CN114477308A - MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof - Google Patents
MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114477308A CN114477308A CN202210149294.9A CN202210149294A CN114477308A CN 114477308 A CN114477308 A CN 114477308A CN 202210149294 A CN202210149294 A CN 202210149294A CN 114477308 A CN114477308 A CN 114477308A
- Authority
- CN
- China
- Prior art keywords
- zif
- absorbing material
- mofs
- mnfe
- manganese ferrite
- 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.)
- Pending
Links
- 239000011358 absorbing material Substances 0.000 title claims abstract description 82
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 69
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 60
- 239000011572 manganese Substances 0.000 title claims abstract description 60
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000011258 core-shell material Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910017163 MnFe2O4 Inorganic materials 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 23
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 23
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 29
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- BSCMKVMJAHJNJW-UHFFFAOYSA-L 3-[2-carboxyethyl(dichloro)stannyl]propanoic acid Chemical compound OC(=O)CC[Sn](Cl)(Cl)CCC(O)=O BSCMKVMJAHJNJW-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- XLAPHZHNODDMDD-UHFFFAOYSA-N 4-methylpyridine-3-carbonitrile Chemical compound CC1=CC=NC=C1C#N XLAPHZHNODDMDD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 229910001053 Nickel-zinc ferrite Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/04—Ferrous oxide [FeO]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Composite Materials (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention relates to a MOFs derivative double-layer coated manganese ferrite wave-absorbing material and a preparation method and application thereof. The double-layer coated manganese ferrite wave-absorbing material takes manganese ferrite as a core, ferrous oxide or cobalt oxide is arranged in the middle, and carbon is arranged on the outer layer. The double-layer core-shell structure of the wave-absorbing material improves interface polarization and dipole polarization, increases the complex dielectric constant of the material, enhances interface scattering of a multi-level structure, and optimizes impedance matching of the composite material. As can be seen from example 1, the minimum RL value of the obtained double-layer coated manganese ferrite wave-absorbing material at the frequency of 11.6GHz is-71.65 dB, and the minimum RL value of the non-double-layer coated manganese ferrite wave-absorbing material at the frequency of 13.22GHz is-37.53 dB. Therefore, the MOFs derivative double-layer coated manganese ferrite wave-absorbing material prepared by the invention can realize effective absorption of electromagnetic waves under low thickness and has good chemical stability.
Description
Technical Field
The invention relates to a ferrite wave-absorbing material technology, in particular to a MOFs derivative double-layer coated manganese ferrite wave-absorbing material and a preparation method and application thereof.
Background
Along with the development of science and technology, more and more electronic components and electrical equipment are poured into the life of people, along with that electromagnetic waves of all frequency bands are filled in the living space of people, and the electromagnetic waves inevitably cause certain harm to human bodies. A large number of research results show that the electromagnetic radiation has a cumulative effect on the damage caused by organisms, and if the organisms are exposed to the electromagnetic radiation for a long time, lesions are likely to be induced. In addition, national defense military is also an important application field of the wave-absorbing material, for example, the wave-absorbing material is coated on military equipment such as aircraft, naval vessels, tank missiles and the like, and the effects of attenuating electromagnetic waves and weakening reflected signals can be achieved. Therefore, the development of an efficient electromagnetic wave absorbing material has become an important issue in the field of wave absorption.
Ferrite wave-absorbing materials are widely used due to the advantages of high frequency, wide frequency band, thin coating and the like, and common ferrite soft magnetic materials include zinc ferrite, nickel ferrite, manganese-zinc ferrite, nickel-zinc ferrite and the like. However, when the ferrite is used alone, the application of the ferrite as a wave-absorbing material is limited by the defects of high density, poor corrosion resistance, poor mechanical property and the like. The single-component wave-absorbing material is difficult to achieve effective absorption of electromagnetic waves. Therefore, a carbon material having a low density, good dielectric properties, and stable chemical properties is a preferable material to be compounded with ferrite. The ferrite is compounded with the carbon, so that the material has excellent magnetic loss and dielectric loss, the impedance matching is optimized, the wave-absorbing performance of the material is improved, the service conditions of the wave-absorbing material are widened due to the addition of the carbon material, and the quality problem of the material is also considered.
