CN117548684A - Co@SiO with hollow core-shell structure 2 Preparation method and application of @ PPy - Google Patents
Co@SiO with hollow core-shell structure 2 Preparation method and application of @ PPy Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 43
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 36
- 239000011358 absorbing material Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims description 140
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 244000282866 Euchlaena mexicana Species 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 9
- 239000003929 acidic solution Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract
Co@SiO with hollow core-shell structure 2 A preparation method and application of @ PPy, which belong to the technical field of electromagnetic wave absorbing materials. Firstly, preparing monodisperse Co microspheres with a hollow structure by a solvothermal method, wherein the hollow structure reduces the weight of Co without losing the magnetic loss performance of Co; then coating SiO on the surface of Co microsphere by modified STber method 2 ，SiO 2 The introduction of the layer can not only enhance the interfacial polarization of the composite material, but also prevent Co cores from being corroded by acidic solution, and has no obvious negative influence on the magnetic loss capacity of Co; finally by in situ polymerizationSiO 2 PPy is coated on the surface of the layer; PPy has very strong conductivity loss due to its high conductivity, and high dielectric loss can be obtained without high temperature calcination. Co@SiO with hollow core-shell structure 2 The @ PPy is used as an electromagnetic wave absorbing material.
Description
Technical Field
The invention belongs to the technical field of electromagnetic wave absorbing materials, and particularly relates to a hollow core-shell structure Co@SiO 2 Preparation method and application of @ PPy.
Background
Electromagnetic waves bring great convenience to human life and simultaneously generate a great amount of electromagnetic pollution. Electromagnetic wave absorbing materials are one of the important methods for solving electromagnetic pollution. The ideal electromagnetic wave absorbing material has the characteristics of high absorbing strength, effective absorbing bandwidth, thin matching thickness, light weight and the like. Research shows that the composite and reasonable structural design of the magnetic material and the dielectric material is an important method for obtaining excellent electromagnetic wave absorption performance. Soft magnetic material (Fe, co, ni, CIP, fe) 3 O 4 Etc.) has been widely used in the field of electromagnetic wave absorption due to higher saturation magnetization and larger magnetic loss. However, magnetic metals such as Fe and Co have disadvantages such as high density and poor corrosion resistance. The introduction of dielectric material can protect the magnetic metal and increase dielectric loss. The conductive polymers PPy and PANI have strong dielectric loss, and have the advantages of small density, simple synthesis method, low cost and the like. Based on the above two considerations, researchers have tended to design core-shell magnetic metal/carbon composites with cavities. On the one hand, electromagnetic waves are absorbed by the combined action of strong magnetic and dielectric losses. On the other hand, the introduction of the carbon shell can not only increase dielectric loss, but also protect the internal magnetic metal from corrosion. In general, APS and FeCl 3 Acidic solutions can corrode Co and Fe when preparing PPy and PANI for initiators. Most studies have used phenolic resins or polydopamine as precursors to obtain dielectrics by high temperature calcinationLoss. However, these methods not only add to the high energy-consuming calcination process, but also high temperature calcination may adversely affect the magnetic loss of the magnetic material.
Disclosure of Invention
In order to overcome the defects of the prior material, the invention provides a hollow core-shell structure Co@SiO 2 Preparation method and application of @ PPy.
Firstly, preparing monodisperse Co microspheres with a hollow structure by a solvothermal method, wherein the hollow structure reduces the weight of Co without losing the magnetic loss performance of Co; then coating SiO on the surface of Co microsphere by modified STber method 2 ，SiO 2 The introduction of the layer can not only enhance the interfacial polarization of the composite material, but also prevent Co cores from being corroded by acidic solution, and has no obvious negative influence on the magnetic loss capacity of Co; finally, in situ polymerization is carried out on SiO 2 PPy is coated on the surface of the layer; PPy has very strong conductivity loss due to its high conductivity, and high dielectric loss can be obtained without high temperature calcination; the hollow core-shell structure Co@SiO prepared by the method 2 The @ PPy has excellent electromagnetic wave absorption properties.
