can be selected and adjusted according to the actual production situation, the product requirement and the quality requirement, and the post-treatment of the invention preferably includes one or more of magnetic separation, washing, drying and crushing, more preferably includes more than one of magnetic separation, washing, drying and crushing, and more preferably sequentially includes magnetic separation, washing, drying and crushing.
In order to better ensure the product performance, complete and refine the production process, the preparation method specifically comprises the following steps:
taking a graphene oxide aqueous solution prepared by Shandong European platinum New Material Co., Ltd, ultrasonically dispersing for a certain time, and then dropwise adding a mixed solution of ferrous chloride and ferric chloride in a certain proportion to obtain a precursor solution. Wherein the mass fraction of the graphene oxide aqueous solution is (1 per thousand-1%), the ultrasonic time is 10-120 min, and the weight ratio of ferrous chloride: iron chloride molar ratio (1:10 to 10:1), iron salt: the mass ratio of graphene oxide is (100: 1-5: 1);
2, ultrasonically treating the precursor solution obtained in the step 1, stirring for a period of time (10-120 min), slowly adding a certain amount of ammonia water, adjusting the pH value of the solution to (8-11), and continuously reacting for 1-6 h to obtain a black precipitate solution;
and 3, magnetically sucking the black precipitate solution obtained in the step 2, pouring out supernatant, slowly adding a certain amount of ethanol and tetraethoxysilane, and continuously stirring for 1-6 hours to obtain a reaction product. Wherein the volume ratio of the ethanol to the tetraethoxysilane is (20: 1-200: 1)
And 4, after the reaction product obtained in the step 3 is subjected to magnetic separation, respectively washing with ultrapure water and ethanol for 3 times, then performing vacuum drying and airflow crushing to obtain the graphene oxide composite ferroferric oxide @ silicon dioxide composite wave-absorbing material.
According to the invention, the graphene oxide/ferroferric oxide/silicon dioxide composite material is prepared through the steps, the specific structure of the composite material is not particularly limited, the composite material with the specific structure can be obtained by referring to the preparation method by a person skilled in the art, the person skilled in the art can select and adjust the black precipitate, namely the ferroferric oxide/silicon dioxide composite material according to the actual production condition, the product requirement and the quality requirement. The ferroferric oxide/silicon dioxide composite material is preferably ferroferric oxide @ silicon dioxide nanoparticles. The ferroferric oxide @ silicon dioxide nanoparticle has a core-shell structure, wherein the ferroferric oxide nanoparticle is used as a core, and the silicon dioxide is used as a shell.
The invention has no particular limitation on the specific parameters of the composite material, the composite material with the specific parameters can be obtained by referring to the preparation method by the technical personnel in the field, the technical personnel in the field can select and adjust the composite material according to the actual production condition, the product requirement and the quality requirement, and the particle size of the ferroferric oxide nano-particles is preferably 15-50 nm, more preferably 20-45 nm, more preferably 25-40 nm, and more preferably 30-35 nm. The thickness of the silicon dioxide shell layer is preferably 5-30 nm, more preferably 10-25 nm, and more preferably 15-20 nm. The ferroferric oxide @ silicon dioxide nanoparticles are preferably uniformly distributed on the surface of graphene oxide. The thickness of the graphene oxide sheet is preferably 0.3-2.5 nm, more preferably 0.3-2.5 nm, and even more preferably 0.3-2.5 nm. The sheet diameter of the graphene oxide is preferably 5-20 μm, more preferably 8-18 μm, and more preferably 10-15 μm.
The invention also provides a wave-absorbing material which comprises the graphene oxide/ferroferric oxide/silicon dioxide composite material prepared by the preparation method in any one of the technical schemes.
The invention has no special limitation on the specific form and shape of the wave-absorbing material, and the specific form and shape of the wave-absorbing material known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production condition, the product requirement and the quality requirement, and the wave-absorbing material can contain or only be the graphene oxide/ferroferric oxide/silicon dioxide composite material prepared by the invention. The graphene oxide/ferroferric oxide/silicon dioxide composite material or the wave-absorbing material provided by the invention has wave-absorbing performance.
The invention provides a preparation method of a graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material.
