CN110079271B - Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof - Google Patents

Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof Download PDF

Info

Publication number
CN110079271B
CN110079271B CN201910406790.6A CN201910406790A CN110079271B CN 110079271 B CN110079271 B CN 110079271B CN 201910406790 A CN201910406790 A CN 201910406790A CN 110079271 B CN110079271 B CN 110079271B
Authority
CN
China
Prior art keywords
magnetic
protein
based carbon
nanoparticle composite
graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910406790.6A
Other languages
Chinese (zh)
Other versions
CN110079271A (en
Inventor
岳喜贵
徐攀
左小丹
李梦竹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201910406790.6A priority Critical patent/CN110079271B/en
Publication of CN110079271A publication Critical patent/CN110079271A/en
Application granted granted Critical
Publication of CN110079271B publication Critical patent/CN110079271B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding

Abstract

The invention provides a protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent and a preparation method and application thereof, belonging to the technical field of wave-absorbing materials, wherein the preparation method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent comprises the following steps: 1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 hours to prepare magnetic nanoparticles; 2) mixing the magnetic nanoparticles with egg white, and then carrying out curing treatment to obtain a protein-magnetic nanoparticle compound; 3) carbonizing the protein-magnetic nanoparticle composite obtained in the step 2) to obtain the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent. The material prepared by the composite wave absorbing agent has stronger wave absorbing performance, has the characteristics of wider wave absorbing frequency band, thin absorber matching thickness and the like, and has wider application prospect in the field of wave absorbing materials.

Description

Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent, and a preparation method and application thereof.
Background
In recent years, with the increasing use of wireless devices and electronic devices, electromagnetic interference and electromagnetic wave radiation not only affect the normal operation of the electronic devices, but also bring a great threat to human health. Finding a microwave absorbing material that is capable of absorbing microwave energy and converting it into thermal energy is expected to be an effective way to address this serious electromagnetic interference problem. The wave-absorbing material, also called as microwave absorbing material, stealth material or electromagnetic wave absorbing material, can absorb and attenuate the electromagnetic wave incident on the surface of the material and convert the electromagnetic wave energy into energy of other forms, thereby realizing smaller reflection, scattering and transmission. In terms of composition, the wave-absorbing material mainly comprises two parts, wherein one part is a matrix material with a bonding effect, generally a resin material with good wave-transmitting and thermal stability, and the other part is a wave-absorbing agent which is used as a main body of the wave-absorbing material and mainly plays a role in electromagnetic loss. Therefore, the preparation of the wave absorbing agent with excellent performance is a prerequisite for preparing the wave absorbing material. Generally, an excellent electromagnetic wave absorber must have a wide absorption bandwidth, a strong electromagnetic wave absorption capability, a thin absorber matching thickness, and a low material density.
According to transmission line theory (Qin, f.; Brosseau, c., j.appl.phys.2012,111,061301), it is generally considered that electromagnetic wave absorbing materials can be classified into two broad categories of dielectric loss and magnetic loss according to their electromagnetic wave loss mechanisms. However, it is difficult to obtain ideal impedance matching conditions for a single dielectric loss or magnetic loss material, so that the electromagnetic wave absorption capability is weak, and it is difficult to satisfy the characteristics of high efficiency, wide frequency, and light weight. Therefore, the combination of the dielectric loss carbon material and the magnetic loss material is a good choice for developing an excellent electromagnetic wave absorption material. The effective combination of dielectric loss and magnetic loss components can solve the problem of electromagnetic matching on one hand, so that the electromagnetic wave absorbing material can effectively enter the wave absorbing material, and on the other hand, the combination of multiple loss characteristics can quickly lose the electromagnetic waves entering the material, thereby achieving the characteristics of low reflection and strong absorption force. The carbon material has good dielectric properties, good chemical stability, high mechanical strength and excellent thermal stability. Therefore, the carbon material is combined with the magnetic particles with magnetic loss capacity to prepare the carbon/magnetic particle composite wave absorbing agent (CN 106520071A, CN104927762A), so that the electromagnetic wave can be rapidly lost, and excellent wave absorbing performance can be obtained.
