CN113060731A - Preparation method and application of ternary metal carbonized MOFs material - Google Patents
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Abstract
A preparation method and application of ternary metal carbonized MOFs materials relate to a preparation method and application of carbonized MOFs materials. The invention aims to solve the problems that the existing MOFs material is mainly doped with unitary or binary metals or oxides, the application is limited and the electromagnetic wave absorption effect is poor. The method comprises the following steps: firstly, preparing NiCo-MOFs material; secondly, preparing a NiCo/Zif-8 precursor; and thirdly, calcining to obtain the ternary metal carbonized MOFs material. The ternary metal carbonized MOFs material prepared by the method has a rod-shaped structure, the width of the material is about 800nm, the size is uniform, the dispersibility is good, and the agglomeration phenomenon is avoided. The invention can obtain the ternary metal carbonized MOFs material.
Description
Technical Field
The invention relates to a preparation method and application of a carbonized MOFs material.
Background
Metal Organic Frameworks (MOFs) materials are novel materials formed by linking metal ions and organic ligands. The catalyst has the characteristics of regular spatial structure, high porosity, large specific surface area, magnetism, light weight, conductivity and the like, and has wide application prospects in multiple fields of catalysis, gas storage and separation, drug loading, electromagnetic wave absorption and the like. And the MOFs material after high-temperature pyrolysis forms a carbonized material loaded with magnetic metal nanoparticles, so that the obtained product has higher saturation magnetization and good characteristics in the aspect of electromagnetic wave absorption performance.
The main doped metals in the currently synthesized metal organic carbonized MOFs material include Fe, Co, Ni, Zn, Zr and the like. Such as: chinese patent "a cobalt MOFs electromagnetic wave absorber and a preparation method thereof" (publication number: CN109757091A) synthesizes MOFs precursor by using cobalt salt as a metal source, and carries out high-temperature pyrolysis under the protection of inert gas to prepare the electromagnetic wave absorbent with a one-dimensional rod-shaped structure. The synthesized product has high magnetic conductivity and strong loss performance. Chinese patent "a method for synthesizing carbonized MOFs by solvothermal method" (publication number: CN106957441A) synthesizes a metal-organic framework structure by using iron salt and an organic ligand, and forms a carbonized derivative material by high-temperature calcination. The synthesized material has low cost and simple process. Chinese patent "a method for preparing NiCo-based MOFs material by hydrothermal method" (publication number: CN109166733A) takes nickel salt or cobalt salt, terephthalic acid and N, N-dimethylformamide as reactants, and spherical and lamellar MOFs material is prepared by adjusting reaction conditions under hydrothermal conditions. Chinese patent "MOFs-based carbon-coated ZnO core-shell structure nano material and preparation method thereof" (publication number: CN108786781A) firstly synthesizes zinc oxide by using zinc acetate and diethylene glycol, then prepares ZnO core-shell structure particles by using dimethylimidazole and ZnO, and then calcines the particles to obtain the carbon-coated ZnO nano material. The patent provides a method for coating ZnO by MOFs materials, and the materials have higher pyrolysis temperature. With the progress of research, researchers have been working on the development of carbonized microspheres in which a plurality of metals coexist to improve the properties of products. Such as: in Chinese patent, namely a method and a process for preparing Ni/Co-based MOF material by a hydrothermal method (publication number: CN109166733A), cobalt salt and nickel salt are added into an organic solvent according to a certain proportion, the mixture is transferred to a reaction kettle after being fully dissolved, the Ni/Co-based MOF material is obtained through hydrothermal reaction, and the electrochemical performance of the Ni/Co-based MOF material is analyzed. MOFs materials with different properties are obtained by adjusting different raw material ratios and reaction temperatures. Chinese patent "preparation method of MOFs Nano-materials supporting Nano-Metal particles" (publication number: CN108097316A) synthesizes ZiF-8 materials by using dimethylimidazole and zinc nitrate as reactants, and then disperses nanoparticles in dimethylimidazole and cobalt nitrate, dimethylimidazole and zinc nitrate solutions respectively to form the sandwich MOFs materials. The material improves the dispersibility and selectivity of ZiF-8 particles.
In summary, there are many patents on MOFs, but most of them are still in the synthesis of individual MOFs precursors or in the preparation of carbonized materials. Application patents of the actual MOFs materials in the field of electromagnetic wave absorption are rare, and unitary or binary metals or oxides are mainly doped, so that the actual application value of the final product has certain limitation.