Co@SiO with hollow core-shell structure 2 The preparation method of the@PPy is specifically completed by the following steps:
1. PVP, coCl 2 ·6H 2 O、N 2 H 4 ·H 2 O is dissolved in glycol to obtain solution A;
2. uniformly stirring the solution A, transferring the solution A into a hydrothermal kettle, and then placing the kettle in a 180 ℃ hydrothermal reaction for a period of time to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially carrying out magnetic adsorption separation on a reaction product I, washing and vacuum drying on the obtained solid product to obtain a hollow-structure Co microsphere;
4. dispersing Co microspheres with a hollow structure in a mixed solution of deionized water, ammonia water and absolute ethyl alcohol to obtain a suspension B;
5. adding TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C at room temperature for a period of time to obtain a suspension D;
7. sequentially performing magnetic adsorption separation on the suspension D, washing and vacuum drying the obtained solid product to obtain a hollow structure Co@SiO 2 A microsphere;
8. hollow structure Co@SiO 2 Dispersing the microspheres in deionized water to obtain suspension E;
9. dispersing pyrrole in the suspension E to obtain a suspension F;
10. adding an oxidant into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for a period of time under ice bath conditions to obtain a suspension H;
12. sequentially performing magnetic adsorption separation on the suspension H, washing and vacuum drying the obtained solid product to obtain a hollow core-shell structure Co@SiO 2 @PPy。
Co@SiO with hollow core-shell structure 2 The @ PPy is used as an electromagnetic wave absorbing material.
Compared with the prior art, the invention has the following beneficial effects:
the hollow structure reduces the weight of Co and SiO 2 The introduction of the layer can not only enhance the interfacial polarization of the composite material, but also prevent the Co core from being corroded by the acidic solution, and has no obvious negative effect on the magnetic loss capability of Co. PPy has very strong conductivity loss due to its high conductivity, and high dielectric loss can be obtained without the need for high-temperature calcination process, which consumes high energy. Preparation of hollow core-shell Structure Co@SiO 2 the@PPy composite material has excellent electromagnetic wave absorption performance and has better application potential in the fields of electromagnetic wave absorption and electromagnetic shielding.
Drawings
FIG. 1 is a hollow core-shell structure Co@SiO prepared in example 1 2 SEM image of @ PPy composite;
FIG. 2 is a hollow core-shell structure Co@SiO prepared in example 1 2 Electromagnetic wave absorption performance diagram of the @ PPy composite material;
FIG. 3 is a hollow core-shell structure Co@SiO prepared in example 2 2 SE of the Pop-Pycomposite MaterialM is shown;
FIG. 4 is a hollow core-shell structure Co@SiO prepared in example 2 2 Electromagnetic wave absorption performance diagram of the @ PPy composite material;
FIG. 5 is a hollow core-shell structure Co@SiO prepared in example 3 2 SEM image of @ PPy composite;
FIG. 6 is a hollow core-shell structure Co@SiO prepared in example 3 2 Electromagnetic wave absorption performance diagram of the @ PPy composite material;
FIG. 7 is an SEM image of the hollow-structured Co microspheres described in examples 1-3 after 1h etching with 0.1mol/L HCl.
Detailed Description
The first embodiment is as follows: in this embodiment, a hollow core-shell structure Co@SiO 2 The preparation method of the@PPy is specifically completed by the following steps:
1. PVP, coCl 2 ·6H 2 O、N 2 H 4 ·H 2 O is dissolved in glycol to obtain solution A;
2. uniformly stirring the solution A, transferring the solution A into a hydrothermal kettle, and then placing the kettle in a 180 ℃ hydrothermal reaction for a period of time to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially carrying out magnetic adsorption separation on a reaction product I, washing and vacuum drying on the obtained solid product to obtain a hollow-structure Co microsphere;
4. dispersing Co microspheres with a hollow structure in a mixed solution of deionized water, ammonia water and absolute ethyl alcohol to obtain a suspension B;
5. adding TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C at room temperature for a period of time to obtain a suspension D;
7. sequentially performing magnetic adsorption separation on the suspension D, washing and vacuum drying the obtained solid product to obtain a hollow structure Co@SiO 2 A microsphere;
8. hollow structure Co@SiO 2 Dispersing the microspheres in deionized water to obtain suspension E;
9. dispersing pyrrole in the suspension E to obtain a suspension F;
10. adding an oxidant into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for a period of time under ice bath conditions to obtain a suspension H;
12. sequentially performing magnetic adsorption separation on the suspension H, washing and vacuum drying the obtained solid product to obtain a hollow core-shell structure Co@SiO 2 @PPy。
