CN115784665B - Preparation method of foaming wave-absorbing material based on MOFs (metal-organic frameworks) derivative - Google Patents
Preparation method of foaming wave-absorbing material based on MOFs (metal-organic frameworks) derivative Download PDFInfo
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- 238000005187 foaming Methods 0.000 title claims abstract description 40
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims description 25
- 235000011837 pasties Nutrition 0.000 claims description 21
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 238000009795 derivation Methods 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
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- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 3
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
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- 239000013384 organic framework Substances 0.000 abstract description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 abstract description 2
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Abstract
The invention discloses a preparation method of a foaming wave-absorbing material based on MOFs (metal organic frameworks). Firstly, under the condition of no solvent, a surfactant is introduced, a foaming ZnMo bimetal organic framework derivative is prepared through a mechanical ball milling method, and then the porous molybdenum carbide wave-absorbing material is obtained through high-temperature annealing reaction, cooling to room temperature and acid washing. According to the invention, MOFs precursor is obtained by an in-situ mechanochemical preparation method, and self-foaming is regulated and controlled by adding a surfactant, so that the wave-absorbing material with high porosity and high stability is obtained. The method is an effective method for preparing the porous foaming material, which is simple and convenient to operate, green and safe, good in repeatability and high in efficiency. The obtained material has optimal reflection loss when the thickness is 2.55mm, the minimum reflection loss value is-60.47 dB, and the effective wave absorption frequency width smaller than-10 dB is 4.32GHz.
Description
Technical Field
The invention belongs to the technical field of porous foaming wave-absorbing materials, and particularly relates to a preparation method of a foaming wave-absorbing material based on MOFs derivatization.
Background
Electromagnetic radiation can not only interfere with the normal operation of other surrounding instruments, resulting in malfunctions and signal interruption, but also seriously impair the physical health of humans, and can easily cause various diseases such as cancers and endocrine disorders. Therefore, development of high-performance electromagnetic wave absorbing materials and electromagnetic wave shielding materials to solve the harmful effects of electromagnetic radiation has been unprecedented. The wave absorbing material can effectively absorb electromagnetic waves by effectively converting the electromagnetic waves into heat energy or other forms of energy, and the electromagnetic waves can be basically weakened, so that the development of the high-performance electromagnetic wave absorbing material with wide effective absorption band and good stability has great significance, and the research interest of a plurality of students is also promoted.
With the development of nanotechnology, the introduction of carbon materials greatly improves the performance of electromagnetic wave absorbing materials, but the problems of low absorption strength and narrow absorption band still exist. MOFs (metal organic framework material) is taken as a porous hybrid material self-assembled by metal ions and organic ligands, so that not only can rich carbon sources be provided, but also doping of metal nano ions in a carbon pore canal can be realized, and further, the electromagnetic properties of the material can be effectively regulated and controlled, and an excellent carbon-based wave absorbing material is obtained. Wang Liuying the subject group derives light porous carbon composite materials through flaky carbon-based iron and MOFs, and realizes the regulation of electromagnetic wave absorption performance of the composite materials through regulating and controlling the components of the porous carbon coating layer (application number: 202011391140.8). At present, most MOFs derivative materials are prepared by a hydrothermal synthesis method, the synthesis process is complex, and the growth process is difficult to control; in the preparation process, a large amount of organic solvents are used, so that the environment is polluted; meanwhile, the yield is low, and the mass production is limited. Therefore, the MOFs derived porous wave-absorbing material has the advantages of simple process and environmental protection.
Disclosure of Invention
The invention aims to provide a preparation method of a foaming wave-absorbing material based on MOFs (metal organic frameworks) derivatization, which reduces the use of an organic solvent in the MOFs preparation process, and simultaneously introduces a surfactant to effectively improve the porosity of a target material through self-foaming and regulate and control the pore channel structure.
The technical scheme adopted by the invention is that the preparation method of the foaming wave-absorbing material based on MOFs derivation comprises the following specific operation steps:
step 1, preparing a foaming ZnMo bimetallic MOFs precursor by a mechanical method: uniformly mixing zinc acetate, 2-methylimidazole, molybdic acid and surfactant (polyether F127) powder according to a certain mass ratio, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, starting ball milling, setting the ball milling time to be 120-540 min and the frequency to be 30Hz until the solid reactant becomes pasty slurry A;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and placing the porcelain boat into a blast drying oven for drying at 100 ℃ for 12 hours;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a temperature-controlled programmed tube furnace, heating to 800-1000 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 2-3 hours, and naturally cooling to room temperature to obtain black powder B.
And 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying at 60 ℃, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required wave-absorbing material.