Disclosure of Invention
The invention aims to provide a MOFs derivative double-layer coated manganese ferrite wave-absorbing material, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a MOFs derivative double-layer coated manganese ferrite wave-absorbing material is characterized in that a precursor of the wave-absorbing material is MnFe2O4The core is MOFs, the shell is MOFs, and the proportion of the two is 80-85 wt.% of MnFe2O4、15-20wt.％ MOFs；
The MOFs is zinc-based framework material ZIF-7, and the unit molecular formula of the ZIF-7 is C7H6N2·H2The unit molecular formula of O, Zn or zinc-based framework materials ZIF-8 and ZIF-8 is C8H10N4The unit molecular formula of the Zn or cobalt-based framework materials ZIF-67 and ZIF-67 is C4H6N2One of Co; when MOFs is ZIF-7 or ZIF-8, the wave-absorbing material is MnFe2O4As core, FeO reduced by carbon as intermediate layer, and carbon derived from MOFs as shell to form black MnFe2O4@ FeO/C wave-absorbing material; when the MOFs is ZIF-67, the wave-absorbing material is MnFe2O4As a core, CoO, a derivative of MOFs, as an intermediate layer, and carbon, a derivative of MOFs, as a shell layer, form MnFe2O4@ CoO/C absorbing material.
A preparation method of MOFs derivative double-layer coated manganese ferrite wave-absorbing material comprises the following steps:
step 1, preparing manganese ferrite (MnFe) by using a hydrothermal method in the prior art2O4) Powder: FeCl is added3·6H2O and MnCl2·4H2Fully dissolving O in ethylene glycol, and uniformly stirring at room temperature to form solution A; adding sodium acetate and polyethylene glycol into the solution A, and magnetically stirring for 30 minutes to form a solution B; transferring the B solution to 100mPutting the lining filled with the solution B into a stainless steel reaction kettle, screwing and sealing the lining, and putting the lining into an oven for hydrothermal reaction; then cooling to room temperature along with the furnace, and centrifugally separating to obtain brown precipitate; washing the brown precipitate with absolute ethyl alcohol and deionized water for 3 times; drying the washed brown precipitate in a vacuum drying oven at 60 ℃ for 12 hours, taking out and grinding to obtain dried manganese ferrite powder;
and 4, carbonizing treatment: MnFe synthesized in step 32O4@ ZIF-7 core-shell powder material or MnFe2O4@ ZIF-8 core-shell powder material or MnFe2O4@ ZIF-67 core-shell powder material is calcined under the protection of Ar atmosphere, wherein ZIF-7, ZIF-8 or ZIF-67 is decomposed; sufficient carbon is available for ZIF-7 or ZIF-8 decomposition to make MnFe2O4Part of the iron ions are reduced to generate FeO, and MnFe is formed2O4Taking FeO reduced by carbon as a core, taking the FeO reduced by carbon as an intermediate layer, taking ZIF-7 or ZIF-8 derivative carbon as a double-layer coating structure of a shell layer to obtain black MnFe2O4@ FeO/C wave-absorbing material; the products CoO and C can be obtained by decomposing ZIF-67 at high temperature, and the boiling point of CoO is high, and the CoO is not easy to volatilize, so that MnFe is formed2O4Taking the derivative CoO of ZIF-67 as a core, taking the derivative CoO of ZIF-67 as an intermediate layer, taking the derivative carbon of ZIF-67 as a shell layer to obtain a double-layer coating structure, and finally obtaining MnFe2O4@ CoO/C absorbing material.
FeCl in step 13·6H2O：MnCl2·4H2O: sodium acetate: polyethylene glycol: the mass-volume ratio of the ethylene glycol is 3-5 g: 1-2 g: 10-20 g: 3-5 g: 120-300 ml; wherein polyethylene glycol is used as a dispersing agent.