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the concentration of PVP in the solution A in the first step is 15 g/L-60 g/L; coCl in solution a described in step one 2 ·6H 2 The concentration of O is 15g/L to 60g/L; n in the solution A described in step one 2 H 4 ·H 2 The concentration of O is 50mL/L to 150mL/L. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the time of the hydrothermal reaction in the second step is 4-48 h. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the concentration of the hollow structure Co microspheres in the suspension B in the step four is 0.25 g/L-25 g/L; the volume ratio of the ammonia water to the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water, the ammonia water and the absolute ethyl alcohol in the fourth step is (10-20): 40-60): 300-400; the mass fraction of the ammonia water is 25% -28%. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: and step five, the concentration of TEOS in the turbid liquid C is 5-50 mL/L. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the reaction time in the step six is 0.5 to 12 hours. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: hollow structure Co@SiO in suspension E described in step eight 2 The concentration of the microspheres is 0.25 g/L-25 g/L; and step nine, wherein the concentration of pyrrole in the suspension F is 0.12-50 mL/L. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the oxidant in the step ten is APS and FeCl 3 Or FeCl 3 ·6H 2 O; the concentration of the oxidant in the suspension G is 0.12G/L-150G/L. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: in the first step, the reaction time of the suspension G under the ice bath condition is 4-24 hours. Other steps are the same as those of embodiments one to eight.
Detailed description ten: in this embodiment, a hollow core-shell structure Co@SiO 2 The @ PPy is used as an electromagnetic wave absorbing material.
The following examples are used to verify the benefits of the present invention:
example 1: co@SiO with hollow core-shell structure 2 The preparation method of the@PPy is characterized by comprising the following steps of:
1. 3g polyvinylpyrrolidone (PVP, k29-32, mw=58000), 3g CoCl 2 ·6H 2 O、10mL N 2 H 4 ·H 2 O is dissolved in 100mL of glycol to obtain solution A;
2. stirring the solution A uniformly, transferring the solution A into a hydrothermal kettle, and placing the hydrothermal kettle at 180 ℃ for reaction for 6 hours to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially performing adsorption separation on the obtained reaction product I by using a magnet, washing 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 12 hours at 60 ℃ in vacuum to obtain hollow-structure Co microspheres;
4. dispersing 1.5g of hollow Co microspheres in a mixed solution of 350mL of absolute ethyl alcohol, 50mL of ionized water and 15mL of ammonia water to obtain a suspension B; the mass fraction of the ammonia water is 28%;
5. adding 5mL of TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C for 5 hours at room temperature to obtain a suspension D;
7. carrying out adsorption separation on the suspension D product by using a magnet, washing the suspension D product by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the suspension D product in vacuum at 60 ℃ for 12 hours to obtain a hollow structure Co@SiO 2 A microsphere;
8. 0.5g of hollow Co@SiO 2 Dispersing the microspheres in 100mL of deionized water to obtain a suspension E;
9. dispersing 600 mu L of pyrrole in the suspension E to obtain a suspension F;
10. adding 0.60G of ammonium persulfate into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for 10 hours under ice bath conditions to obtain a suspension H;
12. carrying out adsorption separation on the suspension H by using a magnet, washing the suspension H by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the suspension H for 24 hours at 50 ℃ in vacuum to obtain a hollow core-shell structure Co@SiO 2 @ppy composite material.
FIG. 1 is a hollow core-shell structure Co@SiO prepared in example 1 2 SEM image of @ PPy composite;
from FIG. 1, it can be seen that Co@SiO 2 the@PPy composite material has a double-layer shell, and the inner layer is SiO 2 The outer layer is PPy.
The method for detecting the electromagnetic wave absorbing performance comprises the following steps: uniformly mixing sample powder and paraffin according to the mass ratio of 1:1, pressing into an annular sample, analyzing electromagnetic parameters of the test sample by adopting a vector network, and calculating the electromagnetic wave absorbing performance.
FIG. 2 is a hollow core-shell structure Co@SiO prepared in example 1 2 Electromagnetic wave absorption performance diagram of the @ PPy composite material;
as can be seen from fig. 2: co@SiO of hollow core-shell structure prepared in example 1 2 At high temperature @ PPy compositeThe frequency region has an effective absorption bandwidth of 4.48GHz, and the minimum reflection loss reaches-25.14 dB.
