CN112426980B - Magnetic response two-dimensional material aerogel microsphere and preparation method thereof - Google Patents
Magnetic response two-dimensional material aerogel microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention provides a magnetic response two-dimensional material aerogel microsphere and a preparation method thereof, wherein deionized water, a two-dimensional material and a polymer additive are prepared into a water phase; dissolving a salt of a magnetic element into a salt solution; mixing an organic solvent and a salt solution to obtain a two-phase receiving bath; loading the injector filled with the aqueous phase dispersion liquid on an electrostatic spraying device, and installing a clip needle; placing the two-phase receiving bath under a needle head, and adding a stirrer for stirring; filtering and washing the obtained mixture to obtain two-dimensional material microspheres; and (3) quickly freezing the liquid nitrogen to obtain the two-dimensional material ice microspheres, and freeze-drying the two-dimensional material ice microspheres to obtain the two-dimensional material aerogel microspheres. And reducing the two-dimensional material aerogel microspheres by using a high-temperature thermal reduction method to obtain the magnetic response two-dimensional material aerogel microspheres. The preparation method provided by the invention is simple to operate, high in production efficiency and safe and reliable in production process.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a magnetic response two-dimensional material aerogel microsphere and a preparation method thereof.
Background
Two-dimensional materials are confined to two-dimensional planes due to their carrier transport and thermal diffusion, making such materials exhibit many unique properties. The adjustable band gap characteristic of the band gap is widely applied in the fields of field effect tubes, photoelectric devices, thermoelectric devices and the like; the controllability of the spin degree of freedom and the valley degree of freedom thereof has led to intensive research in the fields of spintronics and valley electronics; due to the special properties of the crystal structure, different two-dimensional materials have anisotropy of different electrical properties or optical properties, including anisotropy of properties such as Raman spectrum, photoluminescence spectrum, second-order harmonic spectrum, light absorption spectrum, thermal conductivity and electric conductivity, and have great development potential in the fields of polarized photoelectric devices, polarized thermoelectric devices, bionic devices, polarized light detection and the like.
Aerogel, generally referred to as a highly dispersed solid material in which colloidal particles or high polymer molecules are agglomerated with each other to form a nanoporous network structure and the pores are filled with a gaseous dispersion medium, has a very low density. Currently, the common aerogels are all in block shapes. The block aerogel is prepared into microspheres with the diameter of 10-1000 microns, namely the aerogel microspheres. Aerogel microspheres refer to microspheres in an aerogel form, and are not microspheres containing aerogel; aerogel is a description of porous morphology.
The aerogel is made into microspheres, so that the application potential of the aerogel is greatly expanded, for example, various existing carbon aerogel microspheres and SiO2Aerogel microspheres, TiO2/SiO2The composite aerogel microspheres and the two-dimensional material aerogel microspheres with the center divergent structure and the like show more excellent properties than the massive aerogel, and particularly in the application of the environment, the aerogel microspheres have better oil-water separation capacity and adsorption performance than the massive aerogel. However, the traditional two-dimensional material aerogel microspheres only have excellent adsorption capacity and lack the separation capacity from the environment after adsorption in an oil-water coexisting environment, so the practical value is greatly reduced, the magnetic response capacity of the two-dimensional material aerogel microspheres can be greatly improved, and the practical application potential of the two-dimensional material in the fields of environment, energy catalysis and the like, particularly in oil-water separation can be greatly improved, and therefore, the preparation research on the micron-sized two-dimensional material aerogel microspheres with the magnetic response characteristic has extremely important value. Due to the structural characteristics (the porosity is over 90%) and the physical properties (light weight) of the aerogel, regular two-dimensional material aerogel microspheres cannot be obtained by conventional mechanical methods such as ball milling and dispersion; on the other hand, in the production process of the two-dimensional material aerogel microspheres reported previously, a large amount of organic reagents such as ethyl acetate, n-hexane and the like are required, and a large amount of liquid nitrogen is also required, so that the environmental pollution is caused, and the energy is extremely consumed. Therefore, a preparation method of a novel two-dimensional material aerogel microsphere with industrial application prospect and magnetic response is in urgent need to be established.
Disclosure of Invention
The objects of the present invention include:
providing a magnetic two-dimensional material aerogel microsphere;
the aerogel microspheres prepared by the method are regular in shape and adjustable in size, have the capability of interacting with a magnet, have a porous network structure, and are light in weight and small in density.
The specific technical scheme is as follows:
the preparation method of the two-dimensional material aerogel microspheres comprises the following steps:
(1) preparing or preparing a bulk two-dimensional material;
(2) uniformly mixing deionized water, a bulk two-dimensional material and a polymer additive, and then performing ultrasonic irradiation for 15-360min to prepare a water phase, wherein the bulk two-dimensional material is peeled into a two-dimensional material in the ultrasonic process and is uniformly mixed with the polymer additive;
(3) dissolving salt of a magnetic element in deionized water to prepare a salt solution required by a receiving bath;
(4) mixing an organic solvent and the salt solution prepared in the step (3) to prepare a two-phase receiving bath;
(5) loading the injector filled with the dispersion liquid obtained in the step (2) on electrostatic spraying equipment, and installing a clip needle head, wherein the applied voltage is 5-20 kV;
(6) placing the two-phase receiving bath obtained in the step (4) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 200 and 1200rpm, and the length of the stirrer is 30-50 mm;
(7) filtering and washing the mixture obtained in the step (6) to obtain two-dimensional material microspheres; quickly freezing liquid nitrogen to obtain two-dimensional material ice microspheres, and freeze-drying the two-dimensional material ice microspheres to obtain two-dimensional material aerogel microspheres;
(8) and reducing the two-dimensional material aerogel microspheres by using a high-temperature thermal reduction method to obtain the magnetic response two-dimensional material aerogel microspheres.