However, the existing carbon-based materials have single source and unsatisfactory wave-absorbing effect.
Disclosure of Invention
In view of the above, the present invention aims to provide a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber, a preparation method and applications thereof; the protein is used as a biomass carbon source material, and the obtained protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent has excellent wave absorbing performance.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber comprises the following steps:
1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 hours to prepare magnetic nanoparticles;
2) mixing the magnetic nanoparticles with egg white, and then carrying out curing treatment to obtain a protein-magnetic nanoparticle compound;
3) carbonizing the protein-magnetic nanoparticle composite obtained in the step 2) to obtain the protein-based carbon/magnetic FeCo nanoparticle composite wave absorbing agent.
Preferably, the reaction in step 1) has a pH of 9 to 11.
Preferably, the temperature of the curing treatment in the step 2) is 85-95 ℃.
Preferably, the time of the curing treatment in the step 2) is 0.5-2.5 h.
Preferably, the carbonization temperature in the step 3) is 600-1200 ℃.
The invention provides a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent prepared by the preparation method.
The invention provides a preparation method of a graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber, which comprises the following steps:
s1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 h to prepare magnetic nanoparticles;
s2) dispersing graphene in concentrated acid, and carrying out ultrasonic treatment, reflux and washing to obtain acidified graphene;
s3) mixing the magnetic nanoparticles, the acidified graphene and the egg white, and curing to obtain a graphene-protein-magnetic nanoparticle compound;
s4) carbonizing the graphene-protein-magnetic nanoparticle composite obtained in the step 2) to obtain a graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent;
step S1) and step S2).
The invention also provides the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent prepared by the preparation method.
The invention also provides an application of the protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent or the graphene-doped protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent in preparing wave absorbing materials.
Preferably, the addition amount of the protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent or the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent in the wave-absorbing material is 30-60%.
The invention has the beneficial effects that: the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber or graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber provided by the invention takes egg white liquid as a carbon source, so that the magnetic nanoparticles are easier to disperse, the preparation method is simple, and the industrial production is easy to realize. The material prepared by the protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent has stronger wave absorbing performance, has the characteristics of wider wave absorbing frequency band, thin absorber matching thickness and the like, and has wider application prospect in the field of wave absorbing materials.
Drawings
FIG. 1 is an XRD spectrum of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber prepared in example 1;
FIG. 2 is a scanning electron micrograph of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber prepared in example 1, wherein the scale A is 500 μm and the scale B is 5 μm;
FIG. 3 is a scanning electron micrograph of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber prepared in example 2, wherein the scale of A is 500 μm and the scale of B is 5 μm;
fig. 4 is a reflection loss RL data plot calculated from electromagnetic parameters of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material tested in example 2;
FIG. 5 is a scanning electron micrograph of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber prepared in example 3, wherein the scale of A is 500 μm and the scale of B is 5 μm;
fig. 6 is an electromagnetic parameter curve of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material prepared in example 4.
Detailed Description
The invention provides a preparation method of a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber, which comprises the following steps: 1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 hours to prepare magnetic nanoparticles; 2) mixing the magnetic nanoparticles with egg white, and then carrying out curing treatment to obtain a protein-magnetic nanoparticle compound; 3) carbonizing the protein-magnetic nanoparticle composite obtained in the step 2) to obtain the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent.