The hydrothermal reaction temperature in the step 1 is 200 ℃ and the reaction time is 12 hours.
The centrifugal rotation speed in the step 1 is 2500-.
The surfactant in the step 2 is sodium polystyrene sulfonate, and the volume concentration of the surfactant is 1-2%.
Manganese ferrite and Zn (NO) in step 33)2·6H2The mass ratio of O is 1.5-2.5: 0.4-0.8; manganese ferrite and Co (NO)3)2·6H2The mass ratio of O is 1.5-2.5: 0.3-0.6.
Dimethyl imidazole in step 3: zn (NO)3)2·6H2The mass ratio of O is 0.6-1.2: 0.4-0.8.
In the step 4, the heating rate is 3-8 ℃/min, the calcination temperature is 600-800 ℃, and the calcination time is 1-4 hours.
A MOFs derivative double-layer coated manganese ferrite wave-absorbing material is applied to a mobile phone, and is rolled into a flexible sheet and attached between a battery and an antenna of the mobile phone, so that the problems of metal interference and wireless charging heating of non-contact communication can be solved.
The invention has the beneficial effects that:
the double-layer coated manganese ferrite wave-absorbing material takes manganese ferrite as a core, a middle layer is ferrous oxide or cobalt oxide, and the outermost layer is carbon. The double-layer core-shell structure of the wave-absorbing material improves interface polarization and dipole polarization, increases the complex dielectric constant of the material, strengthens interface scattering of a multi-level structure, optimizes impedance matching of the composite material, and has great contribution in the aspects of enhancing absorption strength, widening absorption frequency band, reducing material quality and the like. The shell thickness of the wave-absorbing material can be regulated and controlled through the content of MOFs, and the density of the material is reduced due to the composition of the carbonaceous material. Meanwhile, the carbon-coated structural material has good chemical stability and composite characteristics, and allows the material to be served in more extreme environments.
As can be seen from example 1, the minimum RL value of the obtained double-layer coated manganese ferrite wave-absorbing material at the frequency of 11.6GHz is-71.65 dB, and the minimum RL value of the non-double-layer coated manganese ferrite wave-absorbing material at the frequency of 13.22GHz is-37.53 dB. Therefore, the MOFs derivative double-layer coated manganese ferrite wave-absorbing material prepared by the method can effectively absorb electromagnetic waves at low thickness and has good chemical stability.
Drawings
FIG. 1 is an X-ray diffraction diagram of the wave-absorbing material in example 1 of the invention;
FIG. 2 is a transmission electron microscope image of the wave-absorbing material in example 1 of the invention;
FIG. 3 is a high resolution transmission electron microscope image of the wave-absorbing material in example 1 of the present invention;
FIG. 4 is a high-angle ring-shaped dark-field scanning transmission electron microscope image of carbon in the wave-absorbing material in example 1 of the present invention
FIG. 5 is an X-ray photoelectron spectroscopy analysis chart of C1s and Fe 2p of the wave-absorbing material in example 1 of the invention;
FIG. 6 is a comparison graph of the imaginary part of the dielectric constant and the dielectric loss tangent of the wave-absorbing material in example 1 of the invention.
FIG. 7 is a comparison graph of the wave-absorbing properties of the wave-absorbing material before and after coating in example 1 of the present invention.
Detailed Description
Unless otherwise indicated, the experimental methods used in the following examples are all conventional in the art, and the pharmaceutical reagents used are all conventional in the art.
Example detection characterization:
the phase composition of the wave-absorbing material obtained in the example is characterized by means of an X-ray diffractometer of D8 Advance type;
the micro-morphology and the carbon element of the wave-absorbing material obtained in the embodiment are characterized by a Tecnai G2F 30 type transmission electron microscope;
and (3) carrying out chemical valence analysis on the element of the wave-absorbing material obtained in the embodiment by an XPS-ESCALB 250XI type X-ray electron energy spectrometer.
