CN115716641B - MOFs derivative material with electromagnetic wave absorption performance and preparation method thereof - Google Patents
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Abstract
The invention provides a MOFs derivative material with electromagnetic wave absorption performance and a preparation method thereof, comprising the following steps: firstly, synthesizing a zeolite-imidazole salt skeleton precursor ZIFs; mixing with boron carbon nitrogen nanotube composed of urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature, and evaporating water in an oven through an evaporation dish; finally calcining and carbonizing at 800-1000 ℃ to obtain MOFs derivative material. Due to the existence of the boron carbon nitrogen nanotube, good dispersion can be realized, rich non-uniform interfaces are formed in the nanocomposite, the nanocomposite has strong interface polarization effect and high dielectric loss capacity, the one-dimensional boron carbon nitrogen nanotube microstructure and low dielectric constant further optimize impedance matching of the nanocomposite, and electromagnetic wave absorption performance is improved. The preparation method has the advantages of convenient operation, simple process and low cost, can prepare the electromagnetic wave absorbent with strong absorption, wide frequency band, thin thickness, light weight and high performance, and has good development and application prospect.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a MOFs derivative material with electromagnetic wave absorption performance and a preparation method thereof.
Background
With the rapid development of the electronic industry, electromagnetic radiation or pollution generated by the electronic industry is increasingly harmful to the normal operation of electronic devices and the physical health of human beings, and the electronic industry is attracting attention of more and more researchers. There is a high demand for absorbing materials capable of absorbing and attenuating electromagnetic radiation. The excellent wave absorbing material should have the characteristics of strong absorption, effective Absorption Bandwidth (EAB), light weight and low thickness. Metal Organic Frameworks (MOFs) are periodic structures composed of self-assembly of metal ions or clusters with organic ligands and centers. By a simple carbonization process, MOFs-derived carbon/metal composite materials having a large specific surface area, porous structure and component variability can be prepared and exhibit excellent electromagnetic absorption properties. However, the preparation and mass production costs of the carbonaceous materials are high, and the large-scale application is difficult; the preparation conditions of the magnetic material are difficult to quantify, and the requirement of light weight is not met. There is still a high demand for the development of new materials. Achieving good impedance matching of MOFs-derived absorbers remains a great challenge due to the high dielectric constant of the material itself, inevitably resulting in an imbalance in impedance matching and thus affecting the electromagnetic absorption properties of the absorber. In addition, the unavoidable severe agglomeration of MOFs-derived absorbers prevents the full utilization of the microstructure in practical applications. Therefore, how to prepare MOFs derived materials with better wave-absorbing properties is a problem to be solved in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a MOFs derivative material with electromagnetic wave absorption performance and a preparation method thereof, so as to solve the above-mentioned problems in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of MOFs derivative material with electromagnetic wave absorption performance comprises the following steps:
Firstly, synthesizing a zeolite-imidazole salt skeleton precursor ZIFs; mixing with boron carbon nitrogen nanotube composed of urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature, and evaporating water in an oven through an evaporation dish; finally calcining and carbonizing at 800-1000 ℃ to obtain MOFs derivative material. Embedding MOFs derived metal/metal oxide into boron carbon nitrogen nanotubes, MOFs derived metal/metal oxide nanoparticles achieve satisfactory dispersion, facilitating efficient use of MOF derivative derived conduction losses and magnetic losses.
Further, zeolite-imidazolium framework precursors include ZIF-8 and ZIF-67 precursors.
Further, the preparation of the MOFs derived material comprises the following steps:
Adding 65-130 mg ZIF-8 and 65-130 mg ZIF-67 into a round-bottom flask, adding 3-10 g urea, 0.1-1.0 g polyethylene glycol 2000, 0.05-0.3 g boric acid and 30-100 ml deionized water, dispersing uniformly, stirring continuously, transferring into an evaporating dish, putting into an oven at 80 ℃ for drying, scraping the product after cooling to room temperature, and finally putting into a tube furnace for calcining and carbonizing under the protection of nitrogen to obtain black solid powder, namely the MOFs derivative material.
Further, the temperature of calcination and carbonization in a tube furnace under the protection of nitrogen is 900 ℃.
Further, the temperature rising rate of calcination carbonization in the tube furnace under the protection of nitrogen is 3 ℃/min.