The magnetic nanoparticles are prepared by mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate and reacting at 70-100 ℃ for 1-2 hours. The number ratio of iron ions to cobalt ions in the reaction system is preferably 1: 1-15, and more preferably 1: 5-10. In the invention, the proportion of the ferric chloride hexahydrate, the ferrous chloride tetrahydrate, the cobalt chloride hexahydrate and the water is preferably (3.4-3.8) g, (0.8-1.2) g and (0.25-0.4) g and 150mL, and more preferably 03.6612g, 1.0772g, 0.3244g and 150 mL. In the present invention, the mixing vessel is preferably a three-necked round bottom flask. In the invention, the reaction temperature is preferably 78-82 ℃, and more preferably 80 ℃; the reaction time is preferably 1.2-1.8 h, and more preferably 1.5 h; the reaction is preferably at N2Under protection; stirring is preferably carried out in the reaction process, and the rotating speed of the stirring is preferably 700-900 rpm, and more preferably 800 rpm. In the present invention, the pH of the reaction is preferably 9 to 11, more preferably 10; in the present invention, the pH of the reaction is preferably NH3·H2And O is regulated. After the reaction is finished, preferably collecting the magnetic nanoparticles by using a magnet, and preferably cleaning the collected magnetic nanoparticles to remove impurities; the cleaning preferably comprises deionized water cleaning and ethanol cleaning which are sequentially carried out. Hair brushPreferably, the method further comprises dispersing the magnetic nanoparticles with deionized water for subsequent use after the washing.
After the magnetic nanoparticles are obtained, the magnetic nanoparticles are mixed with egg white liquid, and then the mixture is cured to obtain the protein-magnetic nanoparticle compound. The source of the egg white liquid is not particularly limited in the invention, and the egg white liquid can be from any source. In the practice of the present invention, the egg white is preferably derived from poultry, more preferably from eggs, duck eggs or goose eggs. In the present invention, the egg white is preferably dispersed before being mixed with the magnetic nanoparticles; the egg white liquid is preferably dispersed by using a dispersing machine. In the invention, the magnetic nanoparticles and the egg white are preferably subjected to ultrasonic treatment after being mixed, and the ultrasonic treatment aims to uniformly mix the magnetic nanoparticles and the egg white; in the implementation process of the present invention, the power of the ultrasound is preferably 500W, and the time of the ultrasound is not particularly limited in the present invention, and is preferably uniform. In the invention, the mass ratio of the carbon source to the magnetic nanoparticles in the egg white is preferably 6: 1. in the invention, the curing treatment temperature is preferably 85-95 ℃, and more preferably 90 ℃; the curing time is preferably 0.5 to 2.5 hours, and more preferably 1 to 2 hours. In the present invention, after the solidification treatment, a drying step is preferably further included, in the present invention, the drying is preferably freeze-drying, and the freeze-drying parameters in the present invention are not particularly limited, and may be those conventional in the art.
After the protein-magnetic nanoparticle composite is obtained, the protein-magnetic nanoparticle composite is carbonized to obtain the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent. In the invention, the carbonization temperature is preferably 600-1200 ℃, and more preferably 800-1000 ℃. In the practice of the present invention, the carbonization procedure is preferably as follows: at 25-800 ℃, 5 ℃/min and 155 min; 60min at 800 ℃; at 800-1000 ℃, 5 ℃/min and 40 min; 60min at 1000 ℃; 1000-25 ℃, 5 ℃/min and 195 min. The present invention preferably further comprises a grinding step after the carbonization, the grinding is preferably carried out in a mortar, and the purpose of the grinding in the present invention is to grind the lump product into powder for subsequent processing.
The invention provides a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent prepared by the method.
The invention also provides a preparation method of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber, which comprises the following steps: s1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 h to prepare magnetic nanoparticles; s2) dispersing graphene in concentrated acid, and carrying out ultrasonic treatment, reflux and washing to obtain acidified graphene; s3) mixing the magnetic nanoparticles, the acidified graphene and the egg white, and curing to obtain a graphene-protein-magnetic nanoparticle compound; s4) carbonizing the graphene-protein-magnetic nanoparticle composite obtained in the step 2) to obtain a graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent; step S1) and step S2).
In the invention, the preparation method of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber is different from the preparation method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber in that the curing treatment is addition amount of acidified graphene; the other steps are consistent with the preparation method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent, and the acidification step of the graphene is only described in detail below; other steps are not described in detail.
