CN110480026B - Nano composite material and preparation method and application thereof - Google Patents
Nano composite material and preparation method and application thereof Download PDFInfo
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- CN110480026B CN110480026B CN201910617377.4A CN201910617377A CN110480026B CN 110480026 B CN110480026 B CN 110480026B CN 201910617377 A CN201910617377 A CN 201910617377A CN 110480026 B CN110480026 B CN 110480026B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 150000002815 nickel Chemical class 0.000 claims abstract description 23
- 239000012429 reaction media Substances 0.000 claims abstract description 23
- 150000001868 cobalt Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000004381 surface treatment Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 41
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011358 absorbing material Substances 0.000 abstract description 51
- 239000002131 composite material Substances 0.000 abstract description 43
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- 239000000523 sample Substances 0.000 description 28
- 239000002082 metal nanoparticle Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 10
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a nano composite material and a preparation method and application thereof, relating to the field of functional materials. The preparation method at least comprises the following steps: providing a reaction medium; loading nickel salt and cobalt salt to the aromatic polycarboxylic acid through the reaction medium, and carrying out heat preservation treatment and/or surface treatment to obtain an intermediate; and carrying out heat treatment on the intermediate under the inert gas atmosphere to obtain the nano composite material. The composite material prepared by the invention overcomes the technical defects that the wave-absorbing material in the prior art is difficult to meet the requirements of strong absorption capacity, wide absorption band, light weight, thin matching thickness and the like.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a nano composite material, and a preparation method and application thereof.
Background
In order to solve many problems brought to people's life by electromagnetic radiation and interference in daily life, researchers have been making efforts to develop efficient wave-absorbing materials with strong absorption capacity, wide absorption band, light weight and thin matching thickness. According to the wave-absorbing loss mechanism, wave-absorbing materials can be divided into magnetic loss type and electric loss type wave-absorbing materials. In view of the current state of development of wave-absorbing materials, the microwave absorbing properties of conventional electromagnetic wave-absorbing materials have been improved, but it is still difficult to satisfy all the above requirements ("strong, wide, light, thin") simultaneously with a single component wave-absorbing material. In order to overcome the defects, the method widely adopted at present is to physically mix the dielectric medium and the magnetic medium material and adjust the components of the material so as to enhance or adjust the wave-absorbing performance of the material. Therefore, in order to realize excellent wave-absorbing performance of the composite material, the realization of the adjustable components of the wave-absorbing material is the primary objective of research and development of novel wave-absorbing materials.
The invention provides a nano composite material and a preparation method thereof, which well solve the existing problems.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a metal nanoparticle and nano porous carbon composite wave-absorbing material, a preparation method and application thereof, and overcomes the technical defects that the wave-absorbing material in the prior art is difficult to meet the requirements of strong absorption capacity, wide absorption band, light weight, thin matching thickness and the like.
In order to achieve the above objects or other objects, the present invention provides a method for preparing a nanocomposite, the method at least comprising the steps of:
providing a reaction medium;
loading nickel salt and cobalt salt to the aromatic polycarboxylic acid through the reaction medium, and carrying out heat preservation treatment and surface treatment to obtain an intermediate;
and carrying out heat treatment on the intermediate under the inert gas atmosphere to obtain the nano composite material.
In one embodiment, the molar ratio of the nickel salt to the cobalt salt is 0 to 3.0.
In one embodiment, the reaction medium is one of methanol, ethanol, and dimethylformamide. The molar ratio of the total amount of the nickel salt and the cobalt salt to the reaction medium was 4.4: 1728-1800.
In one embodiment, the molar ratio of the aromatic polycarboxylic acid to the nickel salt is 0.4 to 0.6. The aromatic polycarboxylic acid is one or a combination of more of trimesic acid, terephthalic acid and p-toluic acid.
In one embodiment, the nickel salt is one or more of nickel nitrate, nickel acetate and nickel chloride. The cobalt salt is one or a combination of more of cobalt nitrate, cobalt acetate and cobalt chloride.
In one embodiment, the heat treatment temperature in the heat treatment process is 500-700 ℃. The heating rate of the heat treatment in the heat treatment process is 5-20 ℃/min. And the heat treatment and heat preservation time is 60-180 min.
In one embodiment, the heat preservation temperature in the heat preservation treatment process is 120-150 ℃. The heat preservation time in the heat preservation treatment process is 24-32 h.
In one embodiment, the surface treatment comprises washing, drying and cooling. And the washing comprises the steps of centrifuging the sample subjected to heat preservation treatment, respectively washing with the reaction medium and deionized water, and respectively washing for three times. The drying is to place the sample in an oven and dry the sample at 60-80 ℃ for 12-24 h.
In one embodiment, the inert gas is one of nitrogen or argon.
The invention also provides a nano composite material prepared by the preparation method.
In one embodiment, the wave-absorbing bandwidth of the nano composite material is 3.3-18.0 GHz.
The invention also provides application of the nano composite material prepared by the preparation method in the field of electromagnetic wave absorption materials.
The invention prepares the NiCo metal nano-particles and nano porous carbon composite wave-absorbing material with high absorption performance by using a NiCo bimetal metal organic framework material as a template through the synergistic effect of the nickel-cobalt metal nano-magnetic particles (NiCo) and porous carbon. The method adopted by the invention is simple, stable and controllable, and the obtained composite wave-absorbing material has excellent wave-absorbing performance and stable performance.
Drawings
FIG. 1 is a graph of the magnetic properties of the NiCo metal nanoparticles and the nanoporous carbon composite wave-absorbing material in the embodiment;
FIG. 2 is an X-ray diffraction (XRD) spectrum of the NiCo metal nano-particles and the nano porous carbon composite wave-absorbing material in the embodiment;
FIG. 3 shows Ni in example1Co2Transmission Electron Microscope (TEM) micrograph of @ NPC;
FIG. 4 shows Ni in example1Co1Transmission Electron Microscope (TEM) micrograph of @ NPC;
FIG. 5 shows Ni in example2Co1Transmission Electron Microscope (TEM) micrograph of @ NPC;
FIG. 6 is a specific surface area curve diagram of NiCo metal nanoparticles and nanoporous carbon composite wave-absorbing material in the embodiment;
FIG. 7 shows Ni in example1Co2The wave absorbing performance curve chart of @ NPC;
FIG. 8 shows Ni in example1Co1The wave absorbing performance curve chart of @ NPC;
FIG. 9 shows Ni in example2Co1The wave absorbing performance curve chart of @ NPC;
FIG. 10 is a wave-absorbing property curve of Ni @ NPC in the comparative example;
FIG. 11 is a wave-absorbing property curve of Co @ NPC in the comparative example;
FIG. 12 is a schematic flow chart of the method of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
The invention provides a preparation method of a nano composite material, which at least comprises the following steps:
adding nickel salt and cobalt salt into a reaction medium according to a molar ratio of 0-3.0, and mixing, wherein the total amount of the nickel salt and the cobalt salt is maintained at 4.4mmol, and stirring at room temperature for 2-4h to obtain a solution A;
dissolving aromatic polycarboxylic acid in the reaction medium, stirring for 2-4h at room temperature to obtain a solution B, adding the solution A into the solution B, stirring at room temperature, and loading nickel salt and cobalt salt to the aromatic polycarboxylic acid through the reaction medium to obtain a precursor reaction solution;
transferring the precursor reaction solution into a hydrothermal kettle, preserving the temperature for 24-32 hours at the temperature of 120-150 ℃ in a constant temperature box, and cooling to room temperature; centrifuging the obtained sample, respectively cleaning the precipitate with the organic solvent and deionized water, respectively cleaning for three times, and drying the obtained sample in an oven at 60-80 ℃ for 12-24 hours to obtain an intermediate (namely a precursor);
and heating the intermediate to 500-700 ℃ at the heating rate of 5-20 ℃/min in the inert gas atmosphere, preserving the heat for 60-180 minutes, and then cooling to room temperature to obtain a product, thereby obtaining the nano composite material.
In the above reaction medium, methanol is most compatible with nickel salt and cobalt salt, and the examples given below are methanol and trimesic acid.
In one embodiment, the present invention provides a method of preparing a nanocomposite, the method comprising at least the steps of:
nickel nitrate hexahydrate and cobalt nitrate hexahydrate in molar ratio n(Ni+)/n(Co+)Mixing and dissolving in 40mL of methanol at a ratio of 1/2, wherein the total amount of nickel nitrate hexahydrate and cobalt nitrate hexahydrate is maintained at 4.4mmol, and stirring at 25 ℃ for 2 hours to obtain A1A solution;
dissolving 2.4mmol of trimesic acid in 30mL of methanol, and stirring at 25 ℃ for 2 hours to obtainB1A solution;
the A is added1Solution is added to the B1In the solution, stirring at 25 ℃ for 2 hours, loading nickel salt and cobalt salt to aromatic polycarboxylic acid through the reaction medium to obtain A1B1Precursor reaction solution;
the A is added1B1Transferring the precursor reaction solution into a 100mL Teflon hydrothermal kettle, preserving the temperature for 32 hours in a constant temperature box at 120 ℃, and cooling to room temperature; centrifuging the obtained sample, respectively cleaning the precipitate with methanol and deionized water for three times, and drying the obtained sample in an oven at 60 ℃ for 24 hours;
heating the dried sample to 500 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving the temperature for 180 minutes, and then cooling to room temperature to obtain a product, thereby obtaining the nano composite material, specifically Ni1Co2The composite wave-absorbing material of metal nano-particles and nano-porous carbon is marked as Ni1Co2@NPC。
The reason why the above-mentioned total amount of nickel nitrate hexahydrate and cobalt nitrate hexahydrate was maintained at 4.4mmol was that: (1) the optimal proportion of the metal ions and the organic ligands in the self-assembly experiment; (2) the highest specific surface area is achieved by the synergistic effect between the bimetallic nickel and the cobalt.
In one embodiment, the present invention provides a method of preparing a nanocomposite, the method comprising at least the steps of:
nickel nitrate hexahydrate and cobalt nitrate hexahydrate in molar ratio n(Ni+)/n(Co+)The total amount of nickel nitrate hexahydrate and cobalt nitrate hexahydrate was maintained at 4.4mmol dissolved in 40mL of methanol at a ratio of 1/1, and the mixture was stirred at 25 ℃ for 2 hours to obtain a2A solution;
2.4mmol of trimesic acid was dissolved in 30mL of methanol and stirred at 25 ℃ for 2 hours to obtain B2A solution;
the A is added2Solution is added to the B2In the solution, stirring at 25 ℃ for 2 hours, loading nickel salt and cobalt salt to aromatic polycarboxylic acid through the reaction medium to obtain A2B2Precursor reaction solution;
the A is added2B2Transferring the precursor reaction solution into a 100mL Teflon hydrothermal kettle, preserving heat for 28 hours at 135 ℃ in a constant temperature box, cooling to room temperature, centrifuging the obtained sample, respectively cleaning the precipitate with methanol and deionized water for three times, placing the obtained sample in a 60 ℃ oven, and drying for 24 hours;
heating the dried sample to 600 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, preserving the temperature for 120 minutes, and then cooling to room temperature to obtain a required product, thereby obtaining the nano composite material, specifically Ni1Co1The composite wave-absorbing material of metal nano-particles and nano-porous carbon is marked as Ni1Co1@NPC。
In one embodiment, the present invention provides a method of preparing a nanocomposite, the method comprising at least the steps of:
nickel nitrate hexahydrate and cobalt nitrate hexahydrate in molar ratio n(Ni+)/n(Co+)The total amount of nickel nitrate hexahydrate and cobalt nitrate hexahydrate was maintained at 4.4mmol dissolved in 40mL of methanol at a ratio of 2/1, and the mixture was stirred at 25 ℃ for 2 hours to obtain a3A solution;
2.4mmol of trimesic acid was dissolved in 30mL of methanol and stirred at 25 ℃ for 2 hours to obtain B3A solution;
the A is added3Solution is added to the B3In the solution, stirring at 25 ℃ for 2 hours, loading nickel salt and cobalt salt to aromatic polycarboxylic acid through the reaction medium to obtain A3B3Precursor reaction solution;
the A is added3B3Transferring the precursor reaction solution into a 100mL Teflon hydrothermal kettle, preserving heat for 24 hours in a constant temperature box at 150 ℃, cooling to room temperature, centrifuging the obtained sample, respectively cleaning the precipitate with methanol and deionized water for three times, placing the obtained sample in a 60 ℃ drying oven, and drying for 24 hours;
heating the dried sample at a temperature rise rate of 20 ℃/min in an argon atmosphereHeating to 700 ℃ and preserving heat for 60 minutes, and then cooling to room temperature to obtain the product, thereby obtaining the nano composite material, specifically Ni2Co1The composite wave-absorbing material of metal nano-particles and nano-porous carbon is marked as Ni2Co1@NPC。
In a first aspect, the present invention provides a process for the preparation of a nanocomposite, said process comprising at least the following steps:
1.28g of nickel nitrate hexahydrate was dissolved in 40mL of methanol with the total amount of nickel nitrate hexahydrate maintained at 4.4mmol, and the mixture was stirred at 25 ℃ for 2 hours to obtain A4A solution;
2.4mmol of trimesic acid was dissolved in 30mL of methanol and stirred at 25 ℃ for 2 hours to obtain B4A solution;
the A is added4Solution is added to the B4In the solution, stirring at 25 ℃ for 2 hours, loading nickel salt and cobalt salt to aromatic polycarboxylic acid through the reaction medium to obtain A4B4Precursor reaction solution;
the A is added4B4Transferring the precursor reaction solution into a 100mL Teflon hydrothermal kettle, preserving heat for 24 hours in a constant temperature box at 150 ℃, cooling to room temperature, centrifuging the obtained sample, respectively cleaning the precipitate with methanol and deionized water for three times, placing the obtained sample in a 60 ℃ drying oven, and drying for 24 hours;
and heating the dried sample to 600 ℃ at a heating rate of 20 ℃/min in an argon atmosphere, preserving the temperature for 60 minutes, and then cooling to room temperature to obtain a product, thereby obtaining the nano composite material, specifically the Ni metal nano particle and nano porous carbon composite wave-absorbing material, which is recorded as Ni @ NPC.
In a first aspect, the present invention provides a process for the preparation of a nanocomposite, said process comprising at least the following steps:
1.28g of cobalt nitrate hexahydrate was dissolved in 40mL of methanol with the total amount of nickel nitrate hexahydrate maintained at 4.4mmol, and the mixture was stirred at 25 ℃ for 2 hours to obtain A5A solution;
dissolving 2.4mmol of trimesic acid in water30mL of methanol was stirred at 25 ℃ for 2 hours to obtain B5A solution;
the A is added5Solution is added to the B5In the solution, stirring for 2 hours at 25 ℃, loading nickel salt and cobalt salt to aromatic polycarboxylic acid through the reaction medium to obtain A5B5Precursor reaction solution;
the A is added5B5Transferring the precursor reaction solution into a 100mL Teflon hydrothermal kettle, preserving heat for 24 hours in a constant temperature box at 150 ℃, cooling to room temperature, centrifuging the obtained sample, respectively cleaning the precipitate with methanol and deionized water for three times, placing the obtained sample in a 60 ℃ drying oven, and drying for 24 hours;
and heating the dried sample to 700 ℃ at a heating rate of 20 ℃/min in an argon atmosphere, preserving the temperature for 60 minutes, and then cooling to room temperature to obtain a product, thereby obtaining the nano composite material, specifically the Co metal nano particle and nano porous carbon composite wave-absorbing material, which is recorded as Co @ NPC.
Performance testing
The phase structure, specific surface area, magnetic property and wave-absorbing property of the NiCo metal nanoparticles and the nano porous carbon composite wave-absorbing material in the embodiment and the phase structure, specific surface area, magnetic property and wave-absorbing property of the single metal nanoparticles and the nano porous carbon composite wave-absorbing material in the comparative example are provided in table 1.
1. For detecting the magnetic property of the NiCo metal nanoparticle and nanoporous carbon composite wave-absorbing material in the embodiment, please refer to fig. 1 and table 1, the magnetic property of the composite material is obtained by a physical property measurement system (manufactured by quantum design ltd), as shown in fig. 1, wherein a curve a represents Ni1Co2@ NPC, curve b represents Ni1Co1@ NPC, curve c represents Ni2Co1@ NPC, it can be seen from the figure that the magnetic performance of curve a is better than that of curve b, and the magnetic performance of curve b is better than that of curve c.
2. Phase structure determination is performed on the NiCo metal nanoparticles and the nanoporous carbon composite wave-absorbing material in the embodiment, please refer to table 1 and fig. 2, and the method adoptsThe radiation source is Cu-Kalpha
Respectively carrying out phase structure determination on the composite wave-absorbing materials prepared in 3 embodiments by X-ray diffraction (XRD for short), wherein a curve a represents Ni1Co2@ NPC, curve b represents Ni1Co1@ NPC, curve c represents Ni2Co1@ NPC. As can be seen from FIG. 2, the prepared composite wave-absorbing material is mainly a NiCo phase, XRD data are analyzed, the crystal size of the NiCo phase is calculated by using a WPF refinement module of Jade software, and the crystal sizes of the NiCo phase prepared in 3 embodiments are 20nm, 32nm and 46nm respectively. Thus, the different molar ratios of Ni and Co and the heat treatment temperature in the present invention have no effect on the phase of the final material, but as the thermal decomposition temperature increases, the NiCo metal nanoparticles gradually increase in size.
3. The NiCo metal nanoparticles and the nanoporous carbon composite wave-absorbing material in the embodiment are subjected to microscopic morphology analysis, please refer to fig. 3 to 5, and the sample morphologies of the composite wave-absorbing material prepared in 3 embodiments are respectively observed through a transmission electron microscope (TEM for short), wherein fig. 3 represents Ni1Co2Microtopography of @ NPC, FIG. 4 represents Ni1Co1Microtopography of @ NPC, FIG. 5 represents Ni2Co1Microtopography of @ NPC. As can be seen from the figure, the composite wave-absorbing materials prepared in 3 embodiments are all of core-shell structure, Ni1Co2The NiCo metal nanoparticles in the @ NPC are 24nm, Ni1Co1The NiCo metal nanoparticles in the @ NPC are 35nm, Ni2Co1The NiCo metal nanoparticles in @ NPC are 50 nm.
4. Specific surface area measurement is performed on the NiCo metal nanoparticles and the nanoporous carbon composite wave-absorbing material in the embodiment, please refer to table 1 and fig. 6, a Quad-rasorb-SI instrument is adopted to record nitrogen adsorption-release curves of the composite wave-absorbing material prepared in 3 embodiments, and Brunauer-Emmett-teller (bet) method is adopted to measure the specific surface areas of the three, and the result is shown in fig. 6, which shows that 3 embodiments are implementedThe specific surface area of the composite wave-absorbing material prepared in the example is 91m in sequence2/g、73m2/g、70m2The specific surface area of the composite wave-absorbing material is gradually reduced along with the increase of the thermal decomposition temperature; this is mainly caused by the continuous collapse of NiCo-MOFs nanoparticles during the thermal decomposition process and the continuous growth of magnetic nanoparticles. But the prepared nano electromagnetic composite material still has porosity and higher specific surface area, which is beneficial to improving the microwave absorption performance of the composite material.
The test method for testing the nitrogen adsorption-release curve comprises the following steps: and testing the nitrogen adsorption-release curve of the samples obtained at different thermal decomposition temperatures by adopting the same experimental operation method and treatment mode. The specific method comprises the following steps: (1) starting the instrument, and adjusting a pressure reducing valve by a nitrogen cylinder; (2) loading the sample with determined mass into a sample tube for degassing treatment; the degassing temperature is 300 ℃, and the degassing time is four hours; (3) analyzing the degassed sample, filling the Dewar flask with liquid nitrogen, opening software to set program parameters of an analysis station and starting analysis; (4) and processing the data to obtain numerical values such as the specific surface area and the aperture distribution of the sample.
5. The wave absorbing performance of the NiCo metal nanoparticles and the nanoporous carbon composite wave absorbing material in the embodiment is tested, please refer to table 1 and fig. 7 to 9, the composite wave absorbing material in 3 embodiments is respectively taken and uniformly dispersed in paraffin, so that the composite wave absorbing material accounts for 40% of the total mass of the composite wave absorbing material and the paraffin, and the composite wave absorbing material is pressed into ring pieces with the outer diameter of 7.0mm, the inner diameter of 3.04mm and different thicknesses, wherein the thicknesses are respectively 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm and 5 mm.
The electromagnetic parameters are tested by adopting a vector network analyzer, and the wave absorbing performance is obtained by calculation, wherein the testing frequency range is 2-18GHz, and the specific process is as follows: an Agilent N5224A vector network analyzer is adopted, a coaxial line method is used for measuring a network scattering parameter S parameter, and the relative complex dielectric constant and the relative complex permeability of a sample material are calculated according to the transmission line reflection and transmission coefficient of the material sample. According to the following formula:
Zin＝Z0(μr/r)1/2tan h[j(2πfd/c)×(μr·r)1/2] (1)
obtaining the reflection loss RL value of the sample to the electromagnetic wave, wherein Z isinAn input impedance for the absorber; z0Is a free space impedance; u. ofrIs a relative complex permeability; f is the electromagnetic wave frequency; j is the transmission coefficient; d is the absorber thickness; c is the speed of light;ris the relative complex dielectric constant.
The change curve of the reflection loss of the obtained composite wave-absorbing material along with the frequency is shown in fig. 7 to 9. As can be seen from FIG. 9, Ni, a product obtained in the example1Co2The thickness range of the @ NPC composite wave-absorbing material is 2-5mm, and the wave-absorbing bandwidth (RL) of the material<-10dB) of 4.0 to 18.0GHz, RL at a frequency of 8.8GHz and a specimen thickness of 3.0mmminIs-42.5 dB. As can be seen from FIG. 8, Ni, a product obtained in the example1Co1The thickness range of the @ NPC composite wave-absorbing material is 1.5-5mm, and the wave-absorbing bandwidth (RL)<-10dB) of 3.9 to 18.0GHz, RL at a frequency of 14.5GHz and a specimen thickness of 2.0mmminIs-22.3 dB. As can be seen from FIG. 7, Ni, a product obtained in the example2Co1The thickness range of the @ NPC composite wave-absorbing material is 1.5-5mm, and the wave-absorbing bandwidth (RL)<-10dB) of 3.3 to 18.0GHz, RL at a frequency of 14.2GHz and a specimen thickness of 2.0mmminIs-28.9 dB.
FIGS. 10 and 11 are respectively the change curves of the reflection loss with the frequency of the composite wave-absorbing material of Ni @ NPC and Co @ NPC in the comparative example, and as can be seen from FIGS. 7 to 11 and Table 1, compared with the wave-absorbing material with single component of Ni @ NPC and Co @ NPC, the NiCo @ NPC composite wave-absorbing material has excellent wave-absorbing performance.
TABLE 1
The symbols in table 1 have the following meanings:
Mssaturation magnetization, HcCoercive force, RLmin-minimum reflection loss, f-bandwidth, d-matching thickness.
In summary, the nanocomposite prepared by one or more embodiments of the invention has excellent wave-absorbing performance with wide-frequency strong absorption. The synergistic effect between the metal nano magnetic particles (NiCo) and the nano porous carbon promotes the excellent wave-absorbing performance of the nano composite wave-absorbing material through the combined action of electric loss and magnetic loss. The nano composite material prepared by one or more embodiments of the invention is applied to the field of electromagnetic wave absorbing materials, so that the aim of adjusting the components of the material is fulfilled, and the wave absorbing performance of the material is further enhanced.
According to one or more embodiments of the invention, the nano composite wave-absorbing material with wide frequency and strong absorption can be prepared through simple chemical synthesis and thermal decomposition processes. The technological parameters of the invention can effectively regulate and control the phase composition and microstructure of the composite material, and finally regulate and control the wave-absorbing performance of the composite material. The preparation process of the composite wave-absorbing material is controllable, stable, simple and feasible, thereby greatly promoting the industrial production and having important significance for the wide application and development of the nano composite wave-absorbing material. Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. A method for preparing a nanocomposite, characterized in that the method at least comprises the following steps:
providing a reaction medium;
loading nickel salt and cobalt salt to the aromatic polycarboxylic acid through the reaction medium, and carrying out heat preservation treatment and surface treatment to obtain an intermediate;
carrying out heat treatment on the intermediate under the inert gas atmosphere to obtain the nano composite material;
wherein the molar ratio of the total amount of the nickel salt and the cobalt salt to the reaction medium is 4.4: 1728-1800; the wave-absorbing bandwidth of the nano composite material is 3.3-18.0 GHz; adding nickel salt and cobalt salt into a reaction medium according to a molar ratio of 0-3.0, mixing, wherein the total amount of the nickel salt and the cobalt salt is maintained at 4.4mmol, and stirring at room temperature for 2-4h to obtain a solution A; dissolving aromatic polycarboxylic acid in the reaction medium, stirring for 2-4h at room temperature to obtain a solution B, adding the solution A into the solution B, stirring at room temperature, and loading nickel salt and cobalt salt to the aromatic polycarboxylic acid through the reaction medium to obtain a precursor reaction solution; transferring the precursor reaction solution into a hydrothermal kettle, preserving the temperature for 24-32 hours at the temperature of 120-150 ℃ in a constant temperature box, and cooling to room temperature; centrifuging the obtained sample, respectively cleaning the precipitate with an organic solvent and deionized water, respectively cleaning for three times, and drying the obtained sample in an oven at 60-80 ℃ for 12-24 hours to obtain an intermediate; and heating the intermediate to 500-700 ℃ at the heating rate of 5-20 ℃/min in the inert gas atmosphere, preserving the heat for 60-180 minutes, and then cooling to room temperature to obtain a product, thereby obtaining the nano composite material.
2. The method according to claim 1, wherein the molar ratio of the nickel salt to the cobalt salt is 0 to 3.0.
3. The method of claim 1, wherein the reaction medium is one of methanol, ethanol, and dimethylformamide.
4. The method according to claim 1, wherein the molar ratio of the aromatic polycarboxylic acid to the nickel salt is 0.4 to 0.6.
5. The method according to claim 1, wherein the aromatic polycarboxylic acid is one or more selected from the group consisting of trimesic acid, terephthalic acid and p-toluic acid.
6. The method according to claim 1, wherein the nickel salt is one or more of nickel nitrate, nickel acetate and nickel chloride.
7. A nanocomposite obtained by the production method as claimed in any one of claims 1 to 6.
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