According to the invention, a normal-pressure coprecipitation method is adopted, chemical reaction is carried out at normal temperature and normal pressure, the limitation of a solvent thermal method on equipment and conditions is avoided, graphene oxide and ferroferric oxide are creatively compounded firstly, and a divalent iron source and a third-order iron source are adopted simultaneously, so that the graphene oxide can be directly compounded with ferroferric oxide primary particles, and then silicon dioxide is coated. The graphene oxide/ferroferric oxide/silicon dioxide composite wave-absorbing material prepared by the invention has excellent wave-absorbing performance, improves the temperature resistance and oxidation resistance of the material, and has good application prospect in the field of electromagnetic wave absorption.
Experimental results show that the preparation method provided by the invention can effectively improve the electromagnetic absorption strength and the electromagnetic absorption width of the magnetic graphene material, the maximum absorption strength reaches-28.2 dB, the effective absorption width is 4.0GHz, and the temperature resistance and the oxidation resistance are also obviously improved.
For further illustration of the present invention, the following describes in detail a method for preparing a graphene oxide/ferroferric oxide/silica composite material according to the present invention with reference to examples, but it should be understood that the examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific procedures are given, which are only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Taking an oxidized graphene aqueous solution, ultrasonically dispersing for a certain time, and then dropwise adding a mixed solution of ferrous chloride and ferric chloride in a certain proportion to obtain a precursor solution. Wherein the mass fraction of the graphene oxide aqueous solution is 3 per mill, the ultrasonic time is 20min, and the content of ferrous chloride: iron chloride molar ratio 2:1, iron salt: the mass ratio of the graphene oxide is 20: 1;
2, subjecting the precursor solution obtained in the step 1 to ultrasonic treatment and stirring for a period of 20min, slowly adding a certain amount of ammonia water, adjusting the pH value of the solution to 9.5, and continuously reacting for 3h to obtain a black precipitate solution;
and 3, magnetically sucking the black precipitate solution obtained in the step 2, pouring out supernatant, slowly adding a certain amount of ethanol and tetraethoxysilane, and continuously stirring for 2 hours to obtain a reaction product. Wherein the volume ratio of the ethanol to the ethyl orthosilicate is 40: 1;
and 4, after magnetically separating the reaction product obtained in the step 3, respectively washing the reaction product for 3 times by using ultrapure water and ethanol, then carrying out vacuum drying and airflow crushing to obtain the graphene oxide composite ferroferric oxide @ silicon dioxide composite wave-absorbing material, namely the graphene oxide/ferroferric oxide/silicon dioxide composite material.
Referring to fig. 1, fig. 1 is a process flow diagram of a preparation process provided in an embodiment of the present invention.
The graphene oxide/ferroferric oxide/silicon dioxide composite material prepared in the embodiment 1 of the invention is characterized.
Referring to fig. 2, fig. 2 is a scanning electron microscope photograph of the graphene oxide/ferroferric oxide @ silica composite material prepared in example 1 of the present invention.
As can be seen from fig. 2, the graphene oxide/ferroferric oxide @ silica composite material successfully prepared in this embodiment has a particle size of about 50nm, and the ferroferric oxide @ silica nanoparticles are uniformly distributed on the surface of the graphene oxide.
Referring to fig. 3, fig. 3 is a transmission electron microscope photograph of the graphene oxide/ferroferric oxide @ silica composite material prepared in example 1 of the present invention.
As can be seen from fig. 3, the ferroferric oxide @ silica nanoparticles prepared in this example have a core-shell structure, the core is a ferroferric oxide nanoparticle primary particle, the size of the core is about 30nm, the shell is silica, and the ferroferric oxide @ silica nanoparticles are uniformly distributed on the surface of graphene oxide.
The graphene oxide/ferroferric oxide/silicon dioxide composite material prepared in the embodiment 1 of the invention is detected.
The result of the detection by a spectrophotometer shows that the hydroxyl clearance rate is 92 percent, which shows that the composite material has better temperature resistance and oxidation resistance.
The powder product obtained in the embodiment 1 and solid paraffin are uniformly mixed according to the mass ratio of 4:6, a special mold is utilized to press the powder product into a coaxial type with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm, an Agilent TE5071C vector network analyzer is used for testing the wave absorbing performance, the testing frequency is 2-18 GHz, and the thickness is 2 mm.
Referring to fig. 4, fig. 4 is an electromagnetic reflectance curve of the graphene oxide/ferroferric oxide @ silica composite material prepared in the embodiment of the present invention.