In the invention, graphene is dispersed in concentrated acid for ultrasonic treatment, reflux and washing to obtain acidified graphene. In the invention, the concentrated acid is preferably a mixture of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is preferably (2-4) to 1, and more preferably 3 to 1. In the invention, the mass-to-volume ratio of the graphene to the concentrated acid is preferably (3-5) g:150mL, and more preferably 4g:150 mL. In the invention, the ultrasonic temperature is preferably 38-42 ℃, and more preferably 40 ℃; the ultrasonic treatment time is preferably 25-35 min, and more preferably 30 min. In the invention, the reflux temperature is preferably 75-85 ℃, and more preferably 80 ℃; the refluxing time is preferably 1.5-2.5 h, and more preferably 2 h. In the invention, after the reflux, the temperature is preferably reduced, and the temperature is preferably naturally reduced; washing the acidified graphene when the temperature is reduced to room temperature is preferable; the washing is preferably carried out by using deionized water, and the washing is preferably stopped when the washed deionized water is neutral; the method for testing the pH value of the deionized water has no special requirements, and the conventional test strip method and the pH meter test method in the field can be used.
After the acidified graphene is obtained, the magnetic nanoparticles, the acidified graphene and egg white liquid are mixed and then are subjected to curing treatment to obtain the graphene-protein-magnetic nanoparticle compound. The curing method and parameters refer to the preparation method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent, and are not described herein again.
In the invention, after the graphene-protein-magnetic nanoparticle composite is obtained, the obtained graphene-protein-magnetic nanoparticle composite is carbonized to obtain the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber, and the specific method refers to the preparation method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber, which is not described herein again.
The invention also provides the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent prepared by the preparation method.
The invention also provides an application of the protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent or the graphene-doped protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent in preparing wave absorbing materials. In the present invention, the addition amount of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber or graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber is preferably 30% to 60%, and more preferably 50%. In the invention, the wave-absorbing material preferably takes paraffin as a matrix; the preferred circular ring of the wave-absorbing material is filled with the wave-absorbing material; in a specific embodiment of the invention, the wave-absorbing material has an outer diameter of preferably 6.9mm, an inner diameter of preferably 3.14mm and a thickness of preferably 2 mm.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The synthesis method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber comprises the following reaction steps:
(1) into a 250mL three-necked round-bottomed flask were charged 150mL of water, ferric chloride hexahydrate (3.6612g, 13.55mmol), ferrous chloride tetrahydrate (1.0772g, 5.42mmol), and cobalt chloride hexahydrate (0.3244g, 1.36mmol) in the presence of N2Under the protection of (2), the solution is rapidly heated to 80 ℃ while being mechanically stirred (800rpm), and then a certain amount of NH is added to the above mixture3·H2Adjusting the pH value to 10, heating at 80 ℃ for reaction for 1h, collecting with a magnet, thoroughly washing with deionized water and ethanol, removing impurities, weighing to obtain 0.9522g of iron-cobalt oxide, and dispersing the iron-cobalt oxide with 30mL of deionized water for further use;
(2) and (2) adding 34.19g of egg white into a 100mL beaker, dispersing the egg white into a uniform solution by using a dispersion machine, adding 10mL of the iron-cobalt oxide obtained in the step (1) into the dispersed liquid protein, carrying out ultrasonic treatment on the mixture until the mixture is uniform, carrying out ultrasonic heating to 90 ℃ for curing treatment for 1h, and then dehydrating the mixture by using a freeze dryer to obtain 3.2g of a dried protein/magnetic iron-cobalt oxide compound.
(3) And (2) placing the dried protein/iron-cobalt oxide compound in a ceramic crucible, transferring the ceramic crucible to a high-temperature tube furnace, treating at 800 ℃ for 1h, and then continuously heating to 1000 ℃ for 1h (programmed heating: 25-800 ℃, 5 ℃/min, 155min, 800 ℃, 60min, 800-1000 ℃, 5 ℃/min, 40min, 1000 ℃, 60min, 1000-25 ℃, 5 ℃/min, 195 min). And (3) further mechanically grinding the carbonized product to obtain 1.6g of protein-based carbon/magnetic Fe Co nano particle composite wave absorbing agent.
The XRD spectrogram of the prepared protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber is shown in figure 1, and the XRD representation shows that after high-temperature carbonization treatment, iron and cobalt oxides are reduced into iron and cobalt simple substances, so that magnetic loss components are brought to protein-based carbon.