Example 2: co@SiO with hollow core-shell structure 2 The preparation method of the@PPy is characterized by comprising the following steps of:
1. 3g polyvinylpyrrolidone (PVP, k29-32, mw=58000), 3g CoCl 2 ·6H 2 O、10mL N 2 H 4 ·H 2 O is dissolved in 100mL of glycol to obtain solution A;
2. stirring the solution A uniformly, transferring the solution A into a hydrothermal kettle, and placing the hydrothermal kettle at 180 ℃ for reaction for 6 hours to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially performing adsorption separation on the obtained reaction product I by using a magnet, washing 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 12 hours at 60 ℃ in vacuum to obtain hollow-structure Co microspheres;
4. dispersing 1.5g of hollow Co microspheres in a mixed solution of 350mL of absolute ethyl alcohol, 50mL of ionized water and 15mL of ammonia water to obtain a suspension B; the mass fraction of the ammonia water is 28%;
5. adding 5mL of TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C for 5 hours at room temperature to obtain a suspension D;
7. carrying out adsorption separation on the suspension D product by using a magnet, washing the suspension D product by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the suspension D product in vacuum at 60 ℃ for 12 hours to obtain a hollow structure Co@SiO 2 A microsphere;
8. 0.5g of hollow Co@SiO 2 Dispersing the microspheres in 100mL of deionized water to obtain a suspension E;
9. dispersing 660 mu L of pyrrole in the suspension E to obtain a suspension F;
10. adding 0.66G of ammonium persulfate into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for 10 hours under ice bath conditions to obtain a suspension H;
12. carrying out the magnet for suspension HAdsorption separation, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 50 ℃ in vacuum for 24 hours to obtain a hollow core-shell structure Co@SiO 2 @ppy composite material.
FIG. 3 is a hollow core-shell structure Co@SiO prepared in example 2 2 SEM image of @ PPy composite;
as can be seen from fig. 3: co@SiO with hollow core-shell structure 2 The @ PPy composite was successfully prepared, this example had fewer broken shells and increased discrete PPy due to the increased content of pyrrole added compared to example 1.
FIG. 4 is a hollow core-shell structure Co@SiO prepared in example 2 2 Electromagnetic wave absorption performance diagram of the @ PPy composite material;
as can be seen from fig. 4: co@SiO of hollow core-shell structure prepared in example 2 2 the@PPy composite material has the maximum effective absorption bandwidth of 5.2GHz, the minimum reflection loss reaches-65.83 dB, and the excellent electromagnetic wave absorption effect is achieved.
Example 3: co@SiO with hollow core-shell structure 2 The preparation method of the@PPy is characterized by comprising the following steps of:
1. 3g polyvinylpyrrolidone (PVP, k29-32, mw=58000), 3g CoCl 2 ·6H 2 O、10mL N 2 H 4 ·H 2 O is dissolved in 100mL of glycol to obtain solution A;
2. stirring the solution A uniformly, transferring the solution A into a hydrothermal kettle, and placing the hydrothermal kettle at 180 ℃ for reaction for 6 hours to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially performing adsorption separation on the obtained reaction product I by using a magnet, washing 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 12 hours at 60 ℃ in vacuum to obtain hollow-structure Co microspheres;
4. dispersing 1.5g of hollow Co microspheres in a mixed solution of 350mL of absolute ethyl alcohol, 50mL of ionized water and 15mL of ammonia water to obtain a suspension B; the mass fraction of the ammonia water is 28%;
5. adding 5mL of TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C for 5 hours at room temperature to obtain a suspension D;
7. carrying out adsorption separation on the suspension D product by using a magnet, washing the suspension D product by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the suspension D product in vacuum at 60 ℃ for 12 hours to obtain a hollow structure Co@SiO 2 A microsphere;
8. 0.5g of hollow Co@SiO 2 Dispersing the microspheres in 100mL of deionized water to obtain a suspension E;
9. dispersing 760 mu L of pyrrole in the suspension E to obtain a suspension F;
10. adding 0.76G of ammonium persulfate into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for 10 hours under ice bath conditions to obtain a suspension H;
12. carrying out adsorption separation on the suspension H by using a magnet, washing the suspension H by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the suspension H for 24 hours at 50 ℃ in vacuum to obtain a hollow core-shell structure Co@SiO 2 @ppy composite material.
FIG. 5 is a hollow core-shell structure Co@SiO prepared in example 3 2 SEM image of @ PPy composite;
as can be seen from fig. 5: co@SiO with hollow core-shell structure 2 The @ PPy composite was successfully prepared, and in this example, more discrete PPy was present due to the more pyrrole content than in examples 1 and 2, the more complete coating, but the core-shell structure was seen.
FIG. 6 is a hollow core-shell structure Co@SiO prepared in example 3 2 Electromagnetic wave absorption performance diagram of the @ PPy composite material;
as can be seen from fig. 6: co@SiO with hollow core-shell structure 2 The @ PPy composite material has excellent electromagnetic wave absorption performance. The effective absorption bandwidth is 3.96GHz at the thickness of 1.66mm, and the minimum reflection loss reaches-61.66 dB. The effective absorption bandwidth reaches 5.4GHz when the thickness is 1.83mm, the minimum reflection loss reaches-50.70 dB, and the wider absorption effect is achieved under the thinner thickness.
Example 4: co@SiO with hollow core-shell structure 2 The preparation method of the@PPy composite material is specifically completed by the following steps:
1. 0.5g PVP (k 29-32, mw=58000), 1g CoCl 2 ·6H 2 O、6mL N 2 H 4 ·H 2 O is dissolved in 100mL of glycol to obtain solution A;
2. stirring the solution A uniformly, transferring the solution A into a hydrothermal kettle, and placing the hydrothermal kettle at 180 ℃ for reacting for 20 hours to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially carrying out adsorption separation on a reaction product I by using a magnet, washing 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 24 hours at 50 ℃ in vacuum to obtain hollow-structure Co microspheres;
4. dispersing 0.5g of hollow Co microspheres in a mixed solution of 120mL of absolute ethyl alcohol, 40mL of ionized water and 10mL of ammonia water to obtain a suspension B; the mass fraction of the ammonia water is 28%;
5. adding 1mL of TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C for 2 hours at room temperature to obtain a suspension D;
7. carrying out adsorption separation on the suspension D product by using a magnet, washing the suspension D product by using deionized water and absolute ethyl alcohol for 4 times respectively, and drying the suspension D product in vacuum at 60 ℃ for 24 hours to obtain a hollow structure Co@SiO 2 A microsphere;
8. 1.0g of hollow Co@SiO 2 Dispersing the microspheres in 100mL of deionized water to obtain a suspension E;
9. dispersing 1000 mu L of pyrrole in the suspension E to obtain a suspension F;
10. adding 1.0G of ammonium persulfate into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for 6 hours under ice bath conditions to obtain a suspension H;
12. carrying out adsorption separation on the suspension H by using a magnet, washing the suspension H by using deionized water and absolute ethyl alcohol for 3 times respectively, and drying the suspension H for 12 hours at 50 ℃ in vacuum to obtain a hollow core-shell structure Co@SiO 2 @ppy composite material.
Example 5: co@SiO with hollow core-shell structure 2 The preparation method of the@PPy composite material is specifically completed by the following steps:
1. 1g PVP (k 29-32, mw=58000), 1.5g CoCl 2 ·6H 2 O、12mL N 2 H 4 ·H 2 O is dissolved in 100mL of glycol to obtain solution A;
2. stirring the solution A uniformly, transferring the solution A into a hydrothermal kettle, and placing the hydrothermal kettle at 180 ℃ for reaction for 24 hours to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially carrying out adsorption separation on a reaction product I by using a magnet, washing for 4 times by using deionized water and absolute ethyl alcohol respectively, and drying for 20 hours at 50 ℃ in vacuum to obtain hollow-structure Co microspheres;
4. dispersing 2g of hollow Co microspheres in a mixed solution of 300mL of absolute ethyl alcohol, 40mL of ionized water and 10mL of ammonia water to obtain a suspension B; the mass fraction of the ammonia water is 28%;
5. adding 10mL of TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C for 3 hours at room temperature to obtain a suspension D;
7. carrying out adsorption separation on the suspension D product by using a magnet, washing the suspension D product by using deionized water and absolute ethyl alcohol for 5 times respectively, and drying the suspension D product for 24 hours at 55 ℃ in vacuum to obtain a hollow structure Co@SiO 2 A microsphere;
8. 2.0g of hollow Co@SiO 2 Dispersing the microspheres in 400mL of deionized water to obtain a suspension E;
9. dispersing 2000 mu L of pyrrole in the suspension E to obtain a suspension F;
10. adding 6.0G of ammonium persulfate into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for 8 hours under ice bath conditions to obtain a suspension H;
12. carrying out adsorption separation on the suspension H by using a magnet, washing the suspension H by using deionized water and absolute ethyl alcohol for 5 times respectively, and drying the suspension H for 24 hours at 50 ℃ in vacuum to obtain a hollow core-shell structure Co@SiO 2 @ppy composite material.