And 5, mixing the foaming wave-absorbing material, paraffin and carbon nano tubes in a certain proportion, pressing into an annular sample, and testing the reflection loss performance of the sample.
The present invention is also characterized in that,
the mass ratio of zinc acetate, 2-methylimidazole, molybdic acid and surfactant (polyether F127) in step 1 was 5:3:1:3.
And (3) setting the mechanical ball milling time in the step (1) to be 120-540 min.
The zinc acetate in step 1 may be replaced by any one of zinc sulfate, zinc chloride and zinc nitrate.
In the step 2, the temperature of the blast drying box is 50-150 ℃ and the time is 12-24 hours.
In the step 3, the annealing process is carried out in an inert atmosphere, the temperature is set to 800-1000 ℃, and the heat preservation time is 2-3 hours.
The temperature rising rate in the step 3 is 5-8 ℃/min.
The molar concentration of hydrochloric acid used in step 4 was 1.0mol/L.
The drying temperature in the step 4 is 30-120 ℃.
According to the invention, a simple and green solvation-free mechanochemical synthesis method is adopted to prepare the MOFs material in situ, and a surfactant is introduced in the preparation process simultaneously to regulate the morphology and the performance of the product through a spontaneous foaming technology, so that bubbles in a foam structure provide rich paths for the propagation of incident electromagnetic waves, and an ideal electromagnetic wave absorption material is obtained.
The key steps in the invention are synthesized by the following principle:
firstly, a foaming ZnMo bimetallic MOFs precursor is obtained by a simple method, foaming is carried out simultaneously in the process of preparing the MOFs by mechanical ball milling, the pore space of a product is increased, the porosity of a final product is improved by rich bubbles in a foam structure, the pore channel structure of the final product is regulated and controlled, and a rich path is provided for the propagation of incident electromagnetic waves.
And secondly, a simple and controllable mechanical ball milling operation method is adopted, a surfactant (polyether F127) is introduced, the ball milling time is controlled, and the chemical adsorption and chemical reaction of the surfactant on the powder surface are promoted by utilizing the mechanical activation in the ball milling process.
The beneficial effects of the invention are as follows:
(1) The invention adopts an environment-friendly, simple and controllable mechanochemical preparation process, directly synthesizes the ZnMo bimetal organic framework precursor by mechanical ball milling of raw materials, and does not use any organic solvent in the process. Meanwhile, the introduction of the surfactant in the process promotes the self-foaming process of the precursor material, so that the high-porosity material is obtained, and the porous molybdenum carbide material is generated in the subsequent heat treatment process.
(2) The porous wave-absorbing material prepared by the invention has optimal reflection loss when the thickness is 2.55mm, the minimum reflection loss value is-60.47 dB, the effective wave-absorbing frequency width smaller than-10 dB is up to 4.32GHz, and the wave-absorbing performance of the wave-absorbing material is effectively improved.
(3) The wave-absorbing material prepared by the invention meets the application requirements of 'thin, light, wide and strong' of the wave-absorbing material, and has the advantages of simple preparation process, easy operation, green environmental protection, high efficiency and short time.
Drawings
FIG. 1 is a flow chart of a preparation method of the foaming wave-absorbing material based on MOFs derivation;
FIG. 2 is an XRD diffraction pattern of a foamed ZnMo bimetallic organic framework precursor material of the present invention;
FIG. 3 is an XRD diffraction pattern of the foamed wave-absorbing material of the present invention;
fig. 4 is an SEM image of a foam wave-absorbing material derived based on MOFs.
FIG. 5 is a graph of reflection loss of the foamed wave absorbing material of the present invention in the 2-18 GHz band;
FIG. 6 is a bandwidth diagram of the foamed wave absorbing material of the present invention in the 2-18 GHz band;
FIG. 7 is a graph of the real part of dielectric constant of the foamed wave-absorbing material of the present invention in the frequency range of 2 to 18 GHz;
FIG. 8 is a graph of the imaginary part of the dielectric constant of the foamed wave absorbing material of the present invention in the 2-18 GHz band;
FIG. 9 is a graph showing dielectric loss tangent of the foamed wave absorbing material of the present invention in the frequency range of 2 to 18 GHz;
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The preparation method of the foaming wave-absorbing material based on MOFs derivation is shown in figure 1, and the specific operation steps are as follows:
step 1, uniformly mixing zinc acetate, 2-methylimidazole, molybdic acid and surfactant (polyether F127) powder according to a mass ratio of 5:3:1:3, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, starting ball milling, setting the ball milling time to be 360 minutes and the frequency to be 30Hz until a solid reactant becomes pasty slurry A;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and placing the porcelain boat into a blast drying oven for drying at 100 ℃ for 12 hours;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a programmed temperature-controlled tube furnace, heating to 900 ℃ at a heating rate of 8 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain black powder B.
And 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying at 60 ℃, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required wave-absorbing material.
And 5, mixing the foaming wave-absorbing material, paraffin and carbon nano tubes in a certain proportion, pressing into an annular sample, and testing the reflection loss performance of the sample.
Example 2
The preparation method of the foaming wave-absorbing material based on MOFs derivation is shown in figure 1, and the specific operation steps are as follows:
step 1, uniformly mixing zinc acetate, 2-methylimidazole, molybdic acid and surfactant (polyether F127) powder according to a mass ratio of 5:3:1:3, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, starting ball milling, setting the ball milling time to 450 minutes and the frequency to 30Hz until a solid reactant becomes pasty slurry A;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and placing the porcelain boat into a blast drying oven for drying at 100 ℃ for 12 hours;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a programmed temperature-controlled tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain black powder B.
And 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying at 60 ℃, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required wave-absorbing material.
And 5, mixing the foaming wave-absorbing material, paraffin and carbon nano tubes in a certain proportion, pressing into an annular sample, and testing the reflection loss performance of the sample.
Example 3
The invention relates to a preparation method of foaming wave-absorbing material based on MOFs derivation, which comprises the following specific operation steps:
step 1, uniformly mixing zinc chloride, 2-methylimidazole, molybdic acid and surfactant (polyether F127) powder according to a mass ratio of 5:3:1:3, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, starting ball milling, setting the ball milling time to 450 minutes and the frequency to 30Hz until a solid reactant becomes pasty slurry A;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and placing the porcelain boat into a blast drying oven for drying at 100 ℃ for 12 hours;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a programmed temperature-controlled tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain black powder B.
And 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying at 60 ℃, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required wave-absorbing material.
And 5, mixing the foaming wave-absorbing material, paraffin and carbon nano tubes in a certain proportion, pressing into an annular sample, and testing the reflection loss performance of the sample.
Example 4
The invention relates to a preparation method of foaming wave-absorbing material based on MOFs derivation, which comprises the following specific operation steps:
step 1, uniformly mixing zinc nitrate, 2-methylimidazole, molybdic acid and surfactant (polyether F127) powder according to a mass ratio of 5:3:1:3, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, starting ball milling, setting the ball milling time to be 540 minutes and setting the frequency to be 30Hz until a solid reactant becomes pasty slurry A;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and placing the porcelain boat into a blast drying oven for drying at 100 ℃ for 12 hours;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a programmed temperature-controlled tube furnace, heating to 800 ℃ at a heating rate of 8 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain black powder B.
And 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying at 60 ℃, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required wave-absorbing material.
And 5, mixing the foaming wave-absorbing material, paraffin and carbon nano tubes in a certain proportion, pressing into an annular sample, and testing the reflection loss performance of the sample.
Example 5
The invention relates to a preparation method of foaming wave-absorbing material based on MOFs derivation, which comprises the following specific operation steps:
step 1, uniformly mixing zinc acetate, 2-methylimidazole, molybdic acid and surfactant (polyether F127) powder according to a mass ratio of 5:3:1:3, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, starting ball milling, setting the ball milling time to 270 minutes and setting the frequency to 30Hz until a solid reactant becomes pasty slurry A;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and placing the porcelain boat into a blast drying oven for drying at 100 ℃ for 12 hours;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a programmed temperature-controlled tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature to obtain black powder B.
And 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying at 60 ℃, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required wave-absorbing material.
And 5, mixing the foaming wave-absorbing material, paraffin and carbon nano tubes in a certain proportion, pressing into an annular sample, and testing the reflection loss performance of the sample.
As shown in FIG. 2, the XRD diffraction pattern of the precursor material of the foaming ZnMo bimetal organic frame prepared by the invention proves the successful synthesis of the ZnMo bimetal organic frame according to the curve conforming to the standard HZIF-ZnMo.
As shown in FIG. 3, XRD diffraction patterns of the foaming wave-absorbing material based on MOFs and the mechanochemical preparation method of the invention, peaks at about 20 degrees are carbon peaks, and peaks at 36.6 degrees, 42.4 degrees, 61.8 degrees and 74.3 degrees correspond to (111), (200), (220) and (311) crystal planes of MoC (JCPDS-01-089-2868), respectively.
As shown in fig. 4, SEM images of the MOFs-derived foamed wave absorbing material of the present invention are shown. From the figure, it can be seen that the foamed wave-absorbing material has a rich pore structure.
As shown in FIG. 5, the reflection loss diagram of the foam wave absorbing material based on MOFs derivation in the invention in the frequency range of 2-18 GHz is shown, the wave absorbing body has optimal reflection loss when the thickness is 2.55mm, and the minimum reflection loss value is-60.47 dB.
As shown in FIG. 6, the bandwidth diagram of the MOFs-derived foamed wave absorbing material in the frequency range of 2-18 GHz is shown, and the effective wave absorbing frequency smaller than-10 dB reaches 4.32GHz when the thickness is 2.55 mm.
As shown in FIG. 7, the real part diagram of the dielectric constant of the foam wave-absorbing material based on MOFs derivative in the frequency range of 2-18 GHz is shown, the absorption capacity is deteriorated along with the increase of frequency, and the real part value is higher, so that the material has good energy storage capacity, and further the foam material can still maintain high polarization characteristics under the high-frequency condition;
as shown in FIG. 8, the dielectric constant imaginary part diagram of the MOFs-derived foaming wave-absorbing material in the frequency range of 2-18 GHz shows a decreasing trend of loss capacity with the increase of frequency;
as shown in FIG. 9, the dielectric loss tangent diagram of the foam wave-absorbing material derived from MOFs in the frequency range of 2-18 GHz is shown.
Claims (3)
1. The preparation method of the foaming wave-absorbing material based on MOFs is characterized by comprising the following specific operation steps:
step 1, uniformly mixing zinc acetate, 2-methylimidazole, molybdic acid and a surfactant, putting the mixture into a ball milling tank filled with stainless steel grinding balls, sealing, and starting ball milling until a solid reactant becomes pasty slurry A;
the mass ratio of the zinc acetate to the 2-methylimidazole to the molybdic acid to the surfactant in the step 1 is 5:3:1:3; the surfactant is polyether F127;
the ball milling time is set to be 120-540 min, and the frequency is set to be 30Hz;
step 2, separating the pasty slurry A from the stainless steel balls, transferring the pasty slurry A into a porcelain boat, and putting the porcelain boat into a blast drying oven for drying;
step 3, placing the dried sample into a porcelain boat, and adding the sample into N 2 Under the protection of atmosphere, placing the mixture in a program temperature control tube furnace, heating to 800-1000 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 2-3 hours, and naturally cooling to room temperature to obtain black powder B;
step 4, washing the black powder B with hydrochloric acid to remove unreacted molybdic acid, washing with deionized water to be neutral, putting into an oven for drying, cooling to room temperature to obtain a foaming wave-absorbing material, and collecting the required foaming wave-absorbing material;
the molar concentration of hydrochloric acid used in the step 4 is 1.0mol/L; the drying temperature is 60 ℃;
and 5, mixing the foaming wave-absorbing material with paraffin and carbon nano tubes, pressing the mixture into an annular sample, and testing the reflection loss performance of the sample.
2. The method for preparing the foam wave-absorbing material based on MOFs derivation according to claim 1, wherein zinc acetate in the step 1 can be replaced by any one of zinc sulfate, zinc chloride and zinc nitrate.
3. The method for preparing a foam wave-absorbing material based on MOFs derivation according to claim 1, wherein the temperature of the blast drying oven in step 2 is 100 ℃ for 12-24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108834389A (en) * | 2018-07-09 | 2018-11-16 | 安徽理工大学 | A kind of preparation method of the derivative nano combined absorbing material of porous carbon/multi-walled carbon nanotube of bimetallic organic frame |
| CN110723720A (en) * | 2019-10-16 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Light broadband electromagnetic wave absorbing material and preparation method thereof |
| CN114672034A (en) * | 2022-03-11 | 2022-06-28 | 东北大学 | Method for preparing MOFs material by thermally-assisted mechanical ball milling method |
| CN115058616A (en) * | 2022-06-16 | 2022-09-16 | 中国人民解放军火箭军工程大学 | Co/C/CNTs composite wave-absorbing material with one-dimensional micro-nano hierarchical structure and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108834389A (en) * | 2018-07-09 | 2018-11-16 | 安徽理工大学 | A kind of preparation method of the derivative nano combined absorbing material of porous carbon/multi-walled carbon nanotube of bimetallic organic frame |
| CN110723720A (en) * | 2019-10-16 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Light broadband electromagnetic wave absorbing material and preparation method thereof |
| CN114672034A (en) * | 2022-03-11 | 2022-06-28 | 东北大学 | Method for preparing MOFs material by thermally-assisted mechanical ball milling method |
| CN115058616A (en) * | 2022-06-16 | 2022-09-16 | 中国人民解放军火箭军工程大学 | Co/C/CNTs composite wave-absorbing material with one-dimensional micro-nano hierarchical structure and preparation method thereof |
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