The scanning electron micrograph of the prepared protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber is shown in FIG. 2, and it can be seen from the A picture that the interior of the material has a dense macroporous structure, which is mainly caused by sublimation of water during freeze drying and gas escape during carbonization, and further the cross section is enlarged to find that a large amount of iron and cobalt particles are deposited on the surface of the carbon material, and the size of the particles is different between 500 and 900nm, because the iron and cobalt atoms are easy to generate secondary crystallization during high-temperature reduction, so that the sizes of the particles are difficult to keep consistent.
Example 2
The synthesis method of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber comprises the following reaction steps:
(1) dispersing 4g of graphene in a mixture of concentrated sulfuric acid (120mL) and concentrated nitric acid (40mL), performing ultrasonic treatment at 40 ℃ for 30min, then refluxing at 80 ℃ for 2h, cooling to room temperature, slowly adding dropwise water for dilution, and then pouring a large amount of water for washing to neutrality;
(2) 32.48g of egg white liquid of eggs is added into a 100mL beaker and dispersed to be a uniform solution by a dispersion machine, 10mL of iron-cobalt oxide obtained in the step (1) of the example 1 and 1.1g of acidified graphene obtained in the step (1) are added into dispersed liquid protein, ultrasonic treatment is carried out to be a uniform state, ultrasonic heating is carried out to 90 ℃ for solidification treatment for 1h, and then dehydration is carried out by a freeze dryer, so that 3.6g of dried graphene-doped protein/iron-cobalt oxide compound is obtained.
(3) And (2) placing the dried graphene-doped protein/iron-cobalt oxide compound in a ceramic crucible, transferring the ceramic crucible to a high-temperature tube furnace, treating at 800 ℃ for 1h, and then continuously heating to 1000 ℃ for 1h (programmed heating: 25-800 ℃, 5 ℃/min, 155min, 800 ℃, 60min, 800-1000 ℃, 5 ℃/min, 40min, 1000 ℃, 60min, 1000-25 ℃, 5 ℃/min, 195 min). And (3) further mechanically grinding the carbonized product to obtain 1.5g of graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent.
A scanning electron microscope picture of the prepared graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber is shown in FIG. 3, and from the A picture, it can be seen that the material has a dense macroporous structure inside, which is mainly caused by sublimation of water during freeze drying and gas escape during carbonization, and further cross-sectional view amplification shows that the graphene is embedded in a porous carbon matrix, and a large amount of iron and cobalt particles are deposited on the surface of the carbon material, and the particles are different in size between 500 and 900nm, because the iron and cobalt atoms are easy to generate secondary crystallization during high-temperature reduction, the particle sizes are difficult to keep consistent.
The reflection loss RL (luoshao, prunus, sea-demanding bear, maxmin, schweika, jacarassia, inorganic materials article 2015,30,23-28) of the composite wave absorber was calculated by the following formula.
Figure BDA0002061494550000081
Figure BDA0002061494550000091
Figure BDA0002061494550000092
In the formula: z0Is the free space impedance; mu.s0、ε0Is the vacuum permeability and dielectric constant, ε0＝8.854187817×10-12F/m，μ0＝4π×10-7H/m；ZinIs the input impedance of the wave-absorbing material (obtained by calculation by using epsilon ', mu ' and mu ' data); f is the frequency of the electromagnetic wave (range of 2-18 GHz); d is the thickness of the wave-absorbing material; c is the propagation speed of electromagnetic wave in free space, equal to 3X 10 of light speed8m/s；εr(εr═ epsilon' -j epsilon ") and mur(μrMu' -j mu ") is the equivalent relative complex permittivity and complex permeability of the wave-absorbing material, and j is the imaginary unit of the complex permittivity and complex permeability, and has no practical significance. Experiments can be carried out to determine epsilon ', epsilon ', mu ' of the material under different electromagnetic wave frequencies f.
