CN115716641A - MOFs derivative material with electromagnetic wave absorption performance and preparation method thereof - Google Patents
MOFs derivative material with electromagnetic wave absorption performance and preparation method thereof Download PDFInfo
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Abstract
The invention provides a MOFs derivative material with electromagnetic wave absorption performance and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, synthesizing a zeolite-imidazolium framework precursor ZIFs; mixing the mixture with boron carbon nitrogen nano-tubes consisting of urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature, and evaporating water in an oven through an evaporating dish; finally calcining and carbonizing at the environment of 800-1000 ℃ to obtain the MOFs derivative material. Due to the existence of the boron carbon nitrogen nano tube, good dispersion can be realized, rich non-uniform interfaces are formed in the nano composite material, the nano composite material has strong interface polarization effect and high dielectric loss capability, the impedance matching of the nano composite material is further optimized by the one-dimensional boron carbon nitrogen nano tube microstructure and the low dielectric constant, and the 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 prospects.
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, the electromagnetic radiation or pollution generated by the electronic industry is more and more harmful to the normal operation of electronic devices and the health of human beings, and the attention of more and more researchers is attracted. The requirements for absorbing materials capable of absorbing and attenuating electromagnetic radiation are high. An 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 organic ligands and centered metal ions or clusters. The MOFs-derived carbon/metal composite material with large specific surface area, porous structure and component variability can be prepared by a simple carbonization process, and shows excellent electromagnetic absorption performance. However, the preparation and mass production costs of the carbonaceous materials are high, and large-scale application is difficult to a certain extent; the preparation conditions of the magnetic material are difficult to quantify and the requirement of light weight cannot be met. The development of new materials is still highly desired. Achieving good impedance matching of MOFs-derived absorbers remains a significant challenge due to the high dielectric constant of the material itself, inevitably resulting in an imbalance in impedance matching that affects the electromagnetic absorption properties of the absorber. Furthermore, the inevitable severe agglomeration of MOFs derived absorbents prevents the full utilization of the microstructure in practical applications. Therefore, how to prepare the MOFs-derived materials with better wave absorption performance is a problem to be solved in the field.
Disclosure of Invention
In view of the above, the present invention is directed to a MOFs-derived material with electromagnetic wave absorption capability and a method for preparing the same, so as to solve the above-mentioned problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of MOFs derivative materials with electromagnetic wave absorption performance comprises the following steps:
firstly, synthesizing a zeolite-imidazolium salt framework precursor ZIFs; mixing the carbon-nitrogen-boron nanotube with urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature, and evaporating water in an oven through an evaporating dish; finally calcining and carbonizing at the environment of 800-1000 ℃ to obtain the MOFs derivative material. The metal/metal oxide derived from MOFs is embedded into the boron carbon nitrogen nanotube, so that the metal/metal oxide nanoparticles derived from MOFs realize satisfactory dispersion, and the conductive loss and the magnetic loss derived from MOFs are effectively utilized.
Further, zeolite-imidazolium salt framework precursors include ZIF-8 and ZIF-67 precursors.
Further, the preparation of the MOFs derivative material comprises the following steps:
adding 65-130 mg of ZIF-8 and 65-130 mg of ZIF-67 into a round-bottom flask, then adding 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, continuously stirring after uniform dispersion, transferring to an evaporation dish, drying in an oven at 80 ℃, scraping the product after cooling to room temperature, and finally calcining and carbonizing in a tubular furnace under the protection of nitrogen to obtain black solid powder, namely the MOFs derivative material.
Further, the temperature for calcining and carbonizing the mixture in a tubular furnace under the protection of nitrogen is 900 ℃.