As can be seen from FIG. 4, the maximum absorption at 5.17GHz is-28.2 dB, the wave absorption at 4.5-6.2 and 15.7-18GHz is below-10 dB, and the effective absorption width is 4.0 GHz.
Example 2
Taking a graphene oxide aqueous solution prepared by Shandong European platinum New Material Co., Ltd, ultrasonically dispersing for a certain time, and then dropwise adding a mixed solution of ferrous chloride and ferric chloride in a certain proportion to obtain a precursor solution. Wherein the mass fraction of the graphene oxide aqueous solution is 8 per mill, the ultrasonic time is 20min, and the content of ferrous chloride: iron chloride molar ratio 3:1, iron salt: the mass ratio of the graphene oxide is 50: 1;
2, subjecting the precursor solution obtained in the step 1 to ultrasonic treatment and stirring for a period of 20min, slowly adding a certain amount of ammonia water, adjusting the pH value of the solution to 10, and continuously reacting for 3h to obtain a black precipitate solution;
and 3, magnetically sucking the black precipitate solution obtained in the step 2, pouring out supernatant, slowly adding a certain amount of ethanol and tetraethoxysilane, and continuously stirring for 2 hours to obtain a reaction product. Wherein the volume ratio of the ethanol to the ethyl orthosilicate is 160: 1;
and 4, after magnetically separating the reaction product obtained in the step 3, respectively washing the reaction product for 3 times by using ultrapure water and ethanol, then carrying out vacuum drying and airflow crushing to obtain the graphene oxide composite ferroferric oxide @ silicon dioxide composite wave-absorbing material, namely the graphene oxide/ferroferric oxide/silicon dioxide composite material.
The graphene oxide/ferroferric oxide/silicon dioxide composite material prepared in the embodiment 2 of the invention is detected.
The result of the detection by a spectrophotometer shows that the hydroxyl clearance is 87 percent, which shows that the composite material has better temperature resistance and oxidation resistance.
The powder product obtained in the embodiment 2 is uniformly mixed with solid paraffin according to the mass ratio of 4:6, the mixture is pressed into a coaxial type with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by using a special mould, and the wave absorbing performance is tested by using an Agilent TE5071C vector network analyzer, wherein the test frequency is 2-18 GHz, and the thickness is 2 mm.
Referring to fig. 4, fig. 4 is an electromagnetic reflectance curve of the graphene oxide/ferroferric oxide @ silica composite material prepared in the embodiment of the present invention.
As can be seen from FIG. 4, the maximum absorption at 6.78GHz is-17.8 dB, the absorption at the frequency band of 5.8-7.9 GHz is below-10 dB, and the effective absorption width is 2.1 GHz.
Example 3
Taking an oxidized graphene aqueous solution, ultrasonically dispersing for a certain time, and then dropwise adding a mixed solution of ferrous chloride and ferric chloride in a certain proportion to obtain a precursor solution. Wherein the mass fraction of the graphene oxide aqueous solution is 3 per mill, the ultrasonic time is 60min, and the weight fraction of ferrous chloride: iron chloride molar ratio 1:5, iron salt: the mass ratio of the graphene oxide is 8: 1;
2, subjecting the precursor solution obtained in the step 1 to ultrasonic treatment and stirring for a period of 20min, slowly adding a certain amount of ammonia water, adjusting the pH value of the solution to 8.5, and continuously reacting for 3h to obtain a black precipitate solution;
and 3, magnetically sucking the black precipitate solution obtained in the step 2, pouring out supernatant, slowly adding a certain amount of ethanol and tetraethoxysilane, and continuously stirring for 2 hours to obtain a reaction product. Wherein the volume ratio of the ethanol to the ethyl orthosilicate is 80: 1;
and 4, after magnetically separating the reaction product obtained in the step 3, respectively washing the reaction product for 3 times by using ultrapure water and ethanol, then carrying out vacuum drying and airflow crushing to obtain the graphene oxide composite ferroferric oxide @ silicon dioxide composite wave-absorbing material, namely the graphene oxide/ferroferric oxide/silicon dioxide composite material.
The graphene oxide/ferroferric oxide/silicon dioxide composite material prepared in the embodiment 3 of the invention is detected.
The result of the detection by a spectrophotometer shows that the hydroxyl clearance rate is 88 percent, which shows that the composite material has better temperature resistance and oxidation resistance.