Electromagnetic parameters of the material were tested by means of a 3672B-S, CETC vector network analyzer and reflection loss values were calculated. MOFs derivatives obtained in the examples double-layer coated MnFe2O4The mass ratio of the wave-absorbing material to the paraffin is 3: 2, heating and melting by using an experimental heating lamp, stirring and mixing uniformly, pouring into a special mold, and making into circular rings with the outer diameter and the inner diameter of 7mm and 3mm respectively and the thickness of 1.5-2.0 mm; measuring the complex permeability and the complex dielectric constant of the circular ring on a 2-18GHz frequency band, wherein the reflection loss RL of the wave-absorbing material is calculated by adopting the following formula:
in the formula (2), epsilonr、μrAnd d is the complex dielectric constant, complex permeability and thickness of the wave-absorbing material, f is the frequency of the electromagnetic wave, c is the propagation speed of the electromagnetic wave in vacuum, and j is an imaginary unit.
Example 1: ZIF-8 (the unit molecular formula of ZIF-8 is C)8H10N4Zn) derivative double-layer coated manganese ferrite wave-absorbing material preparation:
(1) the formula is as follows:
85wt.％MnFe2O415 wt.% ZIF-8 (wt.% is mass percent)
(2) The preparation process comprises the following steps:
step 1, 3.60g FeCl3·6H2O and 1.32g MnCl2·4H2Fully dissolving O in 160ml of ethylene glycol, and uniformly stirring at room temperature to form solution A; adding 14.4g of sodium acetate and 4.0 g of polyethylene glycol into the solution A to form a solution B, and stirring for 30 minutes by using an HJ-6 magnetic heating stirrer; transferring the solution B into a 100ml polytetrafluoroethylene lining, then putting the polytetrafluoroethylene lining filled with the solution B into a stainless steel reaction kettle, screwing up and sealing, and putting the stainless steel reaction kettle into an oven for hydrothermal reaction at the reaction temperature of 200 ℃ for 12 hours. Cooling to a greenhouse along with the furnace, and performing centrifugal separation at the centrifugal speed of 3000rpm for 10 minutes to obtain a brown precipitate. Washing the obtained brown precipitate with anhydrous ethanol and deionized water sequentially, and repeating for 3 times; finally, drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours, taking out and grinding the mixture to obtain dry manganese ferrite powder;
and 4, carbonizing treatment: MnFe synthesized in step 32O4The @ ZIF-8 core-shell powder material is calcined under the protection of Ar atmosphere, the calcining temperature is 700 ℃, the calcining time is 2 hours, and the heating rate is 5 ℃/min; ZIF-8 decomposes to obtain sufficient carbon to make MnFe2O4Part of iron ions are reduced to generate FeO to form a double-layer coating structure, and black MnFe is obtained2O4@ FeO/C wave-absorbing material.
Example 2: ZIF-8 (the unit molecular formula of ZIF-8 is C)8H10N4Zn) derivative double-layer coated manganese ferrite wave-absorbing material preparation:
(1) the formula is as follows:
80wt.％MnFe2O420 wt.% ZIF-8 (wt.% is mass percent)
(2) The preparation process comprises the following steps:
example 2 differs from example 1 in the Zn (NO) in step 3 of example 13)2·6H2The same procedures as in example 1 were repeated except that O was adjusted to 0.65g and dimethylimidazole was adjusted to 1.08 g.
Example 3: ZIF-67 (the unit molecular formula of ZIF-67 is C)4H6N2Co) derivative double-layer coated manganese ferrite wave-absorbing material preparation:
(1) the formula is as follows:
85wt.％MnFe2O415 wt.% ZIF-67 (wt.% is mass percent)
(2) The preparation process comprises the following steps:
example 3 differs from example 1 in that the metal organic framework material prepared in this example is ZIF-67 having a unit formula of C4H6N2Co, in step 3, Zn (NO)3)2·6H2Replacement of O by Co (NO)3)2·6H2O, mass 0.45g, the other steps were the same as in example 1.
Example 4 ZIF-7 (unit formula of ZIF-7 is C)7H6N2·H2O.Zn) derivative double-layer coated manganese ferrite wave-absorbing material preparation:
(1) the formula is as follows:
85wt.％MnFe2O415 wt.% ZIF-7 (wt.% is mass percent)
(2) The preparation process comprises the following steps:
example 4 differs from example 1 in that the metal organic framework material prepared in this example is ZIF-7 with unit formula C7H6N2·H2O.Zn. In step 3, Zn (NO) is added3)2·6H2The same procedure as in example 1 was repeated except that the mass of O was adjusted to 0.41g and the mass of dimethylimidazole was adjusted to 0.67 g.
Experimental results for example 1:
ZIF-8 (the unit molecular formula of ZIF-8 is C)8H10N4Zn) as carbon source, and black MnFe obtained by high-temperature carbonization2O4The @ FeO/C core-shell nano wave-absorbing material has a double-layer core-shell structure, so that the interface polarization and dipole polarization are improved, the complex dielectric constant of the material is increased, the interface scattering of a multi-level structure is enhanced, the impedance matching of the composite material is optimized, and the changes make great contribution to the aspects of enhancing the absorption strength, widening the absorption frequency band, reducing the material quality and the like. And the material with the carbon coating structure has good chemical stability and composite property, so that the material can be used in more extreme environments.
FIG. 1 shows MnFe obtained by X-ray diffractometer of D8 Advance type2O4The phase composition of @ FeO/C is characterized, the main phase composition being MnFe2O4The diffraction peak of carbon was found at around 41.85 °, and the diffraction peak of FeO was found at around 35.85 ° and 60.38 °.
FIG. 2 shows MnFe obtained by means of a transmission electron microscope of the Tecnai G2F 30 type2O4The surface morphology of the @ FeO/C wave absorbing material is characterized.
FIG. 3 is an enlarged view of a local region of FIG. 2 taken with a transmission electron microscope of Tecnai G2F 30 type, from which high resolution transmission electron micrographs show that the core is MnFe with lattice fringes of 0.491nm2O4The crystal face is (111); the middle layer is FeO, the lattice spacing is 0.216nm, and the middle layer corresponds to a (200) crystal face; the outermost layer is C, the lattice spacing is 0.207nm, and the crystal lattice spacing corresponds to a (002) crystal face.
FIG. 4 is a representation of the carbon element of FIG. 2 by means of a Tecnai G2F 30 high angle annular dark field scanning transmission electron microscope, showing the presence of the C element is detected;
FIG. 5 shows MnFe obtained by XPS-ESCALAB 250XI X-ray electron spectrometer2O4The chemical valence state analysis of C1s and Fe 2p of the @ FeO/C wave-absorbing material is characterized, as shown in the figure, three functional groups of carbon element and MnFe are detected2O4Trivalent iron in the middle and divalent iron in the FeO.
FIG. 6 shows MnFe obtained by means of a 3672B-S, CETC vector network analyzer pair2O4The electromagnetic parameter test of the ring made of the @ FeO/C wave absorbing material shows that when the content of the coated ZIF-8 is 15%, the complex dielectric constant and the dielectric loss tangent of the double-layer coated manganese ferrite wave absorbing material are remarkably improved.
FIG. 7 shows MnFe obtained by 3672B-S, CETC vector network analyzer2O4Testing the complex permeability and the complex dielectric constant of a circular ring made of the @ FeO/C wave absorbing material, and then calculating and simulating the emission loss of the wave absorbing material according to the following formula:
in the formula (2), epsilonr、μrAnd d is the complex dielectric constant, complex permeability and thickness of the wave-absorbing material, f is the frequency of the electromagnetic wave, c is the propagation speed of the electromagnetic wave in vacuum, and j is an imaginary unit. According to calculation, when the content of the coated ZIF-8 is 15%, the minimum RL value of the double-layer coated manganese ferrite wave-absorbing material obtained in example 1 at the frequency of 11.6GHz is-71.65 dB and the minimum RL value of the non-double-layer coated manganese ferrite wave-absorbing material at the frequency of 13.22GHz is-37.53 dB under the matching thickness of 1.796 mm. Therefore, the MOFs derivative double-layer coated manganese ferrite wave-absorbing material prepared by the method can effectively absorb electromagnetic waves at low thickness, has good chemical stability and simple preparation method, and is preferred as the wave-absorbing material.
Claims (10)
1. A MOFs derivative double-layer coated manganese ferrite wave-absorbing material is characterized in that: the precursor of the wave-absorbing material is MnFe2O4The core is MOFs, the shell is MOFs, and the proportion of the two is 80-85 wt.% of MnFe2O4、15-20wt.％MOFs；
The MOFs is zinc-based framework material ZIF-7, and the unit molecular formula of the ZIF-7 is C7H6N2·H2The unit molecular formula of O, Zn or zinc-based framework materials ZIF-8 and ZIF-8 is C8H10N4The unit molecular formula of the Zn or cobalt-based framework materials ZIF-67 and ZIF-67 is C4H6N2One of Co; when MOFs is ZIF-7 or ZIF-8, the wave-absorbing material is MnFe2O4As core, FeO reduced by carbon as intermediate layer, and carbon as shell of MOFs derivative to form black MnFe2O4@ FeO/C wave-absorbing material; when the MOFs is ZIF-67, the wave-absorbing material isMnFe2O4As core, CoO as the derivative of MOFs as intermediate layer, and carbon as the derivative of MOFs as shell layer to form MnFe2O4@ CoO/C absorbing material.
2. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material of claim 1, which is characterized by comprising the following steps of:
step 1, preparing manganese ferrite powder by using a hydrothermal method in the prior art: FeCl is added3·6H2O and MnCl2·4H2Fully dissolving O in ethylene glycol, and uniformly stirring at room temperature to form solution A; adding sodium acetate and polyethylene glycol into the solution A, and magnetically stirring for 30 minutes to form a solution B; transferring the solution B into a 100ml polytetrafluoroethylene lining, putting the lining filled with the solution B into a stainless steel reaction kettle, screwing and sealing, and putting the stainless steel reaction kettle into an oven for hydrothermal reaction; then cooling to room temperature along with the furnace, and carrying out centrifugal separation to obtain a brown precipitate; washing the brown precipitate with absolute ethyl alcohol and deionized water for 3 times; drying the washed brown precipitate in a vacuum drying oven at 60 ℃ for 12 hours, taking out and grinding to obtain dried manganese ferrite powder;
step 2, surface modification of manganese ferrite powder: adding the manganese ferrite powder obtained in the step 1 into deionized water diluted with a surfactant to form a solution C, and carrying out ultrasonic treatment on the solution C at room temperature for 30 minutes; then separating the manganese ferrite powder from the solution C by an external magnet, and washing the manganese ferrite powder for 3 times by using ethanol and deionized water in sequence; then drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours, taking out and grinding the mixture to obtain manganese ferrite powder with modified surface;
step 3, MnFe2O4Synthesis of @ MOFs core-shell powder material: first, a metal nitrate Zn (NO) is taken3)2·6H2O or Co (NO)3)2·6H2Dissolving O and the modified manganese ferrite powder obtained in the step 2 in methanol to form a solution D; dissolving dimethyl imidazole in a methanol solution to form an E solution; secondly, dissolve the E under mechanical agitationDropping the solution into the D solution, and mechanically stirring the solution at room temperature for 2 hours to form the solution containing MnFe2O4@ MOFs in F; then, MnFe is heated by means of an external magnet2O4Separating the @ MOFs core-shell particles from the F solution, and subjecting the separated MnFe to methanol2O4Washing the @ MOFs core-shell particles for three times, drying the washed particles in a vacuum drying oven at 60 ℃ for 12 hours, taking out the particles and grinding the particles to obtain dried MnFe2O4@ MOFs core-shell powder material; when the metal nitrate is Zn (NO)3)2·6H2O, resulting in MnFe2O4@ ZIF-7 core-shell powder material or MnFe2O4@ ZIF-8 core-shell powder material; when the metal nitrate is Co (NO)3)2·6H2O, resulting in MnFe2O4@ ZIF-67 core-shell powder material;
and 4, carbonizing treatment: MnFe synthesized in step 32O4@ ZIF-7 core-shell powder material or MnFe2O4@ ZIF-8 core-shell powder material or MnFe2O4@ ZIF-67 core-shell powder material is calcined under the protection of Ar atmosphere, wherein ZIF-7, ZIF-8 or ZIF-67 is decomposed; sufficient carbon can be obtained by ZIF-7 or ZIF-8 decomposition to make MnFe2O4Part of the iron ions are reduced to generate FeO, and MnFe is formed2O4Taking FeO reduced by carbon as a core, taking the FeO reduced by carbon as an intermediate layer, taking ZIF-7 or ZIF-8 derivative carbon as a double-layer coating structure of a shell layer to obtain black MnFe2O4@ FeO/C wave-absorbing material; the products CoO and C can be obtained by decomposing ZIF-67 at high temperature, and the boiling point of CoO is high and the CoO is not easy to volatilize, so that MnFe is formed2O4Taking the derivative CoO of ZIF-67 as a core, taking the derivative CoO of ZIF-67 as an intermediate layer, taking the derivative carbon of ZIF-67 as a shell layer to obtain a double-layer coating structure, and finally obtaining MnFe2O4@ CoO/C absorbing material.
3. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: FeCl in step 13·6H2O：MnCl2·4H2O: sodium acetate: polyethylene glycol: substances of ethylene glycolThe weight-volume ratio is 3-5 g: 1-2 g: 10-20 g: 3-5 g: 120-300 ml; wherein polyethylene glycol is used as a dispersing agent.
4. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: the hydrothermal reaction temperature in the step 1 is 200 ℃ and the reaction time is 12 hours.
5. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: the centrifugal rotation speed in the step 1 is 2500-.
6. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: the surfactant in the step 2 is sodium polystyrene sulfonate, and the volume concentration of the surfactant is 1-2%.
7. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: manganese ferrite and Zn (NO) in step 33)2·6H2The mass ratio of O is 1.5-2.5: 0.4-0.8; manganese ferrite and Co (NO)3)2·6H2The mass ratio of O is 1.5-2.5: 0.3-0.6.
8. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: dimethyl imidazole in step 3: zn (NO)3)2·6H2The mass ratio of O is 0.6-1.2: 0.4-0.8.
9. The method for preparing the MOFs derivative double-layer coated manganese ferrite wave-absorbing material according to claim 2, wherein the method comprises the following steps: in the step 4, the heating rate is 3-8 ℃/min, the calcining temperature is 600-.
10. The MOFs derivative double-layer coated manganese ferrite wave-absorbing material of claim 1 is applied to a mobile phone, and the wave-absorbing material is rolled into a flexible sheet and is attached between a battery and an antenna of the mobile phone, so that the problems of metal interference and wireless charging heating faced by non-contact communication can be solved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210149294.9A CN114477308A (en) | 2022-02-18 | 2022-02-18 | MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210149294.9A CN114477308A (en) | 2022-02-18 | 2022-02-18 | MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114477308A true CN114477308A (en) | 2022-05-13 |
Family
ID=81481781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210149294.9A Pending CN114477308A (en) | 2022-02-18 | 2022-02-18 | MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114477308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115318339A (en) * | 2022-08-11 | 2022-11-11 | 郑州大学 | ZIF-67-loaded lotus leaf derived biochar and preparation method and application thereof |
| CN115716641A (en) * | 2022-11-11 | 2023-02-28 | 中国船舶重工集团公司第七二五研究所 | MOFs derivative material with electromagnetic wave absorption performance and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN210576425U (en) * | 2019-09-25 | 2020-05-19 | 北京布科思科技有限公司 | UWB antenna device |
-
2022
- 2022-02-18 CN CN202210149294.9A patent/CN114477308A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN210576425U (en) * | 2019-09-25 | 2020-05-19 | 北京布科思科技有限公司 | UWB antenna device |
Non-Patent Citations (2)
| Title |
|---|
