CN110950320A - Light hollow carbon cube wave-absorbing material and preparation method thereof - Google Patents

Light hollow carbon cube wave-absorbing material and preparation method thereof Download PDF

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CN110950320A
CN110950320A CN201911369091.5A CN201911369091A CN110950320A CN 110950320 A CN110950320 A CN 110950320A CN 201911369091 A CN201911369091 A CN 201911369091A CN 110950320 A CN110950320 A CN 110950320A
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cube
wave
hollow carbon
absorbing material
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CN110950320B (en
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强荣
杨红英
王艳芝
魏静
杨雪轲
姚松
别晓龙
李鹏凯
李博
王冰瑶
吕贤一
尤茂宇
乔知远
张逸飞
叶子
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Zhongyuan University of Technology
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Abstract

The invention belongs to the field of material preparation, and particularly relates to a light hollow carbon cube wave-absorbing material and a preparation method thereof. The invention provides a preparation method of a light hollow carbon cubic wave-absorbing material, aiming at solving the problems of unmatched impedance, non-adjustable electromagnetic wave absorption frequency band and the like of a pure carbon wave-absorbing material prepared by the existing method and on the basis of fully utilizing a hard template to construct a hollow structure. The invention selects Cu2The O microspheres are used as hard templates, the light hollow carbon cubes are obtained through the processes of in-situ growth, calcination, template removal and the like, and Cu is adjusted2The thickness of the shell layer of the hollow carbon cube is regulated and controlled by the coating thickness of the poly-dopamine precursor on the O surface, so that the effective regulation and control of the conductivity characteristic of the carbon material can be realized in a small range, the wave-absorbing material with proper conductivity can be obtained according to the requirement, and the impedance matching and wave-absorbing effect of the material can be improved. Development of light hollow carbon cubic wave-absorbing material is hopeful to be applied to building absorptionThe field of wave materials.

Description

Light hollow carbon cube wave-absorbing material and preparation method thereof
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a light hollow carbon cube wave-absorbing material and a preparation method thereof.
Background
With the development of the electronic information industry, electronic products are widely applied, and a series of problems of electromagnetic radiation are brought along with the development of the electronic information industry, so that a lot of influences are brought to the production and the life of people. The important way to reduce electromagnetic radiation is electromagnetic wave absorption, and the wave-absorbing material can promote the electromagnetic energy to be converted into heat energy or eliminate the electromagnetic radiation fundamentally through interference cancellation. The carbon material has the advantages of low density, low price, simple preparation process, adjustable structure and the like, and has great potential in the wave-absorbing field. At present, most reports are focused on 'electromagnetic double-loss' type composite materials, such as magnetic metal/carbon composite wave-absorbing materials, the introduction of the magnetic component adjusts the impedance matching characteristic of the materials to a certain extent, but the electromagnetic wave attenuation is still mainly attributed to the dielectric loss of the carbon component, and the high-density magnetic component is not beneficial to the development of the light wave-absorbing materials.
Recent researches find that the cavity or the porous structure in the material can promote the electromagnetic waves to form repeated oscillation absorption, prolong the interaction time of the electromagnetic waves and the material, increase the effective absorption thickness of the wave-absorbing material, and meanwhile, the cavity or the porous structure is also beneficial to the development of the light building wave-absorbing material. The literature (material guide, 2015,29: 131-; the electric field intensity on the surface of the hollow carbon fiber is increased along with the increase of the diameter and the wall thickness, so that the regulation and control of the conductivity, the impedance matching and the wave absorption performance of the carbon fiber are realized through the wall thickness (the thickness of a carbon layer) and the pore structure of the carbon material, and certain theoretical guidance is provided. At present, most reports use pyrolysis temperature to adjust the conductivity of carbon materials, and because the properties of the carbon materials, such as conductivity, lattice defects and the like, are very sensitive to temperature, the method can only be adjusted and controlled in a large range, and cannot realize effective adjustment and control of the conductivity of the carbon materials. Therefore, the method has important significance in the field of electromagnetic wave absorption by utilizing an effective means to regulate and control the electrical conductivity of the porous carbon material, and is also beneficial to development and application of the light carbon wave-absorbing material in the field of buildings.
