CN109181640B - Preparation method of porous carbon wave-absorbing material with inlaid cobalt and oxide - Google Patents
Preparation method of porous carbon wave-absorbing material with inlaid cobalt and oxide Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011358 absorbing material Substances 0.000 title claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 5
- 239000010941 cobalt Substances 0.000 title abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 57
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 229920003081 Povidone K 30 Polymers 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- -1 diluted methanol Chemical compound 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 10
- 238000000227 grinding Methods 0.000 abstract description 8
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 7
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 31
- 239000002105 nanoparticle Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 16
- 239000013384 organic framework Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
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Abstract
A preparation method of porous carbon wave-absorbing material with embedded cobalt and oxide belongs to the technical field of microwave absorbing materials. The invention takes a metal organic framework ZIF-67 as a precursor, and obtains Co/Co through one-step carbonization3O4A method for preparing a nano porous carbon composite wave-absorbing material. Synthesizing ZIF-67 powder of a metal organic framework by adopting a diffusion method and a coprecipitation method, calcining the ZIF-67 powder in an inert atmosphere at 500-800 ℃, cooling the powder to a certain temperature, taking out the powder, air-cooling, and oxidizing Co into Co3O4After completely cooling, grinding and collecting black powder to obtain Co/Co with excellent wave absorbing performance3O4A nano porous carbon composite wave-absorbing material which is embedded. The process has the advantages of simple process, low cost of raw materials, short time-consuming period, no need of any subsequent treatment process and complex synthesis equipment, and provides conditions for practical production and application.
Description
Technical Field
The invention relates to a method for preparing Co/Co by taking a metal organic framework ZIF-67 as a template3O4Inlaid nano porous carbon wave-absorbing material (Co/Co)3O4@ NPC), belonging to the technical field of microwave absorbing materials.
Background
In recent years, the demand for microwave absorbing materials has been increasing, and it is required to satisfy not only higher absorption strength but also practical application requirements, i.e. the materials are required to have lower density, thinner matching thickness and wider absorption band. The traditional classic method for preparing the light wave-absorbing material, such as a core-shell structure, improves the electromagnetic wave absorption performance of the material by a thin shell film; the light carbon material and the magnetic material are compounded, so that the aim of light weight can be fulfilled, the impedance matching can be improved, the dielectric loss and the magnetic loss are matched, and the wave absorbing performance of the material is improved to a high degree. Therefore, the composite material of the carbon-based material and the magnetic material has great development in the wave absorbing field.
The porous metal structure type wave-absorbing material is prepared by taking a metal organic framework as a precursor, has the characteristics of structure and functional material, has the characteristics of light weight and high strength, and has a series of functions of heat preservation, shock absorption, sound absorption, electromagnetic shielding and the like. When the electromagnetic wave is transmitted in the porous material, besides the electromagnetic loss of the electromagnetic wave caused by the wave-absorbing medium, the foam cavities and the structures among the foam holes in the wave-absorbing material can also have certain functions of scattering, reflecting and the like on the electromagnetic wave, and the process can generate great loss on the electromagnetic wave. Therefore, compared with a solid material, the porous material has excellent wave-absorbing performance.
As a hotspot for development in recent years, the metal organic framework has the advantages of being wide in variety, large in specific surface area, high in porosity, simple in preparation process and the like, a cobalt-based imidazole organic framework (ZIF-67) is selected as a precursor, a carbon and cobalt composite material can be obtained in a one-step pyrolysis mode, in addition, the ZIF-67 has high thermal stability, and a carbon material obtained after sintering also has high graphitization property, so that the metal organic framework has important conditions for development into a light wave-absorbing material.
With regard to the preparation of the nano composite material by taking ZIF-67 as a precursor and the study of the performance of the nano composite material, the prior reports on the electrocatalysis, the capacitor and the gas adsorption performance of the nano composite material have no mature results on the wave absorbing performance, and the wave absorbing performance of the powder prepared in the prior reports is not ideal. According to the report of Journal of Materials Chemistry C2016, 4,186, the electromagnetic absorption performance of a Co @ NPC (NPC represents a carbon skeleton of a nanopore) sample obtained by carbonizing ZIF-67 serving as a precursor at 700 ℃ in nitrogen is researched, but the impedance matching performance is poor due to the high relative dielectric constant and low relative magnetic permeability, most electromagnetic waves are reflected on the surface of the material and cannot enter the material, so that the Co @ NPC sample shows poor microwave absorption performance, and the application of the Co @ NPC sample in a wave-absorbing material is limited. To improve impedance matching, TiO is obtained by hydrolyzing n-butyl titanate with Co @ NPC as core2Is a shell, namely the surface of Co @ NPC obtained by carbonizing ZIF-67 is directly coated with TiO2Obtaining Co @ NPC @ TiO2A core-shell structure. As a result, it was found that TiO could be controlled by the amount of hydrolysis of tetrabutyl titanate2The thickness of the shell is 1.5mm when 1.2ml of tetrabutyl titanate is added, and Co @ NPC @ TiO is prepared2The optimal value of the reflection loss is-31.7 dB. Firstly, the method obtains Co @ NPC in a one-step carbonization mode,but has poor wave absorbing performance, and is coated with TiO2Improved wave-absorbing performance, but poor maximum reflection loss, low yield, and coated TiO2The shell is not uniform.
According to the research on the microwave absorption performance of CuO @ NPC prepared by Zhang Xingzhang 28156569 of Nanjing university of aerospace and the like, Co @ NPC is prepared firstly, then a mixture of porous carbon loaded with copper nitrate is obtained by a method of impregnating the Co @ NPC with copper nitrate (obtained by removing metal Co in the Co @ NPC by 10 wt% of HF), and then the mixture is calcined under a proper condition to obtain a CuO-inlaid porous carbon composite (CuO @ NPC). Research shows that the CuO @ NPC composite material obtained under the calcination condition of 300 ℃ greatly improves the defect of poor impedance matching of the porous carbon, thereby improving the microwave absorption performance of the porous carbon. When the frequency of the CuO @ NPC is 14.9GHz and the matching thickness is 1.55mm at the temperature of-300 ℃, the optimal RL value can reach-57.5 dB, and the frequency bandwidth is 4.7 GHz. The method obviously improves the wave absorbing performance of Co @ NPC prepared by taking ZIF-67 as a precursor, but HF is used for many times in the experimental process, the danger coefficient is high, and the reflection loss in a low-frequency area is poor.
According to the invention patent (CN106563816A) of Li Cuiyan et al, Shanxi university of science and technology, a carbon source with a pore structure is soaked in a nickel salt solution for 20-30 h, then stirred and crushed by a stirrer, centrifuged, the centrifuged product is freeze-dried, the dried product is heated at 200-250 ℃ to decompose nickel salt, then the dried product is heated at 300-400 ℃ to carbonize a biomass material, and finally the biomass material is heated at 500-800 ℃ to realize catalytic graphitization of carbon, so that the composite material of porous carbon-loaded graphene coated nano nickel particles is obtained. The powder prepared by the method has small particle size, large specific surface area and more relative atoms on the particle surface, so that the interaction area with electromagnetic waves is large, and the energy of the dissipated electromagnetic waves is increased, thereby integrally improving the electromagnetic wave absorption performance of the material, but the preparation time is long, and the composite material of porous carbon loaded graphene coated nano nickel particles cannot be prepared at normal temperature.
According to the research report of Liuzhi et al, Jilin university, the Graphite Nanosheets (GNS) is introduced into the precursor by an in-situ polymerization methodIn polyamic acid solution with FeCl3As a pore size regulator and a magnetic particle source, the porous carbon/nano graphite microchip/ferromagnetic particle composite wave absorbing agent is prepared by the steps of pore forming by a liquid-induced phase separation method, thermal imidization, carbonization and the like. In this experiment, FeCl3The additive amount of the FeCl can influence the pore size of the material and the wave absorbing performance of the material, and finally the FeCl is determined3The addition amount is 0.2 wt.%, the average pore diameter is 120nm, the electromagnetic wave absorption performance is optimal, and when the thickness is 2.6mm, the maximum reflection loss of 93.4/GNS-5.1/Fe-1.5 to the electromagnetic wave of 8GHz reaches-36.5 dB. The method can influence the carbon crystallization degree of the material simply by controlling the addition amount of the graphite microchip, thereby influencing the electromagnetic wave absorption performance of the material, but the preparation process is complex, the preparation period is long, and the method is not suitable for large-scale production.
Preparation of Fe by Wet chemical coating method according to Material Application in EMC 2015,4, 52-613O4The coated porous carbon fiber mainly comprises the following steps: coarsening the porous carbon fiber washed by acetone and distilled water by 35 wt% concentrated nitric acid for 5h, washing by 10 wt% NaOH alkali for 10min, then washing by distilled water and drying; 1g of the treated porous carbon fiber was weighed and immersed in a sensitizer (30g/L SnCl)2And 37% HCl) and stirred slowly for 1h, and then rinsed with still water; putting the treated fiber into 100mL of silver ammonia solution for reaction for 15min, and filtering; then, the fibers were placed in 100mL of a reaction solution (10mmol/L Fe (NO)3)3And 30mmol/L dimethylaminoborane) at 90 ℃ for 1 h. After the reaction is finished, filtering, cleaning and drying are carried out to obtain mixed powder which is Fe3O4Coated porous carbon fibers. Compared with a sample which is not coated, the dielectric loss and the magnetic loss of the porous carbon fiber sample coated with ferroferric oxide are both increased, but the whole wave absorbing performance is general, strong acid and strong base are used for multiple times in the preparation process, and the danger coefficient is high.
Disclosure of Invention
The invention aims to provide a method for preparing Co/Co by one-step carbonization3O4Inlaid nano porous carbon composite wave-absorbing material (Co/Co for short in the following)3O4@ NPC), firstly preparing a metal organic framework ZIF-67 by a diffusion method and a coprecipitation method, taking the metal organic framework ZIF-67 as a precursor, calcining the ZIF-67 in a high-temperature protective atmosphere, and preparing Co/Co in a one-step carbonization mode3O4The @ NPC is used for testing the wave absorption performance, the preparation method is simple in process, low in raw material cost and simple in operation, the ZIF-67 precursor can be prepared at normal temperature and normal pressure in a one-step carbonization mode, and the powder shows excellent wave absorption performance in the subsequent wave absorption performance test.
The implementation process of the invention is as follows:
1. preparation of the reaction solution
Preparing a ZIF-67 precursor reaction solution: methanol and deionized water are used as solvents, and the organic ligand solution, the metal salt solution and the surfactant are prepared according to the proportion of 0.5-5 mol/L, 0.01-3.00 mol/L and 0.1-100 g/L, and are stirred for 20-30 minutes at the temperature of 20-30 ℃.
2、Co/Co3O4Preparation of inlaid nanoporous carbon composite materials
1) Preparation of ZIF-67 precursor: standing the solution prepared in the step 1 for 12-36 hours at 20-30 ℃, wherein a purple precipitate appears at the bottom of a beaker, and washing the ZIF-67 powder for 2-3 times by using methanol, ethanol and deionized water in sequence until the centrifuged solvent becomes a colorless transparent state, and then drying and collecting to obtain purple powder which is dried ZIF-67 powder;
2)Co/Co3O4preparation of @ NPC: calcining the purple powder obtained in the step 1) under a high-temperature protective atmosphere, wherein the calcining temperature is 500-800 ℃, the heating rate is 3-5 ℃ per minute, the heat preservation time is 3-6 hours, directly taking the powder out of a tubular furnace for air cooling when the temperature is reduced to 150-300 ℃, and collecting black powder after the powder is completely cooled to obtain Co/Co3O4A mosaic nanoporous carbon composite.
The metal salt is CoCl2·6H2O、CoSO4·7H2O and Co (NO)3)2·6H2O, or a salt thereof.
The surfactant is any one of polyvinylpyrrolidone (PVP K30), polyvinylpyrrolidone (PVP K15), Sodium Dodecyl Sulfate (SDS) and cetyltrimethylammonium bromide (CTAB).
The organic ligand solution is obtained by mixing 2-methylimidazole as a solute and methanol and deionized water as solvents.
The solvent is the mixture of methanol and deionized water, namely diluted methanol, wherein the volume ratio of the methanol to the deionized water is any one of 9:1, 8:1 and 7: 1.
The drying in the step 1) is to place the powder in a vacuum drying oven at the temperature of 60-80 ℃ for 10-24 hours.
The invention is characterized in that cheap methanol and deionized water are used as solvents, a ZIF-67 precursor is firstly prepared by a diffusion method and a coprecipitation method, then the dried ZIF-67 powder is calcined in a high-temperature protective atmosphere, and when the temperature is reduced to be near a certain temperature, the powder is taken out for air cooling. The particle size of the product, whether the product is oxidized, the degree of oxidation and the like can be adjusted by changing process factors such as the type of the metal salt, the concentration of the metal salt, the type of the solvent, the reaction temperature, the reaction time, the addition of the surfactant, the calcining temperature, the heating rate, the type of the protective atmosphere, the air cooling temperature and the like, so that the particle size and the morphology of the product are determined, and the excellent performance of the product is further determined.
Compared with the prior art, the preparation method has the advantages of simple process, mild reaction conditions and low preparation cost, the precursor can be directly prepared by a simple diffusion method and a coprecipitation method at normal temperature and normal pressure, and finally the powder with excellent wave absorption performance can also be directly prepared by a one-step carbonization method. Particularly, the Co/Co can be easily realized by changing the process conditions such as the type of metal salt, the concentration of metal salt, the addition of surfactant, the calcination temperature and the initial air cooling temperature3O4The wave-absorbing performance of the product is controlled by controlling and adjusting the components and the particle size of the inlaid porous carbon nano powder. Adopt the bookCo/Co prepared by invention3O4@ NPC in the shape of a rhombic dodecahedron, with a grain size of Co/Co embedded in the dodecahedron3O4The nanoparticles being spherical, Co/Co3O4The particle size of the nano particles is 15-50 nm, the particle size distribution is uniform, and the appearances of the nano particles are shown in figures 1-7; prepared Co/Co3O4The phase analysis of the @ NPC nanopowder is shown in FIG. 8; Co/Co3O4The reflection loss of the @ NPC nanoparticle powder is shown in FIG. 9.
Drawings
FIG. 1 shows the Co/Co prepared in example 13O4@ NPC nanoparticle powder SEM photograph;
FIG. 2 shows Co/Co prepared in example 23O4@ NPC nanoparticle powder SEM photograph;
FIG. 3 shows Co/Co prepared in example 33O4@ NPC nanoparticle powder SEM photograph;
FIG. 4 shows Co/Co prepared in example 43O4@ NPC nanoparticle powder SEM photograph;
FIG. 5 shows the Co/Co prepared in example 53O4@ NPC nanoparticle powder SEM photograph;
FIG. 6 shows Co/Co prepared in example 63O4@ NPC nanoparticle powder SEM photograph;
FIG. 7 shows Co/Co prepared in example 73O4@ NPC nanoparticle powder SEM photograph;
FIG. 8 shows Co/Co prepared in example 73O4@ NPC nanoparticle powder XRD pattern;
FIG. 9 shows Co/Co prepared in example 43O4@ NPC nanoparticle powder reflection loss diagram.
Detailed Description
Example 1:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized water7:1 as solvent, and preparing a solution according to the following proportion.
CoCl2·6H2O-------------------0.04mol/L
PVP K30------------------------0.8g/L
(Metal salt solution)
2-methylimidazolium- -0.6mol/L
(organic ligand solution)
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 60 ℃ for 12 hours, and collecting;
3) the purple powder is dispersed in a magnetic boat for calcination, the magnetic boat is placed in a tube furnace protected by argon, the heating rate is 5 ℃/min, and the temperature is kept at 500 ℃ for 5 h;
4) and (4) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 300 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 32 nm. The morphology is shown in FIG. 1.
Example 2:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized water7:1 as solvent, and preparing a solution according to the following proportion.
CoCl2·6H2O-------------------0.12mol/L
PVP K30------------------------12g/L
2-methylimidazolium-1.2 mol/L
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 60 ℃ for 18 hours, and collecting;
3) the purple powder is dispersed in a magnetic boat for calcination, the magnetic boat is placed in a tube furnace protected by argon, the heating rate is 5 ℃/min, and the temperature is kept at 600 ℃ for 5 h;
4) and (5) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 280 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 30 nm. The morphology is shown in fig. 2.
Example 3:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized water7:1 as solvent, and preparing a solution according to the following proportion.
CoCl2·6H2O-------------------0.40mol/L
PVP K15------------------------40g/L
2-methylimidazolium-1.8 mol/L
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 60 ℃ for 24 hours, and collecting;
3) dispersing the purple powder in a magnetic boat, placing the magnetic boat in a tube furnace protected by argon, heating at a rate of 5 ℃/min, and keeping the temperature at 700 ℃ for 5 h;
4) and (5) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 260 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 28 nm. The morphology is shown in fig. 3.
Example 4:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized waterThe solution is prepared by using a solvent with the ratio of 8:1 according to the following proportion.
CoCl2·6H2O-------------------1.2mol/L
PVP K15------------------------80g/L
2-methylimidazolium-2.4 mol/L
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 70 ℃ for 12 hours, and collecting;
3) the purple powder is dispersed in a magnetic boat for calcination, the magnetic boat is placed in a tube furnace protected by argon, the heating rate is 5 ℃/min, and the temperature is kept at 800 ℃ for 5 h;
4) and (4) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 250 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 28 nm. The morphology is shown in fig. 4. The reflection loss absorption spectrum is shown in fig. 9.
Example 5:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized waterThe solution is prepared by using a solvent with the ratio of 8:1 according to the following proportion.
Co(NO3)2·6H2O------------------0.12mol/L
SDS----------------------12g/L
2-methylimidazolium-3.2 mol/L
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 70 ℃ for 18h, and collecting;
3) the purple powder is dispersed in a magnetic boat for calcination, the magnetic boat is placed in a tube furnace protected by argon, the heating rate is 5 ℃/min, and the temperature is kept at 600 ℃ for 5 h;
4) and (5) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 280 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 28 nm. The morphology is shown in fig. 5.
Example 6:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized waterThe solution is prepared by using a solvent with the ratio of 8:1 according to the following proportion.
Co(NO3)2·6H2O------------------0.4mol/L
CATB-----------------------40g/L
2-methylimidazolium-4.2 mol/L
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 70 ℃ for 24 hours, and collecting;
3) the purple powder is dispersed in a magnetic boat for calcination, the magnetic boat is placed in a tube furnace protected by argon, the heating rate is 5 ℃/min, and the temperature is kept at 700 ℃ for 5 h;
4) and (5) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 260 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 28 nm. The morphology is shown in fig. 6.
Example 7:
1. preparation of the reacted solution:
1) preparing a ZIF-67 precursor reaction solution:
with VMethanol：VDeionized waterThe solution is prepared by using 9:1 solvent according to the following proportion.
Co(NO3)2·6H2O------------------1.2mol/L
CATB-----------------------80g/L
2-methylimidazolium-4.8 mol/L
Temperature- -25 deg.C
Stirring time- -20min
2、Co/Co3O4Preparing the inlaid nano porous carbon composite material:
1) standing the solution prepared by the method at 25 ℃ for 24h to ensure that purple precipitate appears at the bottom of a beaker;
2) centrifugally separating the solution, washing ZIF-67 powder with ethanol for 3 times, drying in a vacuum drying oven at 80 ℃ for 24 hours, and collecting;
3) the purple powder is dispersed in a magnetic boat for calcination, the magnetic boat is placed in a tube furnace protected by argon, the heating rate is 5 ℃/min, and the temperature is kept at 800 ℃ for 5 h;
4) and (4) taking out the magnetic boat for air cooling when the temperature of the tube furnace is reduced to 250 ℃, and grinding and collecting after the magnetic boat is completely cooled.
The obtained powder is rhombic dodecahedron, the organic framework is uniformly distributed, and fine spherical Co nano particles are embedded in holes of the organic framework. The average particle size of the Co nanoparticles was 28 nm. The morphology is shown in FIG. 7. The XRD pattern is shown in figure 8.
Claims (4)
1. Co/Co3O4The preparation method of the inlaid nano porous carbon wave-absorbing material is characterized by comprising the following specific steps:
1) preparation of the reaction solution
Preparing a ZIF-67 precursor reaction solution: methanol and deionized water are used as solvents, and are prepared according to the proportion of 0.5-5 mol/L of organic ligand solution, 0.01-3.00 mol/L of metal salt solution and 0.1-100 g/L of surfactant, and the mixture is stirred for 20-30 minutes at the temperature of 20-30 ℃;
2)Co/Co3O4preparation of inlaid nanoporous carbon composite materials
a) Preparation of ZIF-67 precursor: standing the solution prepared in the step 1) for 12-36 hours at 20-30 ℃, wherein a purple precipitate appears at the bottom of a beaker, and washing the ZIF-67 powder for 2-3 times by using methanol, ethanol and deionized water in sequence until the centrifuged solvent becomes a colorless transparent state, and then drying and collecting to obtain purple ZIF-67 powder;
b)Co/Co3O4preparation of @ NPC: calcining the purple powder obtained in the step a) under a high-temperature protective atmosphere, wherein the calcining temperature is 500-800 ℃, the heating rate is 3-5 ℃ per minute, the heat preservation time is 3-6 hours, when the temperature is reduced to 150-300 ℃, the powder is directly taken out of a tubular furnace for air cooling, and after the powder is completely cooled, black powder is collected, so that Co/Co powder can be obtained3O4A nano porous carbon composite material;
the metal salt is CoCl2·6H2O、CoSO4·7H2O and Co (NO)3)2·6H2Any one of O;
the organic ligand solution is obtained by mixing 2-methylimidazole as a solute and methanol and deionized water as solvents.
2. Co/Co according to claim 13O4The preparation method of the inlaid nano porous carbon wave-absorbing material is characterized in that the surfactant is any one of polyvinylpyrrolidone PVP K30, polyvinylpyrrolidone PVP K15, sodium dodecyl sulfate SDS and cetyltrimethylammonium bromide CTAB.
3. Co/Co according to claim 13O4The preparation method of the inlaid nano porous carbon wave-absorbing material is characterized in that the solvent is a mixture of methanol and deionized water, namely diluted methanol, wherein the volume ratio of the methanol to the deionized water is any one of 9:1, 8:1 and 7: 1.
4. Co/Co according to claim 13O4The preparation method of the inlaid nano porous carbon wave-absorbing material is characterized in that the drying in the step a) is to dry the powder in a vacuum drying oven at the temperature of 60-80 ℃ for 10-24 hours.
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| CN114480907B (en) * | 2020-10-23 | 2022-07-01 | 天津师范大学 | Carbon-based/metal composite material and preparation method thereof |
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