Graphene prepared in this exampleThe reflection loss data of the doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber is shown in FIG. 4. The protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent has excellent loss characteristics on electromagnetic waves, when the thickness of the wave absorbing material is 1.0mm (the thickness is not a concept with the thickness in the embodiment 4. the thickness in the embodiment 4 is the thickness of a sample prepared when electromagnetic parameters of the material are tested, and the thickness is the value assigned when the reflection loss of the material is calculated by combining the electromagnetic parameters with a formula), the maximum loss of the electromagnetic waves is realized, and the reflection loss reaches-51.86 dB. Meanwhile, by adjusting the thickness of the wave-absorbing material, when the thickness is changed between 1.0mm and 5.0mm, the material can realize the 3.76 GHz-11.2 GHz, 11.6 GHz-14.56 GHz and 14.56 GHz-18 GHz frequency bands (C band, X band and K band) of the electromagnetic wavesuBand) absorption in excess of-10 dB (in excess of 90% absorption). Therefore, the graphene-doped protein-based/magnetic Fe Co nanoparticle composite wave absorber material prepared by the embodiment has strong electromagnetic loss capability.
Example 3
The synthesis method of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber comprises the following reaction steps:
(1) adding 30.77g of liquid protein into a 100mL beaker, dispersing the mixture into a uniform solution by using a dispersion machine, adding 10mL of iron-cobalt oxide obtained in the step (1) in the example 1 and 2.2g of acidified graphene obtained in the step (1) in the example 2 into the dispersed liquid protein, carrying out ultrasonic treatment to a uniform state, carrying out ultrasonic heating to 90 ℃ for curing treatment for 1h, and then carrying out dehydration by using a freeze dryer to obtain 4.2g of dried graphene-doped protein/iron-cobalt oxide composite.
(2) And (2) placing the dried graphene-doped protein/iron-cobalt oxide compound in a ceramic crucible, transferring the ceramic crucible to a high-temperature tube furnace, treating at 800 ℃ for 1h, and then continuously heating to 1000 ℃ for 1h (programmed heating: 25-800 ℃, 5 ℃/min, 155min, 800 ℃, 60min, 800-1000 ℃, 5 ℃/min, 40min, 1000 ℃, 60min, 1000-25 ℃, 5 ℃/min, 195 min). And (3) further mechanically grinding the carbonized product to obtain 1.6g of graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent.
A scanning electron microscope photograph of the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material prepared in this embodiment is shown in fig. 5, it can be seen from the a diagram that the material has a dense macroporous structure inside, which is mainly caused by sublimation of water during freeze drying and gas escape during carbonization, and further cross-sectional view enlargement finds that graphene is embedded in a porous carbon matrix, and as the addition amount of graphene increases, crystalline carbon has more opportunities to interact and cluster together to form clusters in the composite material, and a large amount of iron and cobalt particles are deposited on the surface of the carbon material, and the size of the particles is different between 500 nm and 900nm, which is because iron and cobalt atoms are likely to undergo secondary crystallization during high-temperature reduction, so that the particle size is difficult to maintain consistent.
Example 4
Application of protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material
The method is characterized in that paraffin is used as a matrix, the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material prepared in example 1 is used as a wave absorber, a test sample with the wave absorber filling amount of 50% is prepared, and the method can be realized through the following steps:
(1) evenly mixing paraffin and a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material according to the mass percent of a wave absorber/(the wave absorber + the paraffin) of 50%;
(2) pressing the mixture of the wave absorbing agent and the paraffin wax obtained in the step into a test ring with the outer diameter of 6.9mm, the inner diameter of 3.14mm and the thickness of 2mm by using an oil press through a die;
(3) electromagnetic parameters (epsilon ', epsilon ", mu', mu) of the prepared test ring in the range of 2-18 GHz are tested by using Agilent N5244APNA-X, and the reflection loss RL (Luohuo, Liqian, bear sea, Makeming, Schweika, Jiacaixia, inorganic material science 2015,30,23-28) of the composite wave absorbing agent is calculated by using the following formula.