Disclosure of Invention
In order to solve the technical problems, the invention provides a light hollow carbon cube wave-absorbing material and a preparation method thereof, and Cu is fully utilized2The O template constructs a hollow structure, and solves the problems of unmatched impedance of the pure carbon wave-absorbing material, non-adjustable electromagnetic wave absorption frequency band and the like.
The technical scheme of the invention is realized as follows:
a preparation method of a light hollow carbon cube wave-absorbing material comprises the following steps:
(1) preparing aqueous solution of copper salt, adding into the tableStirring surfactant for 10min, dropwise adding NaOH solution until the solution turns blue, dropwise adding reducing solution under stirring, continuously reacting until the solution turns orange red, washing precipitate in the solution with deionized water and ethanol, and vacuum drying to obtain Cu2An O cube;
(2) dispersing dopamine into a trihydroxymethyl aminomethane buffer solution to obtain a dopamine dispersion solution, and adding the Cu obtained in the step (1) under stirring2Continuously reacting for 4-6h with O cube, centrifuging, washing, drying to collect solid, namely Cu2O @ PDA cube;
(3) mixing Cu2Placing the O @ PDA cube in a tube furnace with atmosphere protection for high-temperature calcination to obtain Cu2O@C-xComposite material of Cu2O@C-xThe composite material is placed in an acid solution and stirred for 24 hours to remove the template, the template is repeatedly removed for 3 to 5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
The copper salt in the step (1) is Cu (NO)3)2、CuSO4、CuCl2、Cu(CH3COO)2·H2One or more of O; the surfactant is one or more of polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, triethanolamine and sodium lauryl sulfate; the reducing solution is one or a mixed solution of ascorbic acid and hydrazine hydrate.
The mass ratio of the copper salt to the surfactant in the step (1) is (0.1-1) to (5-50); the concentration of the aqueous solution of the copper salt is 0.001-0.01 g/mL.
In the step (1), the concentration of the NaOH solution is 1-8mol/L, and the concentration of the reducing solution is 1-5 mol/L.
The concentration of the tris buffer solution in the step (2) is 10 mmol/L, pH and is 7.0-9.5; the concentration of dopamine in the dopamine dispersion liquid is 0.2-0.8 mg/mL.
Cu in the step (2)2The addition amount of the O cube does not exceed the mass of dopamine.
Cu in the step (3)2O@C-xComposite material, product C-xIn (1)xIs dopamine and Cu in the step (2)2Mass ratio of O-cube.
And (3) the acidic solution in the step (3) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
The light hollow carbon cube wave-absorbing material prepared by the preparation method is characterized in that: the wave-absorbing material is of a hollow structure, and the conductivity and the wave-absorbing effect of the material are regulated and controlled by the thickness of the carbon layer.
The invention has the following beneficial effects:
first, the present invention utilizes Cu2The O cube is used as a template, the light hollow carbon cube is obtained through in-situ growth, calcination, template removal and other process technologies, the impedance matching characteristic of the carbon material is effectively adjusted through the hollow structure, and most electromagnetic waves can be guaranteed to enter the carbon material to complete the attenuation process.
Secondly, the polydopamine is a precursor, the carbon layer is a derivative, and Cu is used for preparing the polydopamine2The thickness of the shell layer of the hollow carbon cube is regulated and controlled by the coating thickness of the polydopamine precursor on the surface of O, the regulation and control method can realize the regulation of the content of the carbon component in unit volume, and meanwhile, the wave-absorbing material with proper conductivity can be obtained according to the requirement, thereby being beneficial to improving the wave-absorbing frequency band and the absorption effect of the material.