Disclosure of Invention
The invention aims to solve the problems that the existing MOFs material is mainly doped with unitary and binary metals or oxides, the application is limited and the electromagnetic wave absorption effect is poor, and provides a preparation method and application of a ternary metal carbonized MOFs material.
A preparation method of ternary metal carbonized MOFs material is completed according to the following steps:
firstly, preparing NiCo-MOFs materials:
dissolving terephthalic acid in N, N-dimethylformamide to obtain a terephthalic acid/N, N-dimethylformamide solution;
secondly, adding cobalt salt and nickel salt into a terephthalic acid/N, N-dimethylformamide solution, and performing ultrasonic treatment to obtain a mixed solution I; transferring the mixed solution I into a hydrothermal reaction kettle, and carrying out hydrothermal reaction to obtain a reaction product I;
thirdly, cooling the reaction product I to room temperature, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying to obtain a NiCo-MOFs material;
secondly, preparing a NiCo/Zif-8 precursor:
firstly, dispersing NiCo-MOFs materials into methanol to obtain a NiCo-MOFs material/methanol solution;
② Zn (NO)3)2Adding dimethylimidazole and NiCo-MOFs material/methanol solution to obtain a mixed solution II;
thirdly, stirring the mixed solution II for 30-90 min under the heating condition, cooling to room temperature, finally centrifuging, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying to obtain a NiCo/Zif-8 precursor;
thirdly, calcining:
transferring the NiCo/Zif-8 precursor into a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 400-600 ℃ under the protection of the inert gas, and calcining at 400-600 ℃ to obtain the NiCo/ZnO carbonized material, namely the ternary metal carbonized MOFs material.
The principle and the advantages of the invention are as follows:
firstly, synthesizing a MOFs material precursor with a core-shell structure, and calcining at high temperature to form a NiCo/ZnO carbonized material with Ni and Co/C as cores and ZnO/C as shells, namely the ternary metal carbonized MOFs material;
secondly, the thickness of the core shell can be controlled by regulating and controlling conditions for the ternary metal/carbonized material obtained by a hydrothermal method and high-temperature carbonization;
the ternary metal carbonized MOFs material prepared by the method is doped with nickel and cobalt metals with good electrical property, so that the material has the characteristics of high magnetic conductivity, strong loss capacity and the like;
in the ternary metal carbonized MOFs material prepared by the method, ZnO is used as a green channel, the dielectric constant is reduced by compounding the ZnO, the entrance amount and the electromagnetic matching degree of incident waves are improved, and the ZnO and the internal metal material have synergistic effect so as to optimize the electromagnetic wave absorption effect;
fifthly, the ternary metal carbonized MOFs material prepared by the method is of a rod-shaped structure, the width is about 800nm, the size is uniform, the dispersibility is good, and the agglomeration phenomenon is avoided;
the invention synthesizes a one-dimensional magnetic rod-shaped material with microwave absorption performance through simple raw materials, a ZnO/C layer provides an effective path for electron transmission, and the ZnO/C layer and an internal NiCo/C material jointly act, so that the matching degree of electric loss and magnetic loss is improved, the electromagnetic wave absorption performance of the material is enhanced, and the problem that the single metal MOFs carbonized material is limited in the field of electromagnetic wave absorption is effectively solved.
The invention can obtain the ternary metal carbonized MOFs material.
Drawings
FIG. 1 is a transmission electron microscope image of the ternary metal carbonized MOFs material prepared in example 1;
FIG. 2 is an XRD pattern of the ternary metal carbonized MOFs material prepared in example 1;
FIG. 3 is an electromagnetic wave absorption diagram of samples with different thicknesses, wherein 10% of the mass of the sample is the ternary metal carbonized MOFs material prepared in example 1, and 90% of the mass of the sample is paraffin.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the preparation method of the ternary metal carbonized MOFs material is completed according to the following steps:
firstly, preparing NiCo-MOFs materials:
dissolving terephthalic acid in N, N-dimethylformamide to obtain a terephthalic acid/N, N-dimethylformamide solution;
secondly, adding cobalt salt and nickel salt into a terephthalic acid/N, N-dimethylformamide solution, and performing ultrasonic treatment to obtain a mixed solution I; transferring the mixed solution I into a hydrothermal reaction kettle, and carrying out hydrothermal reaction to obtain a reaction product I;
thirdly, cooling the reaction product I to room temperature, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying to obtain a NiCo-MOFs material;
secondly, preparing a NiCo/Zif-8 precursor:
firstly, dispersing NiCo-MOFs materials into methanol to obtain a NiCo-MOFs material/methanol solution;
② Zn (NO)3)2Adding dimethylimidazole and NiCo-MOFs material/methanol solution to obtain a mixed solution II;
thirdly, stirring the mixed solution II for 30-90 min under the heating condition, cooling to room temperature, finally centrifuging, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying to obtain a NiCo/Zif-8 precursor;
thirdly, calcining:
transferring the NiCo/Zif-8 precursor into a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 400-600 ℃ under the protection of the inert gas, and calcining at 400-600 ℃ to obtain the NiCo/ZnO carbonized material, namely the ternary metal carbonized MOFs material.
The principle and advantages of the embodiment are as follows:
firstly, synthesizing a MOFs material precursor with a core-shell structure, and calcining at high temperature to form a NiCo/ZnO carbonized material with Ni and Co/C as cores and ZnO/C as shells, namely the ternary metal carbonized MOFs material;
secondly, the thickness of the core shell can be controlled by regulating and controlling conditions for the ternary metal/carbonized material obtained by a hydrothermal method and high-temperature carbonization;
third, the ternary metal carbonized MOFs material prepared by the embodiment is doped with nickel and cobalt metals with good electrical property, so that the material has the characteristics of high magnetic conductivity, strong loss capacity and the like;
in the ternary metal carbonized MOFs material prepared by the embodiment, ZnO is used as a green channel, the dielectric constant is reduced by compounding the ZnO, the incoming amount and the electromagnetic matching degree of incident waves are improved, and the ZnO and the internal metal material have synergistic effect so as to optimize the electromagnetic wave absorption effect;
fifthly, the ternary metal carbonized MOFs material prepared by the embodiment has a rod-like structure, the width of about 800nm, uniform size, good dispersibility and no agglomeration phenomenon;
the cost of the raw materials such as cobalt nitrate, nickel nitrate, zinc nitrate, terephthalic acid and the like is low, the one-dimensional magnetic rod-shaped material with microwave absorption performance is synthesized by simple raw materials, the ZnO/C layer provides an effective path for electron transmission and is combined with an internal NiCo/C material, and the matching degree of electric loss and magnetic loss is improved, so that the electromagnetic wave absorption performance of the material is enhanced, and the problem that the single metal MOFs carbonized material is limited in the field of electromagnetic wave absorption is effectively solved.
The embodiment can obtain the ternary metal carbonized MOFs material.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the mass fraction of the terephthalic acid in the phthalic acid/N, N-dimethylformamide solution in the first step is 10-50%; the cobalt salt in the first step is Co (NO)3)2.6H2O; the nickel salt in the first step is Ni (NO)3)2.6H2And O. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the molar ratio of the cobalt salt to the nickel salt in the first step is (1-10) to 1; the volume ratio of the nickel salt substance in the first step to the terephthalic acid/N, N-dimethylformamide solution is 1mol (3000 mL-5000 mL); the power of the ultrasound in the first step is 100W-300W, and the ultrasound time is 1 min-3 min. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the temperature of the hydrothermal reaction in the first step is 140-180 ℃, and the time of the hydrothermal reaction is 18-24 h. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the centrifugal cleaning in the step one is to use absolute ethyl alcohol as a cleaning agent, the volume ratio of the absolute ethyl alcohol to the collected lower-layer solid is 1:10, the centrifugal cleaning is carried out at the centrifugal speed of 3000 r/min-5000 r/min, the centrifugal cleaning frequency is 3-5 times, and the centrifugal cleaning time is 4-8 min each time; the drying temperature in the step one is 70-90 ℃, and the drying time is 8-12 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the mass ratio of the NiCo-MOFs material to the methanol in the second step is 1 (100-500); step two, Zn (NO) in the mixed solution II3)2The mass fraction of (A) is 1-20%; and in the second step, the mass fraction of the dimethyl imidazole in the mixed solution II is 1-20%. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the second step, the mixed solution II is transferred into a round-bottom flask, heated to 50-80 ℃, and stirred for 30-90 min under the conditions that the temperature is 50-80 ℃ and the stirring speed is 100-300 r/min. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the centrifugal cleaning in the second step is to use absolute ethyl alcohol as a cleaning agent, the volume ratio of the absolute ethyl alcohol to the collected lower-layer solid is 1:10, the centrifugal cleaning is carried out at the centrifugal speed of 3000 r/min-5000 r/min, the centrifugal cleaning frequency is 3-5 times, and the centrifugal cleaning time is 4-8 min each time; the drying temperature in the second step is 70-90 ℃, and the drying time is 8-12 h. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: in the third step, the tubular furnace is heated to 400-600 ℃ from room temperature at the heating rate of 1-20 ℃/min under the protection of inert gas, calcined for 1-2 h, and then kept at 400-600 ℃ for 1-5 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that the ternary metal carbonized MOFs material is used for absorbing electromagnetic waves.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of ternary metal carbonized MOFs material is completed according to the following steps:
firstly, preparing NiCo-MOFs materials:
dissolving 0.01mol of terephthalic acid in 33mL of N, N-dimethylformamide to obtain a terephthalic acid/N, N-dimethylformamide solution;
②, 2.909g of Co (NO)3)2.6H2O and 2.907g Ni (NO)3)2.6H2Adding O into the terephthalic acid/N, N-dimethylformamide solution obtained in the first step, and then carrying out ultrasonic treatment for 3min under the ultrasonic power of 100W to obtain a mixed solution I; transferring the mixed solution I into a 100mL hydrothermal reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 20h to obtain a reaction product I;
thirdly, cooling the reaction product I to room temperature, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying at the temperature of 80 ℃ for 10 hours to obtain a NiCo-MOFs material;
the centrifugal cleaning in the step one is to use absolute ethyl alcohol as a cleaning agent, the volume ratio of the absolute ethyl alcohol to the collected lower-layer solid is 1:10, the centrifugal cleaning is carried out at the centrifugal speed of 4000r/min, the centrifugal cleaning frequency is 3 times, and the centrifugal cleaning time is 5min each time;
secondly, preparing a NiCo/Zif-8 precursor:
dispersing the NiCo-MOFs material obtained in the step one into methanol to obtain a NiCo-MOFs material/methanol solution;
the mass ratio of the NiCo-MOFs material to the methanol in the second step is 1: 400;
② Zn (NO)3)2And dimethylimidazole are added into the NiCo-MOFs material/methanol solution obtained in the second step to obtain a mixed solution II;
step two, Zn (NO) in the mixed solution II3)2The mass fraction of (A) is 12%;
and in the second step, the mass fraction of the dimethyl imidazole in the mixed solution II is 6%.
Transferring the mixed solution II into a round-bottom flask, heating to 70 ℃, stirring for 60min at the temperature of 70 ℃ and at the stirring speed of 200r/min, cooling to room temperature, centrifuging, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying at the temperature of 80 ℃ for 10 hours to obtain a NiCo/Zif-8 precursor;
in the step two, the centrifugal cleaning is performed at a centrifugal speed of 4000r/min by using absolute ethyl alcohol as a cleaning agent and a volume ratio of the absolute ethyl alcohol to collected lower-layer solids of 1:10, wherein the centrifugal cleaning is performed for 3 times, and the time for each centrifugal cleaning is 5 min;
thirdly, calcining:
and transferring the NiCo/Zif-8 precursor into a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace from room temperature to 500 ℃ at the heating rate of 5 ℃/min under the protection of the inert gas, calcining for 2h, and then preserving the temperature for 5h at 500 ℃ to obtain the NiCo/ZnO carbonized material, namely the ternary metal carbonized MOFs material.
FIG. 1 is a transmission electron microscope image of the ternary metal carbonized MOFs material prepared in example 1;
as can be seen from fig. 1, the ternary metal carbonized MOFs material prepared in example 1 has a rod-like appearance and a width of about 800nm, and the core-shell structure can be clearly seen from the figure, in which the inner layer is made of nickel-cobalt material and the outer layer is made of zinc oxide carbonized material.
FIG. 2 is an XRD pattern of the ternary metal carbonized MOFs material prepared in example 1;
as can be seen from FIG. 2, the ternary metal carbide MOFs material prepared in example 1 has obvious diffraction peaks at 31.8 °, 34.5 °, 36.4 °, 47.5 °, 56.7 °, 63.0 ° and 68.0 ° 2 θ, which correspond to the (100), (002), (101), (102), (110), (103) and (112) crystal planes of ZnO respectively and are consistent with the standard card of ZnO (JCPDS No. 36-1451). The shell layer of the product is coated by ZnO, and the ZnO crystal structure is good.
FIG. 3 is an electromagnetic wave absorption diagram of samples with different thicknesses, wherein 10% of the mass of the sample is the ternary metal carbonized MOFs material prepared in example 1, and 90% of the mass of the sample is paraffin;
as can be seen from fig. 3, in addition to the absorption maxima at different thicknesses and different frequency bands, the reflectivities below-10 (absorptivities above 90%) occur at thicknesses of 2, 3, 4 and 5mm, and the optimal reflectivity at thickness of 5mm is-17 dB, which also fully demonstrates that the frequency bands can be absorbed by adjusting the thicknesses. The material can achieve excellent electromagnetic wave absorption effect under the condition of low content.
Claims (10)
1. A preparation method of ternary metal carbonized MOFs materials is characterized in that the preparation method of the ternary metal carbonized MOFs materials is completed according to the following steps:
firstly, preparing NiCo-MOFs materials:
dissolving terephthalic acid in N, N-dimethylformamide to obtain a terephthalic acid/N, N-dimethylformamide solution;
secondly, adding cobalt salt and nickel salt into a terephthalic acid/N, N-dimethylformamide solution, and performing ultrasonic treatment to obtain a mixed solution I; transferring the mixed solution I into a hydrothermal reaction kettle, and carrying out hydrothermal reaction to obtain a reaction product I;
thirdly, cooling the reaction product I to room temperature, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying to obtain a NiCo-MOFs material;
secondly, preparing a NiCo/Zif-8 precursor:
firstly, dispersing NiCo-MOFs materials into methanol to obtain a NiCo-MOFs material/methanol solution;
② Zn (NO)3)2Adding dimethylimidazole and NiCo-MOFs material/methanol solution to obtain a mixed solution II;
thirdly, stirring the mixed solution II for 30-90 min under the heating condition, cooling to room temperature, finally centrifuging, pouring out the supernatant, and collecting the lower-layer solid; centrifugally cleaning the collected lower-layer solid, and drying to obtain a NiCo/Zif-8 precursor;
thirdly, calcining:
transferring the NiCo/Zif-8 precursor into a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 400-600 ℃ under the protection of the inert gas, and calcining at 400-600 ℃ to obtain the NiCo/ZnO carbonized material, namely the ternary metal carbonized MOFs material.
2. The method for preparing the ternary metal carbonized MOFs material according to claim 1, wherein the mass fraction of terephthalic acid in the solution of phthalic acid/N, N-dimethylformamide in the first step is 10-50%; the cobalt salt in the first step is Co (NO)3)2.6H2O; the nickel salt in the first step is Ni (NO)3)2.6H2O。
3. The method for preparing the ternary metal carbonized MOFs material according to claim 1, wherein the molar ratio of the cobalt salt to the nickel salt in the first step (1-10): 1; the volume ratio of the nickel salt substance in the first step to the terephthalic acid/N, N-dimethylformamide solution is 1mol (3000 mL-5000 mL); the power of the ultrasound in the first step is 100W-300W, and the ultrasound time is 1 min-3 min.
4. The method for preparing ternary metal carbonized MOFs material according to claim 1, wherein the temperature of the hydrothermal reaction in the first step is 140-180 ℃ and the time of the hydrothermal reaction is 18-24 h.
5. The method for preparing the ternary metal carbonized MOFs material according to claim 1, wherein the centrifugal cleaning in the step one is performed at a centrifugal speed of 3000r/min to 5000r/min by using absolute ethyl alcohol as a cleaning agent and a volume ratio of the absolute ethyl alcohol to collected lower-layer solids of 1:10, the number of the centrifugal cleaning is 3 to 5, and the time for each centrifugal cleaning is 4 to 8 min; the drying temperature in the step one is 70-90 ℃, and the drying time is 8-12 h.
6. The method for preparing the ternary metal carbonized MOFs material according to claim 1, wherein the mass ratio of the NiCo-MOFs material to the methanol in the second step is 1 (100-500); step two, Zn (NO) in the mixed solution II3)2The mass fraction of (A) is 1-20%; and in the second step, the mass fraction of the dimethyl imidazole in the mixed solution II is 1-20%.
7. The method for preparing ternary metal carbonized MOFs material according to claim 1, wherein the mixed solution II in the second step is transferred to a round bottom flask, heated to 50-80 ℃, and stirred for 30-90 min at 50-80 ℃ and at a stirring speed of 100-300 r/min.