| LONG FENGLAN 等: "Double shell structured MnFe2O4@FeO/C derived from MnFe2O4@ZIF-8 for electromagnetic wave absorption", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 906, pages 1 - 2 * |
| 鲁世斌: "MOFs衍生的金属/金属氧化物与MWGNTs复合材料制备及电磁波吸收性能研究", 《中国博士学位论文全文数据库 基础科学辑》, no. 2, pages 005 - 79 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115318339A (en) * | 2022-08-11 | 2022-11-11 | 郑州大学 | ZIF-67-loaded lotus leaf derived biochar and preparation method and application thereof |
| CN115318339B (en) * | 2022-08-11 | 2023-05-26 | 郑州大学 | ZIF-67-loaded lotus leaf derived biochar and preparation method and application thereof |
| CN115716641A (en) * | 2022-11-11 | 2023-02-28 | 中国船舶重工集团公司第七二五研究所 | MOFs derivative material with electromagnetic wave absorption performance and preparation method thereof |
| CN115716641B (en) * | 2022-11-11 | 2024-05-10 | 中国船舶重工集团公司第七二五研究所 | MOFs derivative material with electromagnetic wave absorption performance and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108154984B (en) | Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof | |
| CN114477308A (en) | MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof | |
| CN111014712B (en) | Co/MnO@C composite electromagnetic wave absorbing material and preparation method and application thereof | |
| CN109825252B (en) | Core-shell structure Fe3O4@C@MoS2Preparation of composite material and application thereof | |
| CN112251193A (en) | Composite wave-absorbing material based on MXene and metal organic framework and preparation method and application thereof | |
| CN112839500A (en) | Yolk shell hollow ferroferric oxide @ air @ carbon nano composite wave-absorbing material and preparation method thereof | |
| CN112743098B (en) | Preparation method of nitrogen-doped porous carbon-coated hollow cobalt-nickel alloy composite wave-absorbing material | |
| CN114195197B (en) | Magnetic porous carbon compound and preparation method and application thereof | |
| CN111704115A (en) | A granular α -Fe2O3Preparation of Fe having microwave absorbing Properties4Method of N | |
| CN110028930B (en) | HalS-Fe3O4@ C composite material and preparation method and application thereof | |
| CN109627488B (en) | Graphene composite nano Fe3O4Radar wave absorbing material and preparation method thereof | |
| CN112996375B (en) | Cu9S5/C composite material and preparation method and application thereof | |
| CN111613901B (en) | Graphene/metal oxide/metal ternary nano composite magnetic material and preparation method thereof | |
| CN108024493B (en) | Lotus seedpod structure mesoporous carbon and nano cobalt compound and preparation method and application thereof | |
| CN114449877A (en) | Core-shell Ni/Co alloy @ nitrogen-doped carbon-based wave-absorbing composite material and preparation method thereof | |
| Ge et al. | The fabrication of FeMnO/RGO as anticorrosive microwave absorbent toward marine environment | |
| CN113438883A (en) | Preparation method and application of binary heterostructure wave-absorbing material molybdenum oxide-molybdenum phosphide | |
| CN116603461A (en) | Carbon nano tube/mesoporous carbon/metal oxide composite aerogel wave-absorbing material and preparation method thereof | |
| CN114980715A (en) | Composite porous microsphere material and preparation method and application thereof | |
| CN114314679A (en) | Polypyrrole-coated ferroferric oxide nanoflower wave-absorbing material, preparation method and application | |
| CN108483508B (en) | Porous flaky Fe3O4Electromagnetic wave absorbing agent and preparation method thereof | |
| CN112280533A (en) | Preparation method of ternary composite wave-absorbing material with hollow structure | |
| CN117998830B (en) | Preparation method of functional reduced graphene oxide/metal-polyphenol framework composite aerogel | |
| CN113278399B (en) | Hard/soft magnetic composite ferrite wave absorbing agent and preparation method thereof | |
| CN114212779B (en) | Preparation method of composite wave-absorbing material and composite 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 |