Further, the heating rate of calcination and carbonization in a tubular 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 Zn (NO) was weighed out 3 ) 2 ·6H 2 Dissolving O in 60mL deionized water, dispersing into uniform solution A, dissolving 0.657g 2-methylimidazole in 60mL deionized water, dispersing into uniform solution B, rapidly pouring solution B into solution A, stirring at room temperature for 12 hr, centrifugingWashing and then drying in an oven to obtain white solid powder ZIF-8;
weigh 0.291g Co (NO) 3 ) 2 ·6H 2 Dissolving O in 60mL of deionized water to disperse the O into a uniform solution C, weighing 0.657g of 2-methylimidazole, respectively dissolving in 60mL of deionized water to disperse the solution C into a uniform solution D, quickly pouring the solution D into the solution C, violently stirring for 10min, standing and aging at room temperature for 12h, centrifuging, washing, and drying in an oven to obtain purple solid powder ZIF-67.
Furthermore, in the preparation of the precursors of ZIF-8 and ZIF-67, deionized water and ethanol are adopted for washing, and after washing, the washed precursors 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 evaporating dish, drying in an oven at 80 ℃, putting the dried sample into a nitrogen tube furnace, calcining and carbonizing at 900 ℃ for 2h at the heating rate of 3 ℃/min, and obtaining black solid powder, namely the boron carbon nitrogen nanotube BCN.
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 nano-tube, the metal and metal oxide nano-particles can realize good dispersion, and the conductive loss and the magnetic loss derived from the MOFs derivatives can be effectively utilized. The nano composite material forms rich non-uniform interfaces, resulting in strong interface polarization effect and high dielectric loss capability. In addition, the one-dimensional boron carbon nitrogen nanotube microstructure and the low dielectric constant further optimize the impedance matching of the nano composite material, so that the electromagnetic wave absorption performance is improved. The preparation method provided by the invention is convenient to operate, simple in process and low in cost, can be used for preparing the electromagnetic wave absorbent with strong absorption, wide frequency band, thin thickness, light weight and high performance, and has good development and application prospects.
Under the condition of low filling ratio of 20wt%, the effective absorption bandwidth of the synthesized composite material can reach 4.24GHz, the minimum reflection loss at 16.7GHz can reach-54.4 dB, and the thickness of the composite material is only 1.8mm. The research result has the wave-absorbing performance of strong absorption, wide frequency band, thin thickness and light weight, and has wide application market.
The invention also provides the MOFs derivative material with electromagnetic wave absorption performance, which is prepared by the preparation method, the shape of the MOFs derivative material is a hollow tubular carbon nanotube structure, the tube diameter is 100-1000 nm, and metal oxide particles are dispersed in the nanotube structure.
Furthermore, the tubular carbon nanotube elements comprise C, H, O, B, N, metal Co and metal Zn.
Drawings
FIG. 1 is a scanning electron microscope image derived from precursors and MOFs according to the present invention;
FIG. 2 (a) is a graph showing a distribution of the real part ε' of dielectric loss;
FIG. 2 (b) is a graph of the imaginary part ε' of dielectric loss;
FIG. 2 (c) is a diagram showing a dielectric loss tangent distribution;
FIG. 2 (d) is a graph of magnetic loss μ';
FIG. 2 (e) is a graph of the magnetic loss μ ";
FIG. 2 (f) is a magnetic loss tangent distribution diagram;
FIG. 3 (a) is a reflection loss chart of example 1;
FIG. 3 (b) is a reflection loss graph of example 2;
FIG. 3 (c) is a reflection loss chart of example 3;
FIG. 3 (d) is a three-dimensional graph of reflection loss as a function of frequency for different thicknesses of example 1;
FIG. 3 (e) is a three-dimensional graph of reflection loss as a function of frequency for different thicknesses of example 2;
FIG. 3 (f) is a three-dimensional graph of reflection loss as a function of frequency for different thicknesses of example 3.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
A MOFs derivative/carbon nanotube material with electromagnetic wave absorption performance is prepared by embedding zeolite-imidazolium salt frameworks (ZIF-8 and ZIF-67) into boron carbonitride to prepare a nanocomposite. Prepared by a simple pyrolysis method. The invention comprises the following steps: firstly, synthesizing a zeolite-imidazolium salt framework precursor ZIFs, and mixing the ZIFs with a BCN component consisting of urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature. Evaporating water in the oven through the evaporating dish, and finally calcining and carbonizing at high temperature in the tubular 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
5g of urea, 0.5g of polyethylene glycol 2000 and 0.15g of boric acid are weighed and dissolved in 60mL of deionized water, stirred and dissolved uniformly, transferred to an evaporating dish and placed in an oven at 80 ℃ for drying. And (3) putting the dried sample into a nitrogen tube furnace, calcining and carbonizing at 900 ℃ for 2h at the heating rate of 3 ℃/min, and obtaining black solid powder.