Figure BDA0002061494550000101
Figure BDA0002061494550000102
Figure BDA0002061494550000111
In the formula: z0Is the free space impedance; mu.s0、ε0Is the vacuum permeability and dielectric constant, ε0＝8.854187817×10-12F/m，μ0＝4π×10-7H/m；ZinIs the input impedance of the wave-absorbing material (obtained by calculation by using epsilon ', mu ' and mu ' data); f is the frequency of the electromagnetic wave (range of 2-18 GHz); d is the thickness of the wave-absorbing material; c is the propagation speed of electromagnetic wave in free space, equal to 3X 10 of light speed8m/s；εr(εr═ epsilon' -j epsilon ") and mur(μrMu' -j mu ") is the equivalent relative complex permittivity and complex permeability of the wave-absorbing material, and j is the imaginary unit of the complex permittivity and complex permeability, and has no practical significance. Experiments can be carried out to determine epsilon ', epsilon ', mu ' of the material under different electromagnetic wave frequencies f.
An electromagnetic parameter curve of a test sample prepared by mixing the prepared protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber with paraffin is shown in FIG. 6, and the real part and the imaginary part of the dielectric constant and the magnetic permeability in the electromagnetic parameter respectively represent the storage capacity and the loss capacity of the material to the energy of an electromagnetic field, so that the prepared protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber material has relatively strong dielectric loss capacity and magnetic loss capacity. The dielectric loss capacity is stronger for low-frequency electromagnetic waves, and the magnetic loss capacity is stronger for high-frequency electromagnetic waves.
According to the embodiments, the protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent or the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave-absorbing agent provided by the invention has strong wave-absorbing performance, has the characteristics of wide wave-absorbing frequency band, thin absorber matching thickness and the like, and has a wide application prospect in the field of wave-absorbing materials.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber comprises the following steps:
1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 hours to prepare magnetic nanoparticles;
2) mixing the magnetic nanoparticles with egg white, and then carrying out curing treatment to obtain a protein-magnetic nanoparticle compound; the mass ratio of the carbon source to the magnetic nanoparticles in the egg white liquid is 6: 1;
3) carbonizing the protein-magnetic nanoparticle composite obtained in the step 2) to obtain a protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent;
the pH value of the reaction in the step 1) is 9-11.
2. The method according to claim 1, wherein the temperature of the curing treatment in step 2) is 85 to 95 ℃.
3. The preparation method according to claim 2, wherein the curing treatment time in the step 2) is 0.5 to 2.5 hours.
4. The method according to claim 1, wherein the carbonization temperature in step 3) is 600 to 1200 ℃.
5. The protein-based carbon/magnetic Fe Co nanoparticle composite wave absorbing agent prepared by the preparation method of any one of claims 1 to 4.
6. A preparation method of a graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber comprises the following steps:
s1) mixing water, ferric chloride hexahydrate, ferrous chloride tetrahydrate and cobalt chloride hexahydrate, and reacting at 70-100 ℃ for 1-2 h to prepare magnetic nanoparticles;
s2) dispersing graphene in concentrated acid, and carrying out ultrasonic treatment, reflux and washing to obtain acidified graphene;
s3) mixing the magnetic nanoparticles, the acidified graphene and the egg white, and curing to obtain a graphene-protein-magnetic nanoparticle compound;
s4) carbonizing the graphene-protein-magnetic nanoparticle composite obtained in the step S2) to obtain a graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber;
step S1) and step S2).
7. The graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber prepared by the preparation method of claim 6.
8. The use of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber of claim 5 or the graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber of claim 7 in the preparation of wave absorbing materials.
9. The application of claim 8, wherein the addition amount of the protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber or graphene-doped protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber in the wave absorbing material is 30-60%.