8. The method for preparing the ternary metal carbonized MOFs material according to claim 1, wherein the centrifugal cleaning in the second step is performed at a centrifugal speed of 3000r/min to 5000r/min by using absolute ethyl alcohol as a cleaning agent, wherein the volume ratio of the absolute ethyl alcohol to the collected lower-layer solids is 1:10, the centrifugal cleaning is performed for 3 to 5 times, and the time for each centrifugal cleaning is 4 to 8 min; the drying temperature in the second step is 70-90 ℃, and the drying time is 8-12 h.
9. The method for preparing ternary metal carbonized MOFs material according to claim 1, wherein in the third step, the tubular furnace is heated from room temperature to 400-600 ℃ at a heating rate of 1-20 ℃/min under the protection of inert gas, calcined for 1-2 h, and then kept at 400-600 ℃ for 1-5 h.
10. Use of a ternary metal carbonized MOFs material prepared by the preparation method according to claim 1, characterized in that a ternary metal carbonized MOFs material is used for absorbing electromagnetic waves.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097316A (en) * | 2017-12-05 | 2018-06-01 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of the MOFs nano materials of supported nano-gold metal particles |
| CN109166733A (en) * | 2018-09-30 | 2019-01-08 | 北京印刷学院 | A kind of method that hydro-thermal method prepares Ni/Co base MOF material |
| CN110289407A (en) * | 2019-06-26 | 2019-09-27 | 浙江大学 | A kind of carbon coating cobalt-doping zinc oxide nano material for lithium ion battery |
| CN110745806A (en) * | 2019-10-29 | 2020-02-04 | 苏州大学 | Method for preparing multi-stage porous carbon material by using bacteria as template to grow MOF and application of multi-stage porous carbon material in energy storage device |
-
2021
- 2021-03-18 CN CN202110293548.XA patent/CN113060731B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097316A (en) * | 2017-12-05 | 2018-06-01 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of the MOFs nano materials of supported nano-gold metal particles |
| CN109166733A (en) * | 2018-09-30 | 2019-01-08 | 北京印刷学院 | A kind of method that hydro-thermal method prepares Ni/Co base MOF material |
| CN110289407A (en) * | 2019-06-26 | 2019-09-27 | 浙江大学 | A kind of carbon coating cobalt-doping zinc oxide nano material for lithium ion battery |
| CN110745806A (en) * | 2019-10-29 | 2020-02-04 | 苏州大学 | Method for preparing multi-stage porous carbon material by using bacteria as template to grow MOF and application of multi-stage porous carbon material in energy storage device |
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| CN115703633A (en) * | 2021-08-12 | 2023-02-17 | 西南大学 | Micron-sized embroidered spherical porous carbon material and preparation method and application thereof |
| CN115703633B (en) * | 2021-08-12 | 2024-05-31 | 西南大学 | Micron-sized embroidered ball-shaped porous carbon material and preparation method and application thereof |
| CN114346250A (en) * | 2021-12-31 | 2022-04-15 | 广东技术师范大学 | Metal-carbon composite particle and preparation method and application thereof |
| CN114346250B (en) * | 2021-12-31 | 2023-09-26 | 广东技术师范大学 | Metal-carbon composite particles and preparation method and application thereof |
| CN114479762A (en) * | 2022-03-01 | 2022-05-13 | 同济大学 | Magnetic metal/metal oxide/carbon nano composite material, preparation method and application thereof |
| CN114479762B (en) * | 2022-03-01 | 2023-11-28 | 同济大学 | Magnetic metal/metal oxide/carbon nanocomposite material, preparation method and application thereof |
| CN115074085A (en) * | 2022-06-30 | 2022-09-20 | 宿辉 | Preparation method and application of chocolate ball type silicon carbide multilayer composite wave-absorbing material |
| CN115074085B (en) * | 2022-06-30 | 2024-03-26 | 宿辉 | Preparation method and application of chocolate ball type silicon carbide multilayer composite wave-absorbing material |
| CN115350706A (en) * | 2022-08-29 | 2022-11-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of three-element metal MOF (Metal organic framework) derivative catalyst for hydrogenation thermal catalysis |
| CN115722202A (en) * | 2022-11-08 | 2023-03-03 | 中国科学院上海高等研究院 | Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
| CN115722202B (en) * | 2022-11-08 | 2024-03-29 | 中国科学院上海高等研究院 | Yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
| CN115724604A (en) * | 2022-11-23 | 2023-03-03 | 南京航空航天大学 | Preparation method of composite antibacterial cementing material |
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