(2) Preparation of ZIF-8 and ZIF-67 precursors
0.297g of Zn (NO) was weighed 3 ) 2 ·6H 2 O was dissolved in 60mL of deionized water to disperse it to a uniform solution A, and 0.657g of 2-methylimidazole was weighed and dissolved in 60mL of deionized water to disperse it to a uniform solution B. And quickly pouring the solution B into the solution A, stirring for 12h at room temperature, centrifuging, washing with deionized water and ethanol for 3 times respectively, and drying in a 70 ℃ oven to obtain white solid powder ZIF-8.
0.291g of Co (NO) was weighed 3 ) 2 ·6H 2 O was dissolved in 60mL of deionized water to disperse it into a uniform solution C, and 0.657g of 2-methylimidazole was weighed and dissolved in 60mL of deionized water, respectively, to disperse it into a uniform solution D. And rapidly pouring the solution D into the solution C, violently stirring for 10min, standing and aging for 12h at room temperature, centrifuging, respectively washing for 3 times by using deionized water and ethanol, and drying in a 70 ℃ drying oven to obtain purple solid powder ZIF-67.
(3) Preparation of MOFs derived metal/metal oxide/BCN composite nano material
65-130 mg of the prepared ZIF-8 and 65-130 mg of the prepared ZIF-67 are added into a round-bottom flask, and then 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. And (4) performing ultrasonic treatment for 5min to uniformly disperse the mixture, continuously stirring for 10min, transferring the mixture to an evaporating dish, putting the evaporating dish into an oven at 80 ℃ for drying, and scraping the product after cooling to room temperature. And finally, calcining and carbonizing the mixture for 2 hours at 900 ℃ in a tubular furnace under the protection of nitrogen, wherein the heating rate is 3 ℃/min, and obtaining black solid powder. The regulation and control of the electromagnetic absorption performance of the product can be realized by changing the mass ratio of the added ZIF-8 to the ZIF-67.
The MOFs derivative material is in a hollow tubular carbon nanotube structure, the pipe diameter is 100-1000 nm, and metal oxide particles are dispersed in the nanotube structure. The elements of the nanotube comprise C, H, O, B, N, metal Co, zn and the like. Preferably, the tube diameter of the tubular carbon nanotube is about 500 nm.
Example 1:
0.297g of Zn (NO) was weighed 3 ) 2 ·6H 2 Dissolving O and 0.657g 2-methylimidazole in 60mL deionized water respectively to obtain Zn (NO) 3 ) 2 ·6H 2 Dispersing O into a uniform solution A, dispersing 2-methylimidazole into a uniform solution B, quickly pouring the solution B into the solution A, stirring for 12 hours at room temperature, centrifuging, washing with deionized water and ethanol for 3 times respectively, and drying in an oven at 70 ℃ to obtain white solid powder ZIF-8.
0.291g of Co (NO) was weighed 3 ) 2 ·6H 2 O and 0.657g of 2-methylimidazole were dissolved in 60mL of deionized water to obtain Co (NO) 3 ) 2 ·6H 2 Dispersing O into a uniform C solution, dispersing 2-methylimidazole into a uniform D solution, quickly pouring the D solution into the C solution, violently stirring for 10min, standing and aging for 12h at room temperature, centrifuging, washing with deionized water and ethanol for 3 times respectively, and drying in an oven at 70 ℃ to obtain the purple solid powder ZIF-67.
60ml of deionized water is added into ZIF-865mg, ZIF-6765mg, 5g of urea, 20000.5g of polyethylene glycol and 0.15g of boric acid, the mixture is stirred for 10min after 5min of ultrasonic dispersion and then transferred to an evaporation pan, and the evaporation pan is placed into an oven at 80 ℃ for drying. And taking out the dried product, putting the product into a tubular furnace in the nitrogen atmosphere for calcining and carbonizing, wherein the carbonizing temperature is 900 ℃, and the heating rate is 3 ℃/min. Calcination gave a black solid powder, designated S1.
Example 2:
ZIF-8 and ZIF-67 precursors were prepared in the same manner as in example 1.
Adding 60ml of deionized water into ZIF-865mg, ZIF-67130mg, 5g of urea, 20000.5g of polyethylene glycol and 0.15g of boric acid, ultrasonically dispersing for 5min, stirring for 10min, transferring to an evaporation pan, and drying the evaporation pan in an oven at 80 ℃. And taking out the dried product, and putting the product into a tubular furnace in nitrogen atmosphere for calcining and carbonizing, wherein the carbonizing temperature is 900 ℃, and the heating rate is 3 ℃/min. Calcination gave a black solid powder, labeled S2.
Example 3:
ZIF-8 and ZIF-67 precursors were prepared in the same manner as in example 1.
Adding 60ml of deionized water into ZIF-8130mg, ZIF-6765mg, 5g of urea, 20000.5g of polyethylene glycol and 0.15g of boric acid, ultrasonically dispersing for 5min, stirring for 10min, transferring to an evaporation pan, and drying the evaporation pan in an oven at 80 ℃. And taking out the dried product, putting the product into a tubular furnace in the nitrogen atmosphere for calcining and carbonizing, wherein the carbonizing temperature is 900 ℃, and the heating rate is 3 ℃/min. Calcination gave a black solid powder, designated S3.
FIG. 1 scanning electron micrographs of the precursor ZIF-8/ZIF-67/BCN and examples 1-3. Wherein, the picture (a) is a scanning electron microscope picture of ZIF-8, and the appearance of the picture is leaf-shaped; FIG. (b) is a scanning electron micrograph of ZIF-67, which is similar in morphology to FIG. (a) and is leaf-like; the figure (c) is a scanning electron microscope image of BCN, and the appearance of the BCN is in a hollow nano tube shape; FIG. (d) is a SEM image of example 1; FIG. (e) is a SEM image of example 2; FIG. (f) is a SEM image of example 3.
FIG. 2 is an electromagnetic parameter chart of examples 1 to 3. Wherein the graph (a) is a distribution diagram of the real part ε' of dielectric loss; plot (b) is a distribution plot of the imaginary part ε' of dielectric losses; FIG. (c) is a dielectric loss tangent distribution diagram; FIG. (d) is a distribution diagram of magnetic loss μ'; FIG. (e) is a graph of magnetic loss μ "; FIG. f is a magnetic loss tangent distribution diagram.
Fig. 3 reflection loss plots for examples 1-3 and three-dimensional plots of reflection loss versus frequency for different thicknesses. Wherein graphs (a) and (d) are a reflection loss graph and a three-dimensional graph of example 1; FIGS. (b) and (e) are a reflection loss graph and a three-dimensional graph of example 2; fig. (c) and (f) are a reflection loss diagram and a three-dimensional diagram of example 3.
The effect parameters show that the metal and oxide nanoparticles derived from MOFs realize good dispersion due to the existence of boron carbon nitrogen nanotubes, and are beneficial to efficiently utilizing the conduction loss and the magnetic loss derived from the MOF derivatives. The nano composite material forms rich non-uniform interfaces, resulting in strong interface polarization effect and high dielectric loss capability. In addition, the one-dimensional boron carbon nitrogen nanotube microstructure and the low dielectric constant further optimize the impedance matching of the nano composite material, so that the electromagnetic wave absorption performance is improved.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of MOFs derivative materials with electromagnetic wave absorption performance is characterized by comprising the following steps:
firstly, synthesizing a zeolite-imidazolium framework precursor ZIFs; mixing the carbon-nitrogen-boron nanotube with urea, polyethylene glycol 2000 and boric acid in deionized water at room temperature, and evaporating water in an oven through an evaporating dish; finally calcining and carbonizing at the environment of 800-1000 ℃ to obtain the MOFs derivative material.
2. The method for preparing MOFs derivative materials having electromagnetic wave absorption properties according to claim 1, wherein said zeolite-imidazolium salt framework precursor comprises ZIF-8 and ZIF-67 precursors.
3. The method for preparing MOFs derivative materials having electromagnetic wave absorption property according to claim 2, wherein the preparation of MOFs derivative materials comprises the following steps:
adding 65-130 mg of ZIF-8 and 65-130 mg of ZIF-67 into a round-bottom flask, then adding 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, continuously stirring after uniform dispersion, transferring to an evaporation dish, drying in an oven at 80 ℃, scraping the product after cooling to room temperature, and finally calcining and carbonizing in a tubular furnace under the protection of nitrogen to obtain black solid powder, namely the MOFs derivative material.
4. The method for preparing MOFs derivative materials having electromagnetic wave absorption properties according to claim 3, wherein the calcination and carbonization temperature in a tubular furnace under the protection of nitrogen is 900 ℃.
5. The method for preparing MOFs derivative materials having electromagnetic wave absorption property according to claim 3, wherein the temperature rise rate of calcination and carbonization in a tubular furnace under the protection of nitrogen is 3 ℃/min.
6. The method for preparing MOFs derivative materials having electromagnetic wave absorption properties according to claim 2, wherein the preparation of the ZIF-8 and ZIF-67 precursors comprises the following steps:
0.297g Zn (NO) was weighed out 3 ) 2 ·6H 2 Dissolving O in 60mL of deionized water to disperse the O into a uniform solution A, weighing 0.657g of 2-methylimidazole, dissolving the 2-methylimidazole in 60mL of deionized water to disperse the solution A into a uniform solution B, quickly pouring the solution B into the solution A, stirring at room temperature for 12 hours, centrifuging, washing, and drying in an oven to obtain white solid powder ZIF-8;
0.291g of Co (NO) was weighed 3 ) 2 ·6H 2 Dissolving O in 60mL deionized water, dispersing into uniform solution C, dissolving 0.657g 2-methylimidazole in 60mL deionized water, dispersing into uniform solution D, rapidly pouring solution D into solution C, stirring vigorously for 10min,standing and aging for 12h at room temperature, centrifuging, washing, and drying in an oven to obtain purple solid powder ZIF-67.
7. The method for preparing MOFs derivative materials having electromagnetic wave absorption property according to claim 6, wherein in the preparation of the ZIF-8 and ZIF-67 precursors, deionized water and ethanol are adopted for washing, and after washing, the precursors are placed in an oven at 70 ℃ for drying.
8. The preparation method of the MOFs derivative materials with electromagnetic wave absorption property according to claim 1, wherein 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 evaporating dish, drying in an oven at 80 ℃, putting the dried sample into a nitrogen tube furnace, calcining and carbonizing at 900 ℃ for 2h at the heating rate of 3 ℃/min, and obtaining black solid powder, namely the boron carbon nitrogen nanotube BCN.
9. A MOFs derivative material with electromagnetic wave absorption performance is characterized by being prepared by using the preparation method of any one of claims 1 to 8, the shape of the MOFs derivative material is a hollow tubular carbon nanotube structure, the tube diameter is 100-1000 nm, and metal oxide particles are dispersed in the nanotube structure.
10. The MOFs derivative material having electromagnetic wave absorption properties according to claim 9, wherein the tubular carbon nanotube elements comprise C, H, O, B, N and metals of Co and Zn.
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| US20160101192A1 (en) * | 2014-10-08 | 2016-04-14 | Commissariat A L'energie Atomique Et Aux Energies Alternative (Cea) | Porous solid with outer surface grafted with a polymer |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160101192A1 (en) * | 2014-10-08 | 2016-04-14 | Commissariat A L'energie Atomique Et Aux Energies Alternative (Cea) | Porous solid with outer surface grafted with a polymer |
| 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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