The light hollow carbon cube wave-absorbing material is prepared by a template method, so that the density of the material in unit volume can be effectively reduced on the premise of ensuring the wave-absorbing performance, and the material is expected to be applied to the field of building wave-absorbing materials.
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 some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart of the preparation of hollow carbon cubes.
FIG. 2 is Cu2SEM photograph of O cube.
Fig. 3 is an XRD pattern of a hollow carbon cube.
Fig. 4 is a raman spectrum of a hollow carbon cube.
Fig. 5 is a three-dimensional wave absorption diagram of a hollow carbon cube.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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 obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.02 g Cu (Ac)2·H2O was dissolved in 10 mL of deionized water with stirring, followed by addition of 0.5 g of polyethylene glycol (PEG, MW: 2000) and stirring for 10 min. After the PEG was completely dissolved, 50. mu.L of NaOH solution (6.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, indicating that Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of ascorbic acid solution (1 mol/L) was added dropwise to the reaction system, and the reaction was continued for 1 h with the solution gradually turning orange. Washing the precipitate with deionized water and ethanol to remove PEG molecules adsorbed on the surface of the material, and drying in a vacuum drying oven at 40 deg.C to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing a certain amount of Dopamine (DA) in 100 mL of tris-buffer (Tris-buffer) with the concentration of 10 mmol/L and the pH value of 8.5, adding 80 mg of Cu into the mixed solution under stirring2O standThe reaction is continuously stirred for 4 hours, and then the solid product is collected by centrifugation, washing and drying, and the obtained product is Cu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are named as Cu in sequence2O@PDA-0、Cu2O@PDA-0.25、Cu2O@PDA-0.5、Cu2O@PDA-0.75、Cu2O@PDA-1。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 600 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min.
Mixing Cu2O@C-xThe composite material is placed in 1 mol/L HCl solution and stirred for 24 hours to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
As shown in fig. 1: the application selects Cu with mature technology2Obtaining Cu by in-situ polymerization by taking O as a template2The material is subjected to high-temperature calcination, acid corrosion and other processes to obtain a hollow carbon cube, the impedance matching of the material can be effectively adjusted through a hollow structure, and meanwhile, the hollow carbon cube is an effective way for obtaining the light wave-absorbing material.
FIG. 2 is Cu2And (3) an SEM photo of the O cube, wherein the cuprous oxide precursor obtained by the experiment has an irregular cube structure, the side length of the cube is about 3-4 mu m, the surface is flat, and the cuprous oxide precursor is uniformly distributed.
FIG. 3 is an XRD pattern of a hollow carbon cube, broad diffraction peaks from-23.5 degrees confirm that the carbon material is mainly amorphous, and weak diffraction peaks from-44 degrees show that a small amount of microcrystalline graphite is formed during high-temperature calcination.
Fig. 4 is a raman spectrum of a hollow carbon cube. The electrical conductivity of the carbon component can affect the dielectric loss properties of the material, which in turn affects its electromagnetic wave absorption. The composite material is in 1330 cm-1(D band) and 1580 cm-1There are two distinct peaks at (band G),I D/I Gthe value can be in a certain degreeCharacterization of graphitization degree of carbon Material, hollow carbon cube in this experimentI D/I GThe value was 0.8, and the electrical conductivity was good.
Fig. 5 is a two-dimensional reflection loss plot for a hollow carbon cube. The hollow carbon cube shows the optimal reflection loss characteristic, when the thickness of the absorbent is within the range of 1.5-5.0 mm, the maximum reflection loss of the material can achieve effective absorption (-10 dB), the absorption frequency band range is 3.8-17.9 GHz, and the absorption is better in the medium-high frequency range. The maximum reflection loss can reach-29.6 dB when the thickness of the absorbent is 1.4 mm and the frequency is 16.9 GHz.