FIG. 7 is an SEM image of the hollow-structured Co microspheres described in examples 1-3 after 1h of etching with 0.1mol/L HCl; as can be seen from fig. 7: the Co microsphere center is a hollow structure, and the hollow volumes of different microspheres are slightly different.
Claims (10)
1. Co@SiO with hollow core-shell structure 2 The preparation method of the@PPy is characterized by comprising the following steps of:
1. PVP, coCl 2 ·6H 2 O、N 2 H 4 ·H 2 O is dissolved in glycol to obtain solution A;
2. uniformly stirring the solution A, transferring the solution A into a hydrothermal kettle, and then placing the kettle in a 180 ℃ hydrothermal reaction for a period of time to obtain a reaction product I;
3. after the hydrothermal kettle is cooled to room temperature, sequentially carrying out magnetic adsorption separation on a reaction product I, washing and vacuum drying on the obtained solid product to obtain a hollow-structure Co microsphere;
4. dispersing Co microspheres with a hollow structure in a mixed solution of deionized water, ammonia water and absolute ethyl alcohol to obtain a suspension B;
5. adding TEOS into the suspension B, and uniformly stirring to obtain a suspension C;
6. reacting the suspension C at room temperature for a period of time to obtain a suspension D;
7. sequentially performing magnetic adsorption separation on the suspension D, washing and vacuum drying the obtained solid product to obtain a hollow structure Co@SiO 2 A microsphere;
8. hollow structure Co@SiO 2 Dispersing the microspheres in deionized water to obtain suspension E;
9. dispersing pyrrole in the suspension E to obtain a suspension F;
10. adding an oxidant into the suspension F under the ice bath condition to obtain a suspension G;
11. reacting the suspension G for a period of time under ice bath conditions to obtain a suspension H;
12. sequentially performing magnetic adsorption separation on the suspension H, washing and vacuum drying the obtained solid product to obtain a hollow core-shell structure Co@SiO 2 @PPy。
2. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the concentration of PVP in the solution A in the step one is 15 g/L-60 g/L; coCl in solution a described in step one 2 ·6H 2 The concentration of O is 15g/L to 60g/L; n in the solution A described in step one 2 H 4 ·H 2 The concentration of O is 50mL/L to 150mL/L.
3. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the hydrothermal reaction time in the second step is 4-48 hours.
4. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the concentration of the hollow structure Co microspheres in the suspension B in the step four is 0.25 g/L-25 g/L; the volume ratio of the ammonia water to the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water, the ammonia water and the absolute ethyl alcohol in the fourth step is (10-20): 40-60): 300-400; the mass fraction of the ammonia water is 25% -28%.
5. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the concentration of TEOS in the turbid liquid C in the step five is 5-50 mL/L.
6. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the reaction time in the step six is 0.5-12 h.
7. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the hollow structure Co@SiO in the suspension E in the step eight 2 The concentration of the microspheres is 0.25 g/L-25 g/L; and step nine, wherein the concentration of pyrrole in the suspension F is 0.12-50 mL/L.
8. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the @ PPy is characterized in that the oxidant in the step ten is APS or FeCl 3 Or FeCl 3 ·6H 2 O; the concentration of the oxidant in the suspension G is 0.12G/L-150G/L.
9. A hollow core-shell structure co@sio according to claim 1 2 The preparation method of the@PPy is characterized in that the reaction time of the suspension G in the step one under the ice bath condition is 4-24 hours.
10. A hollow core-shell structure Co@SiO prepared by the preparation method as claimed in claim 1 2 The application of the@PPy is characterized in that the hollow core-shell structure Co@SiO 2 The @ PPy is used as an electromagnetic wave absorbing material.
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| CN117862495B (en) * | 2024-03-11 | 2024-06-07 | 中国空气动力研究与发展中心低速空气动力研究所 | FeCo nano-chain metal powder and FeCo@SiO2Microwave absorbing material and preparation method thereof |
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