The powder product obtained in the embodiment 3 is uniformly mixed with solid paraffin according to the mass ratio of 4:6, the mixture is pressed into a coaxial type with the outer diameter of 7.0mm, the inner diameter of 3.0mm and the thickness of 3.0mm by using a special mould, and the wave absorbing performance is tested by using an Agilent TE5071C vector network analyzer, wherein the test frequency is 2-18 GHz, and the thickness is 2 mm.
Referring to fig. 4, fig. 4 is an electromagnetic reflectance curve of the graphene oxide/ferroferric oxide @ silica composite material prepared in the embodiment of the present invention.
As can be seen from FIG. 4, the maximum absorption at 11.32GHz is-13.6 dB, the wave absorption at the frequency band of 9.8-13.1 GHz is below-10 dB, and the effective absorption width is 3.3 GHz.
The above detailed description of the method for preparing a graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material according to the present invention is provided, and the principle and embodiments of the present invention are described herein by using specific examples, which are provided only to help understanding the method and the core concept of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any devices or systems and performing any combination of methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of a graphene oxide/ferroferric oxide/silicon dioxide composite material is characterized by comprising the following steps:
A) mixing the graphene oxide dispersion liquid, a ferric iron source and a ferrous iron source to obtain a precursor solution;
B) performing ultrasonic treatment on the precursor solution obtained in the step, and adding a pH value regulator for reaction to obtain black precipitate;
C) and mixing the black precipitate obtained in the step, a silicon source and an organic solvent again for reaction to obtain the graphene oxide/ferroferric oxide/silicon dioxide composite material.
2. The method of claim 1, wherein the ferric iron source comprises one or more of ferric chloride, ferric sulfate, and ferric nitrate;
the ferrous iron source comprises one or more of ferrous chloride, ferrous sulfate and ferrous nitrate;
the molar ratio of the ferric iron source to the ferrous iron source is (1-10): (10-1);
the mass ratio of the total mass of the ferric iron source and the ferrous iron source to the graphene oxide is (5-100): 1.
3. the preparation method according to claim 1, wherein the graphene oxide dispersion liquid is 0.1-1% by mass;
the mixing is ultrasonic dispersion;
the mixing time is 10-120 min.
4. The method of claim 1, wherein the ultrasound is ultrasonic agitation;
the ultrasonic time is 10-120 min;
the pH value regulator comprises one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and urea.
5. The preparation method according to claim 1, wherein the pH value after the addition of the pH value regulator is 8 to 11;
the reaction time is 1-6 h;
the reaction also comprises a magnetic attraction step.
6. The method of claim 1, wherein the silicon source comprises one or more of ethyl orthosilicate, methyl orthosilicate, tetrabutyl silicate, tetrapropyl silicate, and butyl orthosilicate;
the organic solvent comprises one or more of ethanol, methanol, benzyl alcohol, isopropanol and glycol;
the volume ratio of the silicon source to the organic solvent is 1: (20-200);
the mass ratio of the silicon source to the graphene oxide is (50-800): 1.
7. the preparation method according to claim 1, wherein the time for the remixing reaction is 1-6 hours;
the post-treatment step is also included after the secondary mixing reaction;
the post-treatment comprises one or more of magnetic separation, washing, drying and crushing.
8. The preparation method according to claim 1, wherein the black precipitate is a ferroferric oxide/silica composite material;
the graphene oxide/ferroferric oxide/silicon dioxide composite material has the specific structure as follows:
the ferroferric oxide/silicon dioxide composite material is ferroferric oxide @ silicon dioxide nano particles;
the ferroferric oxide @ silicon dioxide nano-particles have a core-shell structure, wherein the ferroferric oxide nano-particles are used as cores, and the silicon dioxide is used as shells.
9. The preparation method according to claim 8, wherein the particle size of the ferroferric oxide nanoparticles is 15-50 nm;
the thickness of the silicon dioxide shell layer is 5-30 nm;
the ferroferric oxide @ silicon dioxide nanoparticles are uniformly distributed on the surface of graphene oxide;
the thickness of the graphene oxide sheet layer is 0.35-2.5 nm;
the sheet diameter of the graphene oxide is 5-20 mu m.
10. A wave-absorbing material is characterized by comprising the graphene oxide/ferroferric oxide/silicon dioxide composite material prepared by the preparation method of any one of claims 1 to 9.
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