CN115305053A - Cerium-based hollow nano wave-absorbing material and preparation method and application thereof - Google Patents
Cerium-based hollow nano wave-absorbing material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 94
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 51
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011358 absorbing material Substances 0.000 title claims abstract description 49
- 239000002105 nanoparticle Substances 0.000 claims abstract description 68
- 150000000703 Cerium Chemical class 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 230000007547 defect Effects 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000002356 single layer Substances 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- NKAAEMMYHLFEFN-ZVGUSBNCSA-M sodium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Na+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O NKAAEMMYHLFEFN-ZVGUSBNCSA-M 0.000 claims description 2
- 229940045136 urea Drugs 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 69
- 239000000463 material Substances 0.000 abstract description 25
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- -1 organic acid salt Chemical class 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 33
- 238000004458 analytical method Methods 0.000 description 31
- 238000002310 reflectometry Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000175 cerite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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Abstract
The invention discloses a cerium-based hollow nano wave-absorbing material as well as a preparation method and application thereof, belonging to the technical field of nano microwave-absorbing materials. The invention adopts a one-step hydrothermal method to prepare the amorphous structure CeOHCO for the first time 3 Hollow nanoparticles and polycrystalline CeO 2 The wall thickness of the hollow nano particles is 9.0-26.5 nm. The CeOHCO is regulated and controlled by changing the concentration of the surfactant, the quantity ratio of the organic acid salt to the cerium salt and the reaction time in the system 3 The wall thickness and size of the amorphous hollow nanoparticles, and the resulting material has excellent microwave absorption characteristics. The controllable preparation process disclosed by the invention is simple and the product has novel appearance, overcomes the defects of harsh reaction conditions, difficult regulation and control of the appearance of the reaction product, poor experimental repeatability and the like in the conventional preparation process, and has good industrial application potential.
Description
Technical Field
The invention belongs to the technical field of nano microwave absorbing materials, and relates to a preparation method of a cerium-based hollow nano wave absorbing material and application of the cerium-based hollow nano wave absorbing material in preparation of nano electronic equipment, sensors, supercapacitors and photocatalysis or lithium ion batteries.
Background
The hollow structure nano particles have good application prospect in the fields of energy storage, catalysts, fuel cells and the like due to the unique structural characteristics of low density, high specific surface area and the like, so that the hollow structure nano particles are widely researched. In addition, the composite material has the unique advantages of high defect, low density, high surface and interface, adjustable conductivity and the like, and has great application potential in the field of electromagnetic wave absorption.
Solids are currently classified according to atomic order and arrangement into crystalline/quasicrystalline and amorphous. Compared with crystalline solid, the amorphous material has the following four characteristics: (i) long range atomic disorder; (ii) isotropic physical and chemical properties; (iii) Are metastable, but can be relaxed in crystallinity by heat or pressure; (iv) no specific melting point, but a glass transition temperature. Among them, the nano amorphous material is an important amorphous solid, and the specific surface area of the nano amorphous material is larger than that of the bulk material, so that the nano amorphous material can show better performance. CeOHCO 3 Applied to many fields due to the presence of a specific 4f electron shell inside, and is the preparation of CeO 2 One of the most important precursors, ceO after calcination 2 Generally inherit the morphology of the corresponding precursor. CeOHCO which is common at present 3 The appearance of (A) mainly comprises: nanoparticles, spindle-shaped, hollow nanocubes, spherical microcrystals, triangular microcrystalsOrifice plates, and the like. Among them, chinese patent document (CN 102596810B) discloses a method for producing a cerium carbonate compound, in which synthesis of the cerium carbonate compound is achieved by reacting cerite at a temperature of about 50 ℃ or higher, but the product is orthorhombic cerous oxycarbonate hydrate [ Ce 5363B ] 2 O(CO 3 ) 2 ·H 2 O]Hexagonal cerous carbonate [ Ce (OH). ((CO)) 3 )]Or mixtures thereof, it is difficult to obtain a single pure amorphous product; chinese patent document (CN 108178178A) discloses a method for preparing small-particle-size basic cerium carbonate, but the experimental process needs a large amount of pure water to leach and precipitate, and the operation is complicated; chinese patent document (CN 103896322B) discloses a preparation method of dendritic basic cerium carbonate, urea is used as a precipitator, and the basic cerium carbonate is synthesized by a hydrothermal method, but the urea has more pyrolytic reaction and lower experimental yield. In addition, most of the basic cerium carbonate is orthorhombic or hexagonal, and a hollow nanoparticle structure having an amorphous structure has not been reported.
With the rapid development of 5G mobile networks, the development of high-performance electromagnetic wave absorbing structures/wave absorbers is urgently needed to solve the problem of increasingly serious electromagnetic interference. Among various candidate materials, the amorphous nano cerium-based material has wide application prospect in the wave-absorbing field. However, the morphology and size of the existing cerium-based wave-absorbing material are difficult to regulate, the experimental steps are complicated, the conditions are harsh, the operation is complex, the experimental repeatability is poor, and in addition, the wave-absorbing performance of the existing cerium-based wave-absorbing material is difficult to meet the requirements of thinness, lightness, width and strength.
Therefore, the problem to be solved by the skilled person is to develop an amorphous nano cerium-based material with simple process, easy industrialization, controllable morphology and size, and better microwave absorption performance.
Disclosure of Invention
In view of the above, the present invention provides a cerium-based hollow nano wave-absorbing material with simple process and controllable size, aiming at the problems existing in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a cerium-based hollow nano wave-absorbing material is prepared from cerium-based hollow nano wave-absorbing materialCeOHCO 3 And CeO 2 Hollow nanoparticles; wherein, the first and the second end of the pipe are connected with each other,
CeOHCO 3 the hollow nano particles are in an amorphous single-layer shell hollow structure, the outer diameter of the hollow nano particles is 113-348 nm, and the wall thickness of the hollow nano particles is 9.5-26.5 nm;
CeO 2 the hollow nano particles are of a polycrystalline single-layer or double-layer shell hollow structure, the outer diameter of the hollow nano particles is 80-208 nm, and the wall thickness of the hollow nano particles is 9.0-12.5 nm.
The cerium-based hollow nano wave-absorbing material disclosed by the invention has excellent microwave absorption characteristics, wherein the maximum effective bandwidth of the reflectivity of less than or equal to-10 dB is 4.72-10.08 GHz, and the maximum absorption is-37.50-47.93 dB.
The invention also aims to provide a preparation method of the cerium-based hollow nano wave-absorbing material, which is environment-friendly and suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cerium-based hollow nano wave-absorbing material comprises the step of preparing amorphous CeOHCO by adopting a one-step hydrothermal method 3 Hollow nanoparticles and preparation of polycrystalline CeO by annealing process 2 Hollow nanoparticles;
wherein, the CeOHCO 3 The preparation method of the hollow nano particles specifically comprises the following steps:
(1) Weighing a certain mass of surfactant, cerium salt, a carbon source and alkali, dissolving in deionized water, and stirring at room temperature to obtain a uniform mixed solution;
(2) Sealing the mixed solution in a reaction kettle, putting the reaction kettle into an oven, and reacting for a certain time at a certain temperature to obtain a precipitate;
(3) Centrifugally washing and drying the precipitate to finally obtain the amorphous CeOHCO 3 Hollow nanoparticles.
By adopting the technical scheme, the invention has the following beneficial effects:
the preparation method disclosed by the invention is simple to operate, the product morphology is novel, the characteristics of harsh reaction conditions, difficult regulation and control of the reaction product morphology, poor experimental repeatability and the like in the conventional preparation process are overcome, and the preparation method has good industrial application potential.
Furthermore, it is worth mentioning that the present invention provides for the preparation of CeOHCO by a one-step hydrothermal process 3 Compared with the existing method, the nano cerium-based material absorbent obtained by the invention is of an amorphous hollow structure, has great innovation in appearance and property, and has the advantages of high experimental repeatability, simple steps and low requirement on instrument precision.
Further, the invention prepares CeOHCO by a one-step hydrothermal method 3 The amorphous hollow nano-particle not only has novel appearance, but also can regulate and control CeOHCO by changing the concentration of a surfactant, the quantity ratio of organic acid salt to cerium salt and the reaction time in a system 3 The wall thickness and size of the amorphous hollow nanoparticles provide excellent microwave absorption characteristics.
Preferably, the surfactant in the step (1) is polyacrylic acid, and the ratio of the volume of the surfactant to the amount of the cerium salt substance is 0 to 8mL/mmol.
Preferably, the alkali and the carbon source in the step (1) are at least one of sodium hydrogen tartrate, sodium tartrate and urea, and the amount ratio of the carbon source to the cerium salt is (1-4): 1.
More preferably, the cerium salt is cerium chloride, and the concentration of the cerium salt is 0.003 to 0.012mol/L.
Preferably, in the step (2), the reaction time is 0.5-48 h, and the reaction temperature is 160-220 ℃.
Preferably, the rotation speed of centrifugal washing in the step (3) is 3000-10000 rpm, and the centrifugal time is 3-5 min; the drying temperature is 60-90 ℃, and the drying time is 6-10 h.
Further, the polycrystalline CeO 2 The preparation method of the hollow nano particles specifically comprises the following steps:
the prepared amorphous CeOHCO 3 Annealing hollow nano particles at 300-600 ℃ for 1-4 h to obtain polycrystalline CeO with adjustable specific surface area, shell structure and oxygen vacancy defect 2 Hollow nanoparticles;
wherein the heating rate is 2.0-10.0 ℃/min.
And, the polycrystalline CeO 2 The hollow nano particles have the outer diameter of 80-208 nm, the wall thickness of 9.0-12.5 nm and the specific surface area of 19.4-151.2 m 2 The grain size is 2.7-6.0 nm, and the oxygen vacancy concentration is 10-30%;
and the double-shell hollow nano particles are obtained at 300-400 ℃; the single-layer shell hollow nano particles are obtained at 500-600 ℃.
The invention also aims to provide the application of the cerium-based hollow nano wave-absorbing material in sensors, supercapacitors, photocatalysis or lithium ion batteries.
According to the technical scheme, compared with the prior art, the cerium-based hollow nano wave-absorbing material and the preparation method and application thereof provided by the invention have the following excellent effects:
1. the invention adopts a one-step hydrothermal method to prepare the amorphous hollow CeOHCO 3 The wall thickness of the nano-particles is 9.5-26.5 nm. Based on the material, the CeOHCO can be regulated and controlled by changing the concentration of a surfactant, the quantity ratio of organic acid salt to cerium salt, the type of the cerium salt, the reaction temperature and the reaction time in the system 3 The wall thickness and the size of the amorphous hollow nano particles, and the obtained material has excellent microwave absorption property;
2. the invention discloses a CeOHCO 3 The amorphous hollow nano particles are prepared by a one-step hydrothermal method, so that the preparation method has the advantages of simple process, good repeatability and large-scale production; the compound prepared by the method has the excellent characteristics of novel structure, good dispersity and uniformity, adjustable size and the like;
3. the invention discloses the CeOHCO with amorphous property 3 The preparation method of the hollow nanoparticles is convenient to operate, green and environment-friendly, has low requirement on instrument precision, and has good industrial application potential.
Therefore, in conclusion, the cerium-based hollow nano wave-absorbing material disclosed and protected by the invention has great market popularization and application values.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIGS. 1 to 3 are phase, microstructure and SAED patterns of the product obtained in example 1 of the present invention measured under XRD and transmission electron microscope, respectively.
Fig. 4 to 5 show the phase and microstructure of the product obtained in example 2 of the present invention under XRD and transmission electron microscope, respectively. .
FIG. 6 shows the microstructure of the product obtained in example 3 of the present invention measured under a transmission electron microscope.
FIG. 7 shows the microstructure of the product obtained in example 4 of the present invention measured under a transmission electron microscope.
FIG. 8 shows the microstructure of the product obtained in example 5 of the present invention measured under a transmission electron microscope.
FIG. 9 shows the microstructure of the product obtained in example 6 of the present invention measured under a transmission electron microscope.
FIG. 10 shows the microstructure of the product obtained in example 7 of the present invention measured under a transmission electron microscope.
FIG. 11 shows the microstructure of the product obtained in example 8 of the present invention measured under a transmission electron microscope.
FIG. 12 shows the microstructure of the product obtained in example 9 of the present invention measured under a transmission electron microscope.
FIG. 13 shows the microstructure of the product obtained in example 10 of the present invention measured under a transmission electron microscope.
FIG. 14 shows the microstructure of the product obtained in example 11 of the present invention measured by transmission electron microscopy.
FIG. 15 shows the phases of the products of examples 11, 12 and 13 of the present invention measured by XRD.
FIG. 16 shows the microstructure of the product obtained in example 12 of the present invention measured under a transmission electron microscope.
FIG. 17 shows the microstructure of the product obtained in example 13 of the present invention measured under a transmission electron microscope.
FIG. 18 shows the microstructure of the product obtained in example 14 of the present invention measured under a transmission electron microscope.
FIG. 19 shows the microstructure of the product obtained in example 15 of the present invention measured under a transmission electron microscope.
FIG. 20 shows the microstructure of the product obtained in example 16 of the present invention measured under a transmission electron microscope.
FIG. 21 shows the microstructure of the product obtained in example 17 of the present invention measured under a transmission electron microscope.
FIG. 22 shows the morphology of the product of comparative experiment 1 under a scanning electron microscope.
FIG. 23 is the profile of the product of comparative experiment 2 under SEM.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a cerium-based hollow nano wave-absorbing material with simple and convenient process, controllable size and good microwave absorption property.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a cerium-based hollow nano wave-absorbing material comprises the following steps:
0.1863g (0.5 mmol) CeCl 3 ·7H 2 O, dissolved in a 0.024mol/L NaHtar (61.6 mL,1.5 mmol) solution and magnetically stirred at room temperature for 30min to form a cerous tartrate complex. Then, 2mL of PAA was added to the solution, and after stirring for 60 minutes, 0.168mol/L of sodium hydroxide (17.8 mL) was added thereto, and the mixture was stirred for 30 minutes to mix the mixture uniformly. The solution was then transferred to a teflon liner and placed in a high temperature oven to react for 24h at 200 ℃. Naturally cooling the product to room temperature, washing the product with deionized water, and drying the product in a drying oven at 60 ℃ to finally obtain the CeOHCO 3 Amorphous hollow nanoparticles.
The phase and microstructure of the obtained product measured by XRD and transmission electron microscope are shown in FIGS. 1-3. The analysis shows that the product is hollow nanometer particle with amorphous structure, the outer diameter is 144-276 nm and the wall thickness is about 20.5nm.
The heterogeneous material is filled in a substrate material by 50% of mass fraction, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 3.60GHz, the thickness is 2.2mm, and the maximum reflection loss is-42.72 dB.
Example 2
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: PAA is not added, and the other preparation steps and the process parameters are the same.
The phase and microstructure of the obtained product measured by XRD and transmission electron microscope are shown in FIGS. 4-5. From the above analysis, it was found that the product was a polycrystalline CeOHCO 3 Flower-like hierarchical structure.
Analysis shows that CeOHCO is added after PAA is added 3 Phase change.
The heterogeneous material is filled in a substrate material by 50 percent of mass fraction, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 4.80GHz, the thickness is 2.2mm, and the maximum reflection loss is-33.55 dB.
Example 3
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the whole concentration of the reactants is reduced to 1/2 of the original concentration, and the rest preparation steps and process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 6. The analysis shows that the product is hollow nanometer particle with amorphous structure, the outer diameter is 222-348 nm, and the wall thickness is about 21.5nm. Analysis revealed that the wall thickness of the hollow nanoparticles was slightly greater than that of example 1.
Example 4
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the whole concentration of the reactant is enlarged to 2 times of the original concentration, and the rest preparation steps and process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 7. The analysis shows that the product is hollow nanometer particle with amorphous structure, outer diameter of 138-262 nm and wall thickness of 18.0nm. Analysis revealed that the wall thickness of the hollow nanoparticles was slightly smaller than that of example 1.
Example 5
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: tar (r) 2- :Ce 3+ =1:1, and the rest preparation steps and process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 8. The analysis shows that the product is amorphous nano particle with outer diameter of 113-202 nm and wall thickness of 18.0nm. Analysis shows that the hollow nanoparticles have hollow structures.
Example 6
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: tar (r) 2- :Ce 3+ =4:1, and the rest preparation steps and process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 9. The analysis shows that the product is hollow nanometer particle with amorphous structure, outer diameter of 157-287 nm and wall thickness of 20.0nm. Analysis shows that the size and the wall thickness of the hollow nanoparticles are close to those of example 1.
Example 7
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the amount of PAA added is 0.5mL, and the other preparation steps and the process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 10. The analysis shows that the product is hollow nanometer particle with amorphous structure, outer diameter of 167-228 nm and wall thickness of 9.5nm.
Analysis revealed that the wall thickness of the hollow nanoparticles was significantly smaller than in example 1.
The heterogeneous material is filled in a substrate material by 50% of mass fraction, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 6.08GHz, the thickness is 2.3mm, and the maximum reflection loss is-47.90 dB.
Example 8
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the amount of PAA added is 4mL, and the other preparation steps and the technological parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 11. The analysis shows that the product is hollow nanometer particle with amorphous structure, outer diameter 205-317 nm and wall thickness 26.5nm.
Analysis revealed that the wall thickness of the hollow nanoparticles was significantly larger than in example 1, and gradually increased as the amount of PAA increased.
The heterogeneous material is filled in a substrate material by 50% of mass fraction, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 3.92GHz, the thickness is 2.1mm, and the maximum reflection loss is-36.30 dB.
Example 9
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the reaction time is 0.5h, and the other preparation steps and the process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 12. The analysis shows that the product is hollow nanometer particle with amorphous structure, the outer diameter is 130-232 nm and the wall thickness is 13.0nm.
Analysis revealed that the wall thickness of the hollow nanoparticles was significantly smaller than in example 1.
Example 10
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the reaction time is 48h, and the other preparation steps and the process parameters are the same.
The microstructure of the resulting product measured under a transmission electron microscope is shown in FIG. 13. The analysis shows that the product is hollow nanometer particle with amorphous structure, outer diameter of 167-283 nm and wall thickness of 22.0nm.
Analysis shows that the wall thickness of the hollow nanoparticles is slightly larger than that of example 1, and the wall thickness gradually increases with the increase of the reaction time.
Example 11
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the product is annealed at 300 ℃ for 4h, the heating rate is 5.0 ℃/min, and the other preparation steps and technological parameters are the same.
The morphology of the obtained product measured under a transmission electron microscope is shown in figure 14, and the phase XRD is shown in figure 15. As can be seen from the above analysis, the product was a double-layer structured CeO 2 The hollow nano-particle has the diameter of 94-169 nm, the shell thickness of 10.5nm and the specific surface area of 75.88m 2 (ii)/g, the crystal grain size was 2.7nm, and the oxygen vacancy concentration was 10%.
The heterogeneous material is filled in a substrate material by mass fraction of 45%, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 4.06GHz, the thickness is 2.2mm, and the maximum reflection loss is-31.49 dB.
Analysis shows that the wall thickness of the annealed hollow nanoparticles is significantly smaller than in example 1.
Example 12
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the product is annealed for 2 hours at 400 ℃, and the rest preparation steps and technological parameters are the same.
The morphology of the obtained product measured under a transmission electron microscope is shown in figure 16, and the phase XRD is shown in figure 15. As can be seen from the above analysis, the product was a double-layer structured CeO 2 The hollow nano-particle has the diameter of 95-208 nm, the shell thickness of 12.5nm and the specific surface area of 76.8m 2 (ii)/g, the crystal grain size was 3.2nm, and the oxygen vacancy concentration was 10%.
The heterogeneous material is filled in a substrate material by 50 percent of mass fraction, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 5.44GHz, the thickness is 2.6mm, and the maximum reflection loss is-43.28 dB.
Analysis revealed that the wall thickness of the hollow nanoparticles after annealing was significantly smaller than in example 1.
Example 13
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the product is annealed for 1h at 600 ℃, and the rest preparation steps and technological parameters are the same.
The microstructure of the obtained product measured under a transmission electron microscope is shown in FIG. 17, and the phase XRD is shown in FIG. 15. From the above analysis, it can be seen that the product is a hollow CeO having a monolayer structure 2 The nano particles have the diameter of 80-120 nm, the shell thickness of 9.0nm and the specific surface area of 54.21m 2 (ii)/g, the crystal grain size was 6.0nm, and the oxygen vacancy concentration was 10%.
The heterogeneous material is filled in a substrate material by 50% of mass fraction, and the measured reflectivity is shown in table 1, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 4.64GHz, the thickness is 3.0mm, and the maximum reflection loss is-46.89 dB.
Analysis shows that the wall thickness of the hollow nano particles after annealing is obviously smaller than that of the hollow nano particles in the example 1, and the product CeO is increased along with the increase of the annealing temperature 2 The peak of (a) is enhanced, indicating the phaseIs changed over.
Example 14
Compared with the preparation steps disclosed in the embodiment 12, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the heating rate is 2.0 ℃/min, and the other preparation steps and the process parameters are the same.
The microstructure of the obtained product measured under a transmission electron microscope is shown in FIG. 18, and the analysis shows that the product is a hollow CeO with a single-layer structure 2 The diameter of the nano particle is 85-168 nm, and the shell thickness is 10.0nm.
Example 15
Compared with the preparation steps disclosed in the embodiment 12, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the heating rate is 10.0 ℃/min, and the other preparation steps and the technological parameters are the same.
The microstructure of the obtained product measured under a transmission electron microscope is shown in FIG. 19, and the analysis shows that the product is a single-layer hollow CeO 2 The diameter of the nano particle is 88-152 nm, and the shell thickness is 12.0nm.
Example 16
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the reaction temperature is 160 ℃, and the other preparation steps and process parameters are the same.
The microstructure of the obtained product measured under a transmission electron microscope is shown in fig. 20, and the analysis shows that the product is a hollow nanoparticle with an amorphous structure.
Example 17
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the reaction temperature is 220 ℃, and the other preparation steps and process parameters are the same.
The microstructure of the obtained product measured under a transmission electron microscope is shown in fig. 21, and the analysis shows that the product is a hollow nanoparticle with an amorphous structure.
The inventive content is not limited to the content of the above-mentioned embodiments, wherein combinations of one or several of the embodiments may also achieve the object of the invention.
To further verify the excellent effects of the present invention, the inventors also conducted the following experiments:
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB), and the rest preparation steps and process parameters are the same.
The microstructure of the obtained product measured under SEM is shown in fig. 22, and it is understood from the above analysis that other surfactants cannot obtain hollow nanostructures.
Comparative experiment 2
Compared with the preparation steps disclosed in the embodiment 1, the only difference of the preparation method of the cerium-based hollow nano wave-absorbing material is that: the surfactant is added to be polyvinylpyrrolidone K30 (PVP), and the other preparation steps and the process parameters are the same.
The microstructure of the obtained product measured under SEM is shown in fig. 23, and it is understood from the above analysis that other surfactants cannot obtain a hollow nanostructure.
In addition, in order to further illustrate the excellent effects of the present patent application compared with the prior art and to highlight the non-obvious property of the technology, the inventors also measured the wave-absorbing properties of the products obtained in the above-mentioned examples, and the specific data are shown in table 1:
TABLE 1 wave absorption Properties of the products obtained in some of the examples of the invention
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The cerium-based hollow nano wave-absorbing material is characterized in that the cerium-based hollow nano wave-absorbing material is CeOHCO 3 And CeO 2 Hollow nanoparticles; wherein the content of the first and second substances,
CeOHCO 3 the hollow nano particles are in an amorphous single-layer shell hollow structure, the outer diameter of the hollow nano particles is 113-348 nm, and the wall thickness of the hollow nano particles is 9.5-26.5 nm;
CeO 2 the hollow nano particles are of a polycrystalline single-layer or double-layer shell hollow structure, the outer diameter of the hollow nano particles is 80-208 nm, and the wall thickness of the hollow nano particles is 9.0-12.5 nm.
2. The preparation method of the cerium-based hollow nano wave-absorbing material as claimed in claim 1, wherein the method comprises preparing amorphous CeOHCO by a one-step hydrothermal method 3 Hollow nanoparticles and preparation of polycrystalline CeO by annealing process 2 Hollow nanoparticles;
wherein, the CeOHCO 3 The preparation method of the hollow nano particles specifically comprises the following steps:
(1) Weighing a certain mass of surfactant, cerium salt, a carbon source and alkali, dissolving in deionized water, and stirring at room temperature to obtain a uniform mixed solution;
(2) Sealing the mixed solution in a reaction kettle, putting the reaction kettle into an oven, and reacting for a certain time at a certain temperature to obtain a precipitate;
(3) Centrifugally washing and drying the precipitate to finally obtain the amorphous CeOHCO 3 Hollow nanoparticles.
3. The preparation method of the cerium-based hollow nano wave-absorbing material according to claim 2, wherein the surfactant in the step (1) is polyacrylic acid, and the ratio of the volume of the surfactant to the amount of the cerium salt substance is 0-8 mL/mmol.
4. The preparation method of the cerium-based hollow nano wave-absorbing material according to claim 2, wherein the alkali and the carbon source in the step (1) are at least one of sodium hydrogen tartrate, sodium tartrate and urea, and the ratio of the amount of the carbon source to the amount of the cerium salt is (1-4): 1.
5. The method for preparing the cerium-based hollow nano wave-absorbing material as claimed in claim 3 or 4, wherein the cerium salt is cerium chloride, and the quantity concentration of the cerium salt is 0.003-0.012 mol/L.
6. The preparation method of the cerium-based hollow nano wave-absorbing material according to claim 2, wherein in the step (2), the reaction time is 0.5-48 h, and the reaction temperature is 160-220 ℃.
7. The preparation method of the cerium-based hollow nano wave-absorbing material according to claim 2, wherein the rotation speed of the centrifugal washing in the step (3) is 3000-10000 rpm, and the centrifugal time is 3-5 min; the drying temperature is 60-90 ℃, and the drying time is 6-10 h.
8. The preparation method of the cerium-based hollow nano wave-absorbing material as claimed in claim 2, wherein the polycrystalline CeO is 2 The preparation method of the hollow nano particles specifically comprises the following steps:
the prepared amorphous CeOHCO 3 Annealing hollow nano particles at 300-600 ℃ for 1-4 h to obtain polycrystalline CeO with adjustable specific surface area, shell structure and oxygen vacancy defect 2 Hollow nanoparticles;
wherein the heating rate is 2.0-10.0 ℃/min.
9. According to claimThe preparation method of the cerium-based hollow nano wave-absorbing material is characterized in that the polycrystalline CeO 2 The hollow nano particles have the outer diameter of 80-208 nm, the wall thickness of 9.0-12.5 nm and the specific surface area of 19.4-151.2 m 2 Per gram, the grain size is 2.7-6.0 nm, and the oxygen vacancy concentration is 10-30 percent;
and the double-shell hollow nano particles are obtained at 300-400 ℃; the single-layer shell hollow nano-particle is obtained at 500-600 ℃.
10. An application of the cerium-based hollow nano wave-absorbing material according to claim 1 or the cerium-based hollow nano wave-absorbing material prepared by the method according to claim 2 in sensors, supercapacitors, photocatalysis or lithium ion batteries.
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