Further, the preparation of the ZIF-8 and ZIF-67 precursors comprises the following steps:
0.297g of Zn (NO 3)2·6H2 O is dissolved in 60mL of deionized water to be dispersed into a uniform A solution, 0.657g of 2-methylimidazole is dissolved in 60mL of deionized water to be dispersed into a uniform B solution, the B solution is rapidly poured into the A solution to be stirred for 12 hours at room temperature, and the mixture is centrifuged and washed and then dried in an oven to obtain white solid powder ZIF-8;
0.291g of Co (NO 3)2·6H2 O is dissolved in 60mL of deionized water to disperse the Co into a uniform C solution, 0.657g of 2-methylimidazole is respectively dissolved in 60mL of deionized water to disperse the Co into a uniform D solution, the D solution is rapidly poured into the C solution to be vigorously stirred for 10min, and after standing and ageing for 12h at room temperature, the mixture is centrifuged and washed, and then dried in an oven to obtain purple solid powder ZIF-67.
In the preparation of ZIF-8 and ZIF-67 precursors, deionized water and ethanol are used for washing, and the washed products are put into a 70 ℃ oven for drying.
Further, the preparation of the boron carbon nitrogen nanotube BCN comprises the following steps: weighing 5g of urea, 0.5g of polyethylene glycol 2000 and 0.15g of boric acid, dissolving in 60mL of deionized water, stirring and dissolving uniformly, transferring to an evaporation dish, placing in an 80 ℃ oven for drying, placing the dried sample in a nitrogen tube furnace for calcining and carbonizing at 900 ℃ for 2 hours, and obtaining black solid powder, namely boron carbon nitrogen nanotube BCN, at a heating rate of 3 ℃/min.
Compared with the prior art, the preparation method of the MOFs derivative material with the electromagnetic wave absorption performance has the following advantages:
Due to the existence of the boron carbon nitrogen nanotubes, the metal and metal oxide nano particles can be well dispersed, and the conductive loss and the magnetic loss derived from MOFs derivatives can be effectively utilized. A rich heterogeneous interface is formed in the nanocomposite resulting in strong interfacial polarization effects and high dielectric loss capabilities. In addition, the one-dimensional boron carbon nitrogen nanotube microstructure and the low dielectric constant further optimize the impedance matching of the nanocomposite, thereby improving the electromagnetic wave absorption performance. The preparation method of the invention has the advantages of convenient operation, simple process and low cost, can prepare the electromagnetic wave absorbent with strong absorption, wide frequency band, thin thickness, light weight and high performance, and has good development and application prospect.
The effective absorption bandwidth of the composite material can reach 4.24GHz under the condition of low filling ratio of 20wt%, and the minimum reflection loss can reach-54.4 dB at 16.7GHz, and the thickness of the composite material is only 1.8mm. The research result has the advantages of strong absorption, wide frequency band, thin thickness and light weight, and has wide application market.
The invention also provides a MOFs derivative material with electromagnetic wave absorption performance, which is prepared by the preparation method, the morphology of the MOFs derivative material is a hollow tubular carbon nano-tube structure, the tube diameter is 100-1000 nm, and metal oxide particles are dispersed in the nano-tube structure.
Further, the tubular carbon nanotube element includes C, H, O, B, N and metals Co and Zn.
Drawings
FIG. 1 is a diagram of a precursor and MOFs derived scanning electron microscope of the present invention;
FIG. 2 (a) is a graph showing the distribution of the real part ε' of dielectric loss;
FIG. 2 (b) is a plot of the imaginary part ε' of dielectric loss;
FIG. 2 (c) is a dielectric loss tangent distribution diagram;
FIG. 2 (d) is a graph showing the distribution of magnetic loss μ';
FIG. 2 (e) is a graph showing the distribution of magnetic loss μ';
FIG. 2 (f) is a graph showing the distribution of the magnetic loss tangent values;
FIG. 3 (a) is a reflection loss diagram of example 1;
FIG. 3 (b) is a reflection loss diagram of example 2;
FIG. 3 (c) is a reflection loss diagram of example 3;
FIG. 3 (d) is a three-dimensional plot of reflection loss as a function of frequency for different thicknesses of example 1;
FIG. 3 (e) is a three-dimensional plot of reflection loss as a function of frequency for different thicknesses of example 2;
Fig. 3 (f) is a three-dimensional plot of reflection loss as a function of frequency for different thicknesses of example 3.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The MOFs derivative/carbon nanotube material with electromagnetic wave absorbing performance is one kind of nanometer composite material with zeolite-imidazole salt skeleton (ZIF-8 and ZIF-67) embedded into boron-carbon nitride. Is prepared by a simple pyrolysis method. The invention comprises the following steps: firstly, synthesizing zeolite-imidazole salt skeleton precursor ZIFs, and mixing with BCN components consisting of urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature. Evaporating water in an oven through an evaporating dish, and finally calcining and carbonizing at high temperature in a tube furnace to obtain the composite material, namely the MOFs derivative material.
The method comprises the following specific steps:
(1) Preparation of Boron Carbon Nitride (BCN) nanotubes
Weighing 5g of urea, 0.5g of polyethylene glycol 2000 and 0.15g of boric acid, dissolving in 60mL of deionized water, stirring and dissolving uniformly, transferring to an evaporation dish, and drying in an oven at 80 ℃. And (3) placing the dried sample into a nitrogen tube furnace for calcining and carbonizing for 2 hours at 900 ℃, wherein the heating rate is 3 ℃/min, and obtaining black solid powder.
(2) Preparation of ZIF-8 and ZIF-67 precursors
0.297G of Zn (NO 3)2·6H2 O is dissolved in 60mL of deionized water to disperse the Zn into a uniform A solution, 0.657g of 2-methylimidazole is dissolved in 60mL of deionized water to disperse the Zn into a uniform B solution, the B solution is quickly poured into the A solution to be stirred for 12 hours at room temperature, and after centrifugation, washing with deionized water and ethanol for 3 times respectively, the mixture is put into a 70 ℃ oven to be dried, so that white solid powder ZIF-8 is obtained.
0.291G of Co (NO 3)2·6H2 O is dissolved in 60mL of deionized water to disperse the Co into a uniform C solution, 0.657g of 2-methylimidazole is respectively dissolved in 60mL of deionized water to disperse the Co into a uniform D solution, the D solution is rapidly poured into the C solution to be vigorously stirred for 10min, and after standing and ageing for 12h at room temperature, the mixture is centrifuged, washed with deionized water and ethanol for 3 times respectively and then dried in a 70 ℃ oven to obtain purple solid powder ZIF-67.
(3) Preparation of MOFs derived metal/metal oxide/BCN composite nanomaterial
65 To 130mg of ZIF-8 and 65 to 130mg of ZIF-67 prepared above are taken and added into a round bottom flask, and then 3 to 10g of urea, 0.1 to 1.0g of polyethylene glycol 2000, 0.05 to 0.3g of boric acid and 30 to 100ml of deionized water are added. Ultrasonic treatment is carried out for 5min to lead the mixture to be dispersed evenly, stirring is continued for 10min, then the mixture is transferred into an evaporating dish, the evaporating dish is put into an oven with the temperature of 80 ℃ for drying, and the product is scraped after the mixture is cooled to the room temperature. Finally, placing the mixture into a tube furnace for calcining and carbonizing for 2 hours at 900 ℃ under the protection of nitrogen, and heating at a rate of 3 ℃/min to obtain black solid powder. The electromagnetic absorption performance of the product can be regulated and controlled by changing the mass ratio of the added ZIF-8 to the ZIF-67.
As a part of the embodiment of the invention, a MOFs derivative material with electromagnetic wave absorption performance is also provided, and the MOFs derivative material is prepared by the preparation method, has a hollow tubular carbon nano tube structure, the tube diameter is 100-1000 nm, and metal oxide particles are dispersed in the nano tube structure. The elements of the nanotubes include C, H, O, B, N and metals Co, zn, etc. Preferably, the diameter of the tubular carbon nanotubes is about 500 nm.
Example 1:
0.297g of Zn (NO 3)2·6H2 O and 0.657g of 2-methylimidazole are respectively dissolved in 60mL of deionized water to disperse Zn (NO 3)2·6H2 O into a uniform A solution and 2-methylimidazole into a uniform B solution), the B solution is rapidly poured into the A solution and stirred for 12h at room temperature, and after centrifugation, washing with deionized water and ethanol respectively for 3 times, the mixture is put into a 70 ℃ oven to be dried, so that white solid powder ZIF-8 is obtained.
0.291G of Co (NO 3)2·6H2 O and 0.657g of 2-methylimidazole are respectively dissolved in 60mL of deionized water to disperse Co (NO 3)2·6H2 O into a uniform C solution and 2-methylimidazole into a uniform D solution), the D solution is rapidly poured into the C solution and vigorously stirred for 10min, and after standing and ageing for 12h at room temperature, the solution is centrifuged, washed with deionized water and ethanol for 3 times respectively and then put into a 70 ℃ oven to be dried, so that purple solid powder ZIF-67 is obtained.
Adding ZIF-865mg, ZIF-6765mg, urea 5g, polyethylene glycol 20000.5g and boric acid 0.15g into 60ml deionized water, ultrasonically dispersing for 5min, stirring for 10min, transferring to an evaporation dish, and drying the evaporation dish in an oven at 80 ℃. And (3) taking out the product after drying, and placing the product into a tube furnace for calcining and carbonizing at 900 ℃ at a heating rate of 3 ℃/min under the nitrogen atmosphere. After calcination, a black solid powder is obtained, denoted S1.
Example 2:
ZIF-8 and ZIF-67 precursors were prepared in the same manner as in example 1.
Adding ZIF-865mg, ZIF-67130mg, urea 5g, polyethylene glycol 20000.5g and boric acid 0.15g into 60ml deionized water, ultrasonically dispersing for 5min, stirring for 10min, transferring to an evaporation dish, and drying the evaporation dish in an oven at 80 ℃. And (3) taking out the product after drying, and placing the product into a tube furnace for calcining and carbonizing at 900 ℃ at a heating rate of 3 ℃/min under the nitrogen atmosphere. After calcination, a black solid powder is obtained, denoted S2.
Example 3:
ZIF-8 and ZIF-67 precursors were prepared in the same manner as in example 1.
Adding ZIF-8130mg, ZIF-6765mg, urea 5g, polyethylene glycol 20000.5g and boric acid 0.15g into 60ml deionized water, ultrasonically dispersing for 5min, stirring for 10min, transferring to an evaporation dish, and drying the evaporation dish in an oven at 80 ℃. And (3) taking out the product after drying, and placing the product into a tube furnace for calcining and carbonizing at 900 ℃ at a heating rate of 3 ℃/min under the nitrogen atmosphere. After calcination, a black solid powder is obtained, denoted S3.
FIG. 1 is a scanning electron microscope image of the precursor ZIF-8/ZIF-67/BCN and examples 1-3. Wherein the image (a) is a scanning electron microscope image of ZIF-8, and the appearance of the image is seen to be leaf-shaped; FIG. (b) is a scanning electron microscope image of ZIF-67, which has a similar appearance to that of FIG. (a) and is also leaf-shaped; the diagram (c) is a scanning electron microscope diagram of BCN, and the morphology of the diagram is hollow nano-tube shape; FIG. (d) is a scanning electron microscope image of example 1; FIG. (e) is a scanning electron microscope image of example 2; fig. (f) is a scanning electron microscope image of example 3.
Fig. 2 shows electromagnetic parameter diagrams of examples 1 to 3. Wherein graph (a) is a plot of the real part ε' of dielectric loss; FIG. (b) is a plot of the imaginary part ε' of dielectric loss; FIG. (c) is a dielectric loss tangent distribution diagram; graph (d) is a distribution diagram of magnetic loss μ'; FIG. (e) is a graph showing the distribution of magnetic loss μ'; the graph (f) shows the magnetic loss tangent distribution.
Fig. 3 is a graph of reflection loss for examples 1-3 and a three-dimensional graph of reflection loss as a function of frequency for different thicknesses. Wherein fig. (a) and (d) are a reflection loss map and a three-dimensional map of example 1; fig. (b) and (e) are a reflection loss map and a three-dimensional map of example 2; fig. (c) and (f) are a reflection loss map and a three-dimensional map of example 3.
Through the effect parameters, the MOFs derivative metal and oxide nano particles are well dispersed due to the boron carbon nitrogen nano tube, and the MOFs derivative metal and oxide nano particles are beneficial to efficiently utilizing the electric conduction loss and the magnetic loss. A rich heterogeneous interface is formed in the nanocomposite resulting in strong interfacial polarization effects and high dielectric loss capabilities. In addition, the one-dimensional boron carbon nitrogen nanotube microstructure and the low dielectric constant further optimize the impedance matching of the nanocomposite, thereby improving the electromagnetic wave absorption performance.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.
Claims (7)
1. The preparation method of the MOFs derivative material with the electromagnetic wave absorption performance is characterized by comprising the following steps of:
Firstly, synthesizing zeolite-imidazole salt skeleton precursors ZIFs, wherein the zeolite-imidazole salt skeleton precursors comprise ZIF-8 and ZIF-67 precursors; under the condition of room temperature, 65-130 mg of ZIF-8 and 65-130 mg of ZIF-67 are taken and added into a round-bottomed flask, 3-10 g of urea, 0.1-1.0 g of polyethylene glycol 2000, 0.05-0.3 g of boric acid and 30-100 ml of deionized water are added, stirring is continued after uniform dispersion, the mixture is transferred into an evaporating dish, the evaporating dish is put into an oven at 80 ℃ for drying, the product is scraped after cooling to room temperature, and finally the product is put into a tube furnace for calcination and carbonization at 800-1000 ℃ under the protection of nitrogen, so that black solid powder which is the MOFs derivative material is obtained.
2. The method for preparing MOFs derivative materials having electromagnetic wave absorbing properties according to claim 1, wherein the temperature of calcination and carbonization in a tube furnace under nitrogen protection is 900 ℃.
3. The method for preparing MOFs derived materials having electromagnetic wave absorbing properties according to claim 1, wherein the heating rate of calcination and carbonization in a tube furnace is 3 ℃/min under the protection of nitrogen.
4. The method for preparing MOFs derived materials having electromagnetic wave absorbing properties according to claim 1, wherein the preparation of ZIF-8 and ZIF-67 precursors comprises the steps of:
Weighing 0.297 g Zn (NO 3)2•6H2 O is dissolved in 60 mL deionized water to be dispersed into uniform A solution, weighing 0.657 g of 2-methylimidazole is dissolved in 60 mL deionized water to be dispersed into uniform B solution, rapidly pouring the B solution into the A solution, stirring at room temperature for 12h, centrifuging, washing, and drying in an oven to obtain white solid powder ZIF-8;
0.291 g Co (NO 3)2•6H2 O is dissolved in 60 mL deionized water to be dispersed into uniform C solution, 0.657 g of 2-methylimidazole is dissolved in 60 mL deionized water to be dispersed into uniform D solution, the D solution is rapidly poured into the C solution to be vigorously stirred for 10min, and after standing and ageing for 12 h at room temperature, the solution is centrifuged and washed, and then dried in an oven to obtain purple solid powder ZIF-67.
5. The method for preparing MOFs derivative material with electromagnetic wave absorption performance according to claim 4, wherein in the preparation of ZIF-8 and ZIF-67 precursors, deionized water and ethanol are used for washing, and the washed materials are put into a 70 ℃ oven for drying.
6. The MOFs derivative material with electromagnetic wave absorption performance is characterized in that the MOFs derivative material is prepared by the preparation method of any one of claims 1 to 5, the MOFs derivative material is in a hollow tubular carbon nano tube structure, the tube diameter is 100-1000 nm, and metal oxide particles are dispersed in the nano tube structure.
7. The MOFs derivative material having electromagnetic wave absorbing property according to claim 6, wherein the tubular carbon nanotube element comprises C, H, O, B, N and metals Co, zn.
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| KR20190009541A (en) * | 2017-07-19 | 2019-01-29 | 한양대학교 산학협력단 | Novel nanocomposite and preparation method thereof |
| CN112357907A (en) * | 2020-10-21 | 2021-02-12 | 同济大学 | Amorphous boron-nitrogen co-doped carbon nanotube and preparation method and application thereof |
| CN114477308A (en) * | 2022-02-18 | 2022-05-13 | 江西虔悦新材料有限公司 | MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof |
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| CN112357907A (en) * | 2020-10-21 | 2021-02-12 | 同济大学 | Amorphous boron-nitrogen co-doped carbon nanotube and preparation method and application thereof |
| CN114477308A (en) * | 2022-02-18 | 2022-05-13 | 江西虔悦新材料有限公司 | MOFs derivative double-layer coated manganese ferrite wave-absorbing material and preparation method and application thereof |
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