Example 2
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.1 g of CuSO4Dissolved in 10 mL of deionized water with stirring, followed by addition of 5 g of polyvinylpyrrolidone and stirring for 10 min. After the polyvinylpyrrolidone was completely dissolved, 50. mu.L of NaOH solution (6.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, which states Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of ascorbic acid solution (1 mol/L) was added dropwise to the reaction system, and the reaction was continued for 1 h with the solution gradually turning orange. Fully washing the obtained precipitate with deionized water and ethanol to remove polyvinylpyrrolidone molecules adsorbed on the surface of the material, and drying in a vacuum drying oven at 40 ℃ for later use to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing Dopamine (DA) in 100 mL trihydroxymethyl aminomethane buffer solution (tris-buffer), wherein the concentration of the buffer solution is 10 mmol/L, the pH value is 7.0, adding 80 mg Cu into the mixed solution under stirring2Reacting for 4 hours, centrifuging, washing and drying to collect a solid product, wherein the obtained product is Cu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are named as Cu in sequence2O@PDA-0、Cu2O@PDA-0.25、Cu2O@PDA-0.5、Cu2O@PDA-0.75、Cu2O@PDA-1。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 600 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min. Mixing Cu2O@C-xThe composite material is placed in 1 mol/L HCl solution and stirred for 24 h to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
Example 3
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.05 g Cu (NO)3)2Dissolved in 10 mL of deionized water with stirring, followed by addition of 5 g of sodium dodecylbenzenesulfonate and stirring for 10 min. After the sodium dodecylbenzenesulfonate was completely dissolved, 50. mu.L of NaOH solution (8.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, which states Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of ascorbic acid solution (1 mol/L) was added dropwise to the reaction system, and the reaction was continued for 4 h with the solution gradually turning orange. Washing the obtained precipitate with deionized water and ethanol to remove sodium dodecyl benzene sulfonate molecules adsorbed on the surface of the material, and drying in a vacuum drying oven at 40 deg.C to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing Dopamine (DA) in 100 mL trihydroxymethyl aminomethane buffer solution (tris-buffer), wherein the concentration of the buffer solution is 10 mmol/L, the pH value is 9.5, and adding 40 mg of Cu into the mixed solution under stirring2Reacting for 4 hours, centrifuging, washing and drying to collect a solid product, wherein the obtained product is Cu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are named as Cu in sequence2O@PDA-0、Cu2O@PDA-0.5、Cu2O@PDA-1、Cu2O@PDA-1.5、Cu2O@PDA-2。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 900 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min. Mixing Cu2O@C-xThe composite material is placed in 2 mol/L nitric acid solution and stirred for 24 hours to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
Example 4
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.05 g of CuCl2Dissolved in 10 mL of deionized water with stirring, followed by addition of 5 g of triethanolamine and stirring for 10 min. After the triethanolamine was completely dissolved, 50. mu.L of NaOH solution (8.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, indicating that Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of ascorbic acid solution (1 mol/L) was added dropwise to the reaction system, and the reaction was continued for 4 h with the solution gradually turning orange. Washing the precipitate with deionized water and ethanol to remove triethanolamine molecules adsorbed on the surface of the material, and drying in a vacuum drying oven at 40 deg.C to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing Dopamine (DA) in 100 mL trihydroxymethyl aminomethane buffer solution (tris-buffer), wherein the concentration of the buffer solution is 10 mmol/L, the pH value is 9.5, and adding 40 mg of Cu into the mixed solution under stirring2Reacting for 4 hours, centrifuging, washing and drying to collect a solid product, wherein the obtained product is Cu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are named asCu2O@PDA-0、Cu2O@PDA-0.5、Cu2O@PDA-1、Cu2O@PDA-1.5、Cu2O@PDA-2。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 900 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min. Mixing Cu2O@C-xThe composite material is placed in 3 mol/L sulfuric acid solution and stirred for 24 hours to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
Example 5
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.05 g of CuCl2Dissolved in 10 mL of deionized water with stirring, followed by addition of 5 g of triethanolamine and stirring for 10 min. After the triethanolamine was completely dissolved, 50. mu.L of NaOH solution (8.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, indicating that Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of ascorbic acid solution (1 mol/L) was added dropwise to the reaction system, and the reaction was continued for 4 h with the solution gradually turning orange. Washing the precipitate with deionized water and ethanol to remove triethanolamine molecules adsorbed on the surface of the material, and drying in a vacuum drying oven at 40 deg.C to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing Dopamine (DA) in 100 mL trihydroxymethyl aminomethane buffer solution (tris-buffer), wherein the concentration of the buffer solution is 10 mmol/L, the pH value is 9.5, and adding 10 mg of Cu into the mixed solution under stirring2Reacting for 4 hours, centrifuging, washing and drying to collect a solid product, wherein the obtained product is Cu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are sequentially namedNamed as Cu2O@PDA-0、Cu2O@PDA-2、Cu2O@PDA-4、Cu2O@PDA-6、Cu2O@PDA-8。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 900 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min. Mixing Cu2O@C-xThe composite material is placed in 4 mol/L sulfuric acid solution and stirred for 24 hours to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
Example 6
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.08 g of CuCl2The mixture was dissolved in 10 mL of deionized water with stirring, and then 2.5 g of triethanolamine and lauryl alcohol sodium sulfate amine (mass ratio 1: 1) were added and stirred for 10 min. After the triethanol and the laurinol amine sulfate were completely dissolved, 50. mu.L of NaOH solution (8.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, which shows Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of a mixed solution (5 mol/L) of 5% hydrazine hydrate and 30% ascorbic acid was added dropwise to the reaction system, and the reaction was continued for 4 hours while the solution gradually turned orange. Washing the obtained precipitate with deionized water and ethanol to remove adsorbed molecules of triethanolamine and lauryl alcohol sodium sulfate, and drying in vacuum drying oven at 40 deg.C to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing Dopamine (DA) in 100 mL trihydroxymethyl aminomethane buffer solution (tris-buffer), wherein the concentration of the buffer solution is 10 mmol/L, the pH value is 9.5, and adding 10 mg of Cu into the mixed solution under stirring2O cube, reacting for 4 h, centrifuging, washing and drying to collect solid product, wherein the obtained product isCu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are named as Cu in sequence2O@PDA-0、Cu2O@PDA-2、Cu2O@PDA-4、Cu2O@PDA-6、Cu2O@PDA-8。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 900 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min. Mixing Cu2O@C-xThe composite material is placed in 4 mol/L sulfuric acid solution and stirred for 24 hours to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
Example 6
The preparation method of the light hollow carbon cube wave-absorbing material provided by the embodiment comprises the following steps:
firstly, preparing Cu2An O cube: cu2The O cube is obtained by a liquid phase chemical reduction method, and the method comprises the following specific steps: 0.08 g of CuCl2The mixture was dissolved in 10 mL of deionized water with stirring, and then 2.5 g of triethanolamine and lauryl alcohol sodium sulfate amine (mass ratio 1: 1) were added and stirred for 10 min. After the triethanol and the laurinol amine sulfate were completely dissolved, 50. mu.L of NaOH solution (8.0 mol/L) was added dropwise to the mixed solution, and the mixed solution turned blue, which shows Cu (OH)2The precursor has been formed. After the reaction was stirred for 10min, 0.2mL of a mixed solution (5 mol/L) of 5% hydrazine hydrate and 30% ascorbic acid was added dropwise to the reaction system, and the reaction was continued for 4 hours while the solution gradually turned orange. Washing the obtained precipitate with deionized water and ethanol to remove adsorbed molecules of triethanolamine and lauryl alcohol sodium sulfate, and drying in vacuum drying oven at 40 deg.C to obtain Cu2And (4) an O cube.
II, preparing Cu2O @ PDA cube: dispersing Dopamine (DA) in 100 mL trihydroxymethyl aminomethane buffer solution (tris-buffer) with the concentration of 10 mmol/L and the pH value of 9, adding 10 mg Cu into the mixed solution under stirring2Reacting for 4 hours, centrifuging, washing and drying to collect a solid product, wherein the obtained product is Cu2O @ PDA cube. The addition amounts of DA in the reaction process are respectively 0, 20, 40, 60 and 80 mg, and the products are named as Cu in sequence2O@PDA-0、Cu2O@PDA-2、Cu2O@PDA-4、Cu2O@PDA-6、Cu2O@PDA-8。
Thirdly, preparing a hollow carbon cube: mixing Cu2O@PDA-xPlacing the composite material in a tubular furnace protected by inert atmosphere for high-temperature calcination to obtain Cu2O@C-xThe calcination temperature of the composite material is 800 ℃, the heat preservation time is 5 h, and the heating rate is 1 ℃/min. Mixing Cu2O@C-xThe composite material is placed in 3 mol/L sulfuric acid solution and stirred for 24 hours to remove the template, the process is repeated for 3-5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a light hollow carbon cube wave-absorbing material is characterized by comprising the following steps:
(1) preparing a copper salt aqueous solution, adding a surfactant, stirring for 10min, then dropwise adding a NaOH solution, dropwise adding a reducing solution under the stirring condition when the solution turns blue, continuously reacting until the solution turns orange, fully washing precipitates in the solution by deionized water and ethanol, and obtaining Cu by vacuum drying2An O cube;
(2) dispersing dopamine into a trihydroxymethyl aminomethane buffer solution to obtain a dopamine dispersion solution, and adding the Cu obtained in the step (1) under stirring2Continuously reacting for 4-6h with O cube, centrifuging, washing, drying to collect solid, namely Cu2O @ PDA cube;
(3) mixing Cu2O @ PDA cube is placed in airCalcining at high temperature in a tubular furnace under the protection of atmosphere to obtain Cu2O@C-xComposite material of Cu2O@C-xThe composite material is placed in an acid solution and stirred for 24 hours to remove the template, the template is repeatedly removed for 3 to 5 times to ensure that the central template is completely removed, the mixture is washed and dried to obtain a hollow carbon cubic material, and the product is named as C-x。
2. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 1, characterized in that: the copper salt in the step (1) is Cu (NO)3)2、CuSO4、CuCl2、Cu(CH3COO)2·H2One or more of O; the surfactant is one or more of polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, triethanolamine and sodium lauryl sulfate; the reducing solution is one or a mixed solution of ascorbic acid and hydrazine hydrate.
3. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 2, characterized in that: the mass ratio of the copper salt to the surfactant in the step (1) is (0.1-1) to (5-50); the concentration of the aqueous solution of the copper salt is 0.001-0.01 g/mL.
4. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 2, characterized in that: in the step (1), the concentration of the NaOH solution is 1-8mol/L, and the concentration of the reducing solution is 1-5 mol/L.
5. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 1, characterized in that: the concentration of the tris buffer solution in the step (2) is 10 mmol/L, pH and is 7.0-9.5; the concentration of dopamine in the dopamine dispersion liquid is 0.2-0.8 mg/mL.
6. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 1, characterized in that: said step (c) is(2) Middle Cu2The addition amount of the O cube does not exceed the mass of dopamine.
7. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 1, characterized in that: cu in the step (3)2O@C-xComposite material, product C-xIn (1)xIs dopamine and Cu in the step (2)2Mass ratio of O-cube.
8. The preparation method of the light hollow carbon cube wave-absorbing material according to claim 1, characterized in that: and (3) the acidic solution in the step (3) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
9. The light hollow carbon cube wave-absorbing material prepared by the preparation method of any one of claims 1 to 8 is characterized in that: the wave-absorbing material is of a hollow structure, and the conductivity and the wave-absorbing effect of the material are regulated and controlled by the thickness of the carbon layer.
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