CN201910406790.6A 2019-05-15 2019-05-15 Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof Active CN110079271B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910406790.6A CN110079271B (en) 2019-05-15 2019-05-15 Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910406790.6A CN110079271B (en) 2019-05-15 2019-05-15 Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110079271A CN110079271A (en) 2019-08-02
CN110079271B true CN110079271B (en) 2020-03-10

Family

ID=67420368

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910406790.6A Active CN110079271B (en) 2019-05-15 2019-05-15 Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110079271B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110482526B (en) * 2019-09-17 2022-02-08 哈尔滨工业大学 Preparation method of biomass porous carbon electromagnetic wave-absorbing material with egg white as precursor
CN110947950B (en) * 2019-11-05 2021-08-24 中国船舶重工集团公司第七二五研究所 Preparation method of graphene modified FeCo absorbent
CN111574957B (en) * 2020-05-13 2023-03-31 中国科学院合肥物质科学研究院 Wave-absorbing material based on biological waste and magnetic material waste and preparation method thereof
CN112608715B (en) * 2020-12-02 2023-04-07 中国人民解放***箭军工程大学 Low-dimensional structure Co/C/Fe composite wave-absorbing material prepared by taking MOFs as template and preparation method thereof
CN113423254B (en) * 2021-05-26 2023-03-24 西安理工大学 Composite wave absorbing agent with electromagnetic wave absorbing performance and preparation method thereof
CN114101685B (en) * 2021-09-29 2023-06-09 北京环境特性研究所 Low-frequency radar wave absorbent and preparation method thereof
CN114641200B (en) * 2022-04-02 2023-05-05 四川农业大学 Nitrogen-doped microwave absorbing material and preparation method thereof

Also Published As

Publication number Publication date
CN110079271A (en) 2019-08-02

Similar Documents

Publication Publication Date Title
CN110079271B (en) Protein-based carbon/magnetic Fe Co nanoparticle composite wave absorber and preparation method and application thereof
Wang et al. Metal organic frameworks-derived Fe-Co nanoporous carbon/graphene composite as a high-performance electromagnetic wave absorber
CN113025271B (en) Ti 3 C 2 T x Preparation method of MXene @ ZnO composite wave-absorbing material
Li et al. A simple approach to spherical nickel-carbon monoliths as light-weight microwave absorbers
CN109705808A (en) A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof
CN109233740A (en) The method for preparing Fe/Co/C composite wave-suction material based on modified MOF materials pyrolysis
CN109825252B (en) Core-shell structure Fe3O4@C@MoS2Preparation of composite material and application thereof
CN109233741A (en) A kind of preparation method of three-dimensional carbon network load cobalt ferrite nano-particles reinforcement wave absorbing agent
Park et al. Yolk–shell Fe–Fe3O4@ C nanoparticles with excellent reflection loss and wide bandwidth as electromagnetic wave absorbers in the high-frequency band
Zhao et al. Facile synthesis of Ni/ZnO composite: Morphology control and microwave absorption properties
CN111171787B (en) BiFeO 3 /RGO composite wave-absorbing material and preparation method thereof
CN114195197B (en) Magnetic porous carbon compound and preparation method and application thereof
CN103102164B (en) Preparation method of fly ash/NiMnZn ferrite core-shell material
CN110993238A (en) Soft magnetic nanocrystalline metal or alloy flake particles having internal grain orientation and microwave absorbing material
Wang et al. Dispersed spherical shell-shaped palygorskite/carbon/polyaniline composites with advanced microwave absorption performances
CN115173079A (en) ZnFe loaded on coal gasification fine ash carbon residue 2 O 4 Nano microsphere composite material and preparation method thereof
CN112537764A (en) Carbon-based porous composite wave absorbing agent based on natural loofah sponge and preparation method thereof
Heng et al. Microwave absorption enhancement of Fe/C core–shell hybrid derived from a metal-organic framework
CN106241886B (en) A kind of Electromagnetic enhancement carbon magnetic composite and preparation method and application
Hao et al. Synthesis of hollow core–shell ZnFe 2 O 4@ C nanospheres with excellent microwave absorption properties
Li et al. Preparation and microwave absorbing properties of carbon/cobalt ferromagnetic composites
CN109179381B (en) Graphene/ferroferric oxide/copper silicate composite powder and preparation and application thereof
CN115568199A (en) Preparation method of double-shell molybdenum carbide/carbon nanosphere composite wave-absorbing material
CN114058328A (en) Wave-absorbing composite material and preparation method thereof
CN115491178B (en) CoFe (CoFe) 2 O 4 Preparation and application of mesoporous carbon core-shell wave-absorbing material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant