CN114068166A - Hierarchical pore structure carbon-based magnetic composite material and preparation method and application thereof - Google Patents
Hierarchical pore structure carbon-based magnetic composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hierarchical pore structure carbon-based magnetic composite material and a preparation method and application thereof, and the hierarchical pore structure carbon-based magnetic composite material consists of a macroporous-level biomass carbon sheet substrate and a mesoporous-level metal organic framework derivative nano carbon sheet array loaded with magnetic nano particles, wherein the biomass carbon sheet is of a thin-wall sheet structure with surface wrinkles and openings with the pore diameter of 2-60 mu m distributed, the metal organic framework derivative nano carbon sheet is of a leaf-shaped form, and the surface is uniformly distributed with the magnetic nano particles with the particle diameter of 20-100 nm. The invention takes the oroxylum indicum as a substrate, and combines a hydrothermal method and a high-temperature pyrolysis method to grow the cobalt-zinc metal organic framework nano array with a two-dimensional leaf-shaped structure on the surface in situ to obtain a multidimensional and multicomponent micro-nano structure integrating mesoporous carbon, macroporous carbon sheets and magnetic nano particles, and the oroxylum indicum can realize broadband high-strength absorption of electromagnetic waves under the conditions of thin thickness and low filling ratio as a wave-absorbing material, and has a good application prospect.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a hierarchical pore structure carbon-based magnetic composite material, and a preparation method and application thereof.
Background
The rapid development of wireless communication technology brings convenience to people, and simultaneously, a series of electromagnetic interference problems seriously harming human health and prolonging the service life of precision equipment are caused, so that the development of efficient microwave absorbers is urgently needed, and redundant electromagnetic waves are introduced into the microwave absorbers and are converted into heat energy or energy in other forms so as to achieve the purpose of attenuating the electromagnetic waves. At present, wave absorbing materials such as magnetic materials, carbon materials, transition metal sulfides, transition metal carbonitrides, conductive polymers and the like are developed, but the single-component absorbent generally has the problems of unsatisfactory impedance matching, weak attenuation capability and insufficient synergistic effect, and cannot meet the requirements of thin coating thickness, light weight, strong absorption bandwidth and strong reflection loss; in addition, a part of wave-absorbing materials have the problems of complex preparation process, environmental pollution caused by byproducts, low yield, high raw material cost and the like, the application of the wave-absorbing materials in the field of electromagnetic wave absorption is limited, the cost performance of the product and the industrial scale are considered, and the problem of ensuring high-efficiency wave-absorbing performance is the problem which needs to be solved at present.
Compared with the traditional carbon material, the biomass derived carbon material has been widely researched in the field of wave-absorbing materials in recent years due to low price, reproducibility, no toxicity, no harm, unique physical structure and chemical properties. Researches show that the biological carbon material obtained by high-temperature treatment has high dielectric loss capacity, but has the problems of impedance mismatch and weak complex permeability, and cannot obtain excellent electromagnetic wave absorption performance. Therefore, the method of compounding the electrical loss type biomass carbon material with the magnetic loss type material to adjust impedance matching and enhance loss mechanism is an effective way to improve wave absorption performance, but the magnetic particles synthesized by the traditional method such as a hydrothermal method or a coprecipitation method have the problems of high density, agglomeration, poor binding force with a carbon matrix and the like, and are difficult to meet application requirements.
Magnetic nanoparticles obtained by direct high-temperature carbonization of a metal organic framework (MoF) are often uniformly distributed in a carbon matrix, the particle size is relatively uniform, the skin effect caused by aggregation of large magnetic particles can be effectively avoided, a strong anisotropic field, high saturation magnetization and high Snoek limit can be generated in a GHz range, and the appearance, the specific surface area, the pore diameter and the magnetic content of a metal organic framework can be effectively regulated and controlled by regulating the proportion between metal salt and an organic ligand, so that the magnetic mesoporous carbon template is an ideal template for preparing the magnetic mesoporous carbon. However, there are only reports related to the preparation of a hierarchical porous structure carbon-based magnetic composite material as a wave-absorbing material by combining a bimetallic organic framework and a biomass material.
Disclosure of Invention
In view of the above disadvantages of the prior art, the main object of the present invention is to provide a carbon-based magnetic composite material with a hierarchical pore structure, which uses an oroxylum indicum with abundant resources and low cost as a matrix material for ZnCo-MOF growth, has abundant heterogeneous interfaces, a large specific surface area, a large number of defects, multi-sized pores, and uniformly distributed magnetic nanoparticles, is beneficial to realizing the optimization of the magnetoelectric loss synergistic effect, the mechanisms such as interface polarization and multiple reflection/scattering, and impedance matching, and has the advantages of light weight, strong absorption, thin thickness, and wide frequency band as an economical efficient wave absorber.
The invention also aims to provide a preparation method of the carbon-based magnetic composite material with the hierarchical pore structure, which takes oroxylum indicum as a template, adopts hydrothermal reaction to grow bimetallic ZnCo-MOF on the surface of the oroxylum indicum in situ, and prepares the carbon-based magnetic composite material with the hierarchical pore structure by high-temperature pyrolysis in a protective gas atmosphere; the composite material can be endowed with different specific surface areas, graphitization degrees, magnetic contents and multi-size pores by simply changing the molar ratio of the cobalt salt to the zinc salt in the precursor, and the broadband high-strength absorption performance of the composite material on electromagnetic waves under lower filling ratio and thinner thickness can be realized by adjusting the static magnetic performance and electromagnetic parameters of the composite material.
The above object of the present invention is achieved by the following technical solutions:
the invention provides a hierarchical porous structure carbon-based magnetic composite material, which consists of a macroporous-level biomass carbon sheet substrate and a mesoporous-level metal organic framework derivative nano carbon sheet array loaded with magnetic nano particles; wherein:
the biomass carbon sheet is a thin-wall sheet structure with surface wrinkles and holes with the aperture of 2-60 mu m;
the metal organic framework derived nano carbon sheet is in a leaf-shaped form, and magnetic nano particles with the particle size of 20-100 nm are uniformly distributed on the surface of the metal organic framework derived nano carbon sheet.
Preferably, the magnetic nanoparticles are cobalt particles.
Preferably, the metal-organic framework derived nanocarbon sheet has a width of 3 μm and a thickness of 300 nm.
The invention also provides a preparation method of the multilevel pore structure carbon-based magnetic composite material, which comprises the following steps:
(1) washing the oroxylum indicum sequentially with water and ethanol for several times, and drying;
(2) adding cobalt nitrate hexahydrate and zinc nitrate hexahydrate into water, and ultrasonically mixing uniformly to obtain a mixed solution A; adding dimethyl imidazole and oroxylum indicum into water to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, stirring, transferring to a muffle furnace for hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out, washing the product for multiple times by deionized water and alcohol, filtering, separating and drying to obtain a ZnCo-MOF/biomass composite material;
(3) and (3) putting the ZnCo-MOF/biomass composite material into a quartz boat, and pyrolyzing under a protective atmosphere to obtain the Co/C composite material with the porous structure.
Preferably, in the step (1), the washing times are 3-5 times, the drying temperature is 40-60 ℃, and the drying time is 8-12 h.
Preferably, in the step (2), the volume ratio of the A, B mixed solution is 1: 1, the molar concentration ratio of the cobalt salt, the zinc salt and the dimethyl imidazole is 1-2: 1-2: 19, the concentration of the oroxylum indicum is 3-6 g/L.
Preferably, in the step (2), stirring is carried out for 1-10 min; the hydrothermal reaction temperature is 60-80 ℃ and the time is 3-5 hours.
Preferably, in the step (2), the washing times are 3-5 times; the drying temperature is 40-60 deg.C, and the drying time is 8-12 h.
Preferably, in the step (3), the pyrolysis temperature is 700 ℃, the pyrolysis time is 2h, the heating rate is 1-5 ℃/min, and the protective atmosphere is selected from nitrogen and/or argon.
The invention also provides application of the multilevel pore structure carbon-based magnetic composite material as a wave absorbing material or a wave absorbing agent in the field of electromagnetic waves.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional wave-absorbing material, the multi-level pore structure carbon-based magnetic composite material overcomes the defects of single-component absorbent in impedance mismatch and weak loss capability, has a multi-dimensional and multi-component micro-nano structure integrating mesoporous carbon, macroporous carbon sheets and magnetic nanoparticles, and is beneficial to promoting the mechanisms of magnetoelectric loss synergistic effect, interface polarization, multiple reflection/scattering and the like and obtaining good impedance matching and electromagnetic wave attenuation capability. In addition, electromagnetic parameters can be effectively regulated and controlled by regulating the proportion of metal salt in the MoF solution, so that the maximum reflection loss of the composite material reaches-66.9 dB under the conditions that the filling ratio is only 12 wt% and the thickness is 1.66mm, and meanwhile, the effective bandwidth reaches 5.6GHz when the thickness is 1.9mm, thereby realizing the broadband high-strength absorption of electromagnetic waves under the conditions of thin thickness and low filling ratio, and providing a new idea for the development of economic high-performance absorbents.
(2) The preparation method of the carbon-based magnetic composite material with the hierarchical pore structure can effectively simplify the complex synthesis steps of the magnetoelectric common loss type wave-absorbing composite material, has the advantages of simple process, no pollution, low cost and high yield, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an XRD pattern of the products obtained in examples 1-3 and comparative example 1.
Fig. 2 is an SEM image of the products obtained in example 2 and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The products obtained in the preparation of the following examples and comparative examples were obtained using an irradiation source of radiation
X-ray diffraction (abbreviated as XRD) of the sample to determine the crystal structure of the sample.
The products prepared in the following examples and comparative examples were observed by Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) for morphology of the samples.
The products obtained in the following examples and comparative examples were uniformly dispersed in paraffin wax, which accounted for 12% of the total weight, and then molded into coaxial sample rings having an outer diameter of 7.0mm and an inner diameter of 3.04mm by means of a die, and the electrical complex permittivity and complex permeability of the material in the frequency range of 2-18 GHz were measured using a ceyer 3672B-S vector network analyzer with reference to the technical requirements of coaxial line transmission/reflection measurement in american society for testing materials standard ASTM D7449/D7449M-08, and the RL value of the material was calculated according to the transmission line theory.
Example 1
In this embodiment, a hierarchical pore structure carbon-based magnetic composite material based on a bimetallic organic framework and biomass is prepared through the following steps:
(1) washing semen Oroxyli with water and ethanol for 3 times, oven drying in 60 deg.C oven for 24 hr, and removing adsorbed water.
(2) Taking 20ml of water, adding 0.33mmol of cobalt nitrate hexahydrate and 0.66mmol of zinc nitrate hexahydrate, and ultrasonically mixing uniformly to obtain a mixed solution A; taking 20ml of water, adding 6.4mmol of dimethyl imidazole and 200mg of oroxylum indicum to obtain mixed solution B; pouring the mixed solution A into the mixed solution B, stirring for 2min, and then transferring to a muffle furnace for hydrothermal reaction at 70 ℃ for 4 hours; and cooling the reaction product to room temperature, taking out, washing the product for 3 times by using deionized water and alcohol, filtering, separating and drying to obtain the ZnCo-MOF/biomass composite material.
(3) And (3) putting the ZnCo-MOF/biomass composite material into a quartz boat, pyrolyzing the ZnCo-MOF/biomass composite material in an argon atmosphere, heating the ZnCo-MOF/biomass composite material to 700 ℃ at the heating rate of 2 ℃/min, calcining the ZnCo-MOF/biomass composite material for 2 hours at the temperature, and cooling the ZnCo-MOF/biomass composite material to room temperature along with a furnace to obtain a final product S1.
Example 2
In this embodiment, a hierarchical pore structure carbon-based magnetic composite material based on a bimetallic organic framework and biomass is prepared through the following steps:
(1) washing semen Oroxyli with water and ethanol for 3 times, oven drying in 60 deg.C oven for 24 hr, and removing adsorbed water.
(2) Taking 20ml of water, adding 0.495mmol of cobalt nitrate hexahydrate and 0.495mmol of zinc nitrate hexahydrate into the water, and ultrasonically mixing the mixture uniformly to obtain a mixed solution A; taking 20ml of water, adding 6.4mmol of dimethyl imidazole and 200mg of oroxylum indicum to obtain mixed solution B; and pouring the mixed solution A into the mixed solution B, stirring for 2min, and then transferring to a muffle furnace for hydrothermal reaction at 70 ℃ for 4 hours. And cooling the reaction product to room temperature, taking out, washing the product for 3 times by using deionized water and alcohol, filtering, separating and drying to obtain the ZnCo-MOF/biomass composite material.
(3) And (3) putting the ZnCo-MOF/biomass composite material into a quartz boat, pyrolyzing the ZnCo-MOF/biomass composite material in an argon atmosphere, heating the ZnCo-MOF/biomass composite material to 700 ℃ at the heating rate of 2 ℃/min, calcining the ZnCo-MOF/biomass composite material for 2 hours at the temperature, and cooling the ZnCo-MOF/biomass composite material to room temperature along with a furnace to obtain a final product S2.
Example 3
In this embodiment, a hierarchical pore structure carbon-based magnetic composite material based on a bimetallic organic framework and biomass is prepared through the following steps:
(1) washing semen Oroxyli with water and ethanol for 3 times, oven drying in 60 deg.C oven for 24 hr, and removing adsorbed water.
(2) Taking 20ml of water, adding 0.66mmol of cobalt nitrate hexahydrate and 0.33mmol of zinc nitrate hexahydrate, and ultrasonically mixing uniformly to obtain a mixed solution A; taking 20ml of water, adding 6.4mmol of dimethyl imidazole and 200mg of oroxylum indicum to obtain mixed solution B; and pouring the mixed solution A into the mixed solution B, stirring for 2min, and then transferring to a muffle furnace for hydrothermal reaction at 70 ℃ for 4 hours. And cooling the reaction product to room temperature, taking out, washing the product for 3 times by using deionized water and alcohol, filtering, separating and drying to obtain the ZnCo-MOF/biomass composite material.
(3) And (3) putting the ZnCo-MOF/biomass composite material into a quartz boat, pyrolyzing the ZnCo-MOF/biomass composite material in an argon atmosphere, heating the ZnCo-MOF/biomass composite material to 700 ℃ at the heating rate of 2 ℃/min, calcining the ZnCo-MOF/biomass composite material at the temperature for 2 hours, and cooling the ZnCo-MOF/biomass composite material to room temperature along with a furnace to obtain a final product S3.
Comparative example 1
In this comparative example, carbonized oroxylum indicum was prepared by the following steps: washing semen Oroxyli with water and ethanol for 3 times, oven drying in 60 deg.C oven for 24 hr, and removing adsorbed water. Calcining the dried oroxylum indicum in an argon atmosphere at 700 ℃ for 2h, heating at the rate of 2 ℃/min, cooling to room temperature along with the furnace to obtain carbonized oroxylum indicum, and marking as PCS.
The phase change of the product materials prepared in examples 1-3 and comparative example 1 is shown in fig. 1, the corresponding microstructure is shown in fig. 2, and the wave-absorbing property is shown in table 1.
TABLE 1
The symbols in table 1 have the following meanings: RL — reflection loss; RLminMinimum reflection losses.
As can be seen from the XRD pattern of fig. 1, the PCS sample in comparative example 1 has two broad diffraction peaks at 26 ° and 44 °, which are typical graphite carbon diffraction peaks, whereas the composite materials prepared in examples 1-3 have not only the above-mentioned carbon peaks, but also two characteristic peaks attributed to cobalt at 44.5 ° and 51.8 °, and the diffraction peaks of cobalt become sharper and sharper as the content of cobalt salt in the precursor increases, indicating that the purity and crystallinity of the sample are increasing, and both consist of two phases of carbon and cobalt.
From the SEM image of fig. 2, the microstructure of example 2 is represented by that the oroxylum surface is covered by the dense MOF nanosheet array, the metal organic framework derived nanocarbon sheet is in a leaf-like shape, the width is about 3 μm, the thickness is about 300nm, and cobalt particles with the particle size of 20-100 nm are uniformly distributed on the surface (fig. 2 a); the microstructure of comparative example 1 shows a thin and light wall with a large number of pores of 2-60 μm diameter distributed over the corrugated surface (fig. 2 b).
As can be seen from Table 1, the effective wave-absorbing bandwidth (RL) of comparative example 1 is 2.64mm in matching thickness<-10dB) of 4.4GHz, RLminIs-43.7 dB; in the embodiment 1, the effective wave-absorbing bandwidth is 5.5GHz when the matching thickness is 1.8mm, and the RL when the matching thickness is 2.13mmminIs-64.4 dB; in example 2, the effective wave-absorbing bandwidth is 5.6GHz at the matching thickness of 1.9mm, and the RL at the matching thickness of 1.66mmminIs-66.9 dB; in example 3, the effective wave-absorbing bandwidth is 4.4GHz at the matching thickness of 1.83mm, and the RL at the matching thickness of 1.5mmminIs-15.1 dB, and only Ku wave band RL<10dB, and the rest wave bands do not have good wave absorbing performance. Therefore, compared with the comparative example 1, the wave absorbing performance of the composite materials in the embodiments 1 and 2 is broadband high-strength absorption under thin thickness, and the composite materials have great application potential.
Claims (10)
1. A hierarchical pore structure carbon-based magnetic composite material is characterized by comprising a macroporous-level biomass carbon sheet substrate and a mesoporous-level metal organic framework derivative nano carbon sheet array loaded with magnetic nano particles; wherein:
the biomass carbon sheet is a thin-wall sheet structure with surface wrinkles and holes with the aperture of 2-60 mu m;
the metal organic framework derived nano carbon sheet is in a leaf-shaped form, and magnetic nano particles with the particle size of 20-100 nm are uniformly distributed on the surface of the metal organic framework derived nano carbon sheet.
2. The hierarchical pore structure carbon-based magnetic composite according to claim 1, wherein the magnetic nanoparticles are cobalt particles; and/or the width of the metal organic framework derived nano carbon sheet is 3 μm, and the thickness is 300 nm.
3. A method for preparing the hierarchical pore structure carbon-based magnetic composite material according to claim 1 or 2, comprising the steps of:
(1) washing the oroxylum indicum sequentially with water and ethanol for several times, and drying;
(2) adding cobalt nitrate hexahydrate and zinc nitrate hexahydrate into water, and ultrasonically mixing uniformly to obtain a mixed solution A; adding dimethyl imidazole and oroxylum indicum into water to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, stirring, transferring to a muffle furnace for hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out, washing the product for multiple times by deionized water and alcohol, filtering, separating and drying to obtain a ZnCo-MOF/biomass composite material;
(3) and (3) putting the ZnCo-MOF/biomass composite material into a quartz boat, and pyrolyzing under a protective atmosphere to obtain a product, namely the hierarchical pore structure carbon-based magnetic composite material.
4. The preparation method of the hierarchical pore structure carbon-based magnetic composite material according to claim 3, wherein in the step (1), the washing times are 3-5 times, the drying temperature is 40-60 ℃, and the drying time is 8-12 hours.
5. The method for preparing the hierarchical pore structure carbon-based magnetic composite material according to claim 3, wherein in the step (2), the volume ratio of the A, B mixed solution is 1: 1, the molar concentration ratio of the cobalt salt, the zinc salt and the dimethyl imidazole is 1-2: 1-2: 19, the concentration of the oroxylum indicum is 3-6 g/L.
6. The method for preparing the hierarchical pore structure carbon-based magnetic composite material according to claim 5, wherein in the step (2), the volume ratio of the A, B mixed solution is 1: 1, wherein the molar concentration ratio of cobalt salt, zinc salt and dimethylimidazole is selected from 1: 2: 19. 1: 1 or 19, 2: 1: 19, or a pharmaceutically acceptable salt thereof.
7. The preparation method of the hierarchical pore structure carbon-based magnetic composite material according to claim 3, wherein in the step (2), the mixture is stirred for 1-10 min, the hydrothermal reaction temperature is 60-80 ℃, and the time is 3-5 hours.
8. The method for preparing the hierarchical pore structure carbon-based magnetic composite material according to claim 3, wherein in the step (2), the washing times are 3-5 times, the drying temperature is 40-60 ℃, and the drying time is 8-12 hours.
9. The preparation method of the hierarchical pore structure carbon-based magnetic composite material according to claim 3, wherein in the step (3), the pyrolysis temperature is 700 ℃, the pyrolysis time is 2 hours, and the temperature rise rate is 1-5 ℃/min;
and/or the protective atmosphere is selected from nitrogen and/or argon.
10. The application of the hierarchical pore structure carbon-based magnetic composite material as claimed in claim 1 or 2 as a wave absorbing material or a wave absorbing agent in the field of electromagnetic waves.
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| CN115491177B (en) * | 2022-08-26 | 2023-12-19 | 南京航空航天大学 | MOF-derived carbon-based magnetic nano composite electromagnetic wave absorbing material and preparation method thereof |
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