The two-dimensional material is Bi2Se3、Bi2Te3Black phosphorus, boron nitride, CaPS3、CoPS3、FePS3FeSe, GaS, GaSe, GaTe, GeS, graphite, graphene oxide, InSe, MgB2、MnPS3、MoS2、MoSe2、MoTe2、NbB2、PdTe2、PtTe、ReS2、ReSe2、Sb2Te3、SnS2、SnSe、TaS2、TaB2、TaS2、TaS3、TaS3、TaSe2、TiS2、Tl2S、VB2、WS2、WSe2、ZnPS3、Ti2C3And TiC.
Wherein, the polymer additive in the step (2) is selected from one or more of polyacrylamide, polyvinylpyrrolidone, sodium alginate, sodium carboxymethylcellulose, polyoxyethylene, sodium polyacrylate, polyvinyl alcohol, starch, chitin and sodium acetate cellulose.
In the step (2), deionized water, a bulk phase two-dimensional material and a polymer additive are mixed according to the following mass parts: 90-150 parts of: 0.05-2 parts of: 0.05-2 parts of a stabilizer;
in the step (3), the salt of the magnetic element and the deionized water are mixed according to the mass part: 5-40 parts of: 60-95 parts.
The salt of the magnetic element in the step (3) is one or a combination of more of cobalt acetate, nickel acetate, iron acetate, cobalt hydrochloride, nickel hydrochloride, iron hydrochloride, cobalt nitrate, nickel nitrate, iron nitrate, cobalt sulfate, nickel sulfate and iron sulfate.
The organic solvent in the step (4) is any one or more of n-heptane, petroleum ether, toluene, n-hexane and n-octane.
The diameter of the needle head in the step (6) is 0.3-0.6 mm.
Specifically, the high-temperature thermal reduction method comprises the following steps: and (3) placing the two-dimensional material aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 5-10 ℃/min under the Ar atmosphere, and preserving heat for 2-5 h.
The magnetic response two-dimensional material aerogel microspheres obtained by the invention are microspheres which are prepared from two-dimensional materials serving as main components, high polymer materials and iron, cobalt and nickel elements serving as additives and have porous shapes like aerogel; or, the magnetic response two-dimensional material aerogel microspheres of the invention are microspheres which are composed of two-dimensional materials, high molecular materials, iron, cobalt and nickel elements and have a porous appearance like aerogel.
In the preparation method, the initial feeding mass ratio is 0.05-2 parts of two-dimensional material, 0.05-2 parts of polymer additive and 90-150 parts of deionized water, the microspheres are formed by an electrostatic spraying method, an organic solvent and a specific salt solution (containing iron, cobalt and nickel) are used as two-phase receiving baths, the redundant salt solution on the surface can be removed by filtering and washing after the microspheres are formed, and only the two-dimensional material hydrogel microspheres consisting of the two-dimensional material, the polymer additive and the elements of iron, cobalt and nickel are left. The aerogel is endowed with a general porous structure through liquid nitrogen quick freezing and freeze drying, and the two-dimensional material is reduced to obtain the two-dimensional material aerogel microsphere with magnetic response, which consists of the two-dimensional material, a high molecular additive, iron, cobalt and nickel elements. The mass ratio of the two-dimensional material to the polymer additive can be measured by a thermal weight loss method, and the final polymer mass accounts for 0-30%, while the two-dimensional material mass accounts for 70-100%.
The invention has the following advantages:
1. the invention combines the electrostatic spraying method, the sol-gel conversion method and the freeze-drying method for the first time to prepare the magnetic response two-dimensional material aerogel microspheres.
2. The preparation method provided by the invention is simple to operate, high in production efficiency and safe and reliable in production process.
3. The magnetic response two-dimensional material aerogel obtained by the preparation method provided by the invention is regular in microspherical shape, uniform in size, high in specific surface area and porous in network structure.
4. The magnetic response two-dimensional material aerogel microspheres prepared by the preparation method can be in non-contact interaction with a magnet.
Drawings
FIG. 1 is a process diagram of example 1 for preparing magnetic-response two-dimensional material aerogel microspheres;
FIG. 2 is a scanning electron microscope image of a magnetically responsive two-dimensional material aerogel microsphere prepared in example 1;
FIG. 3 is a scanning electron microscope image of the surface of a two-dimensional material aerogel microsphere with magnetic response prepared in example 1.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the present examples are only illustrative of the present invention, and should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) preparing natural crystalline flake graphite into graphene oxide by a chemical oxidation method;
and (3) uniformly mixing 10g of natural crystalline flake graphite, 6g of potassium permanganate and 300ml of concentrated sulfuric acid, then carrying out oxidation reaction at high temperature, centrifuging, washing and dialyzing the obtained product to obtain a bulk phase two-dimensional material, and drying for later use.
(2) Uniformly mixing 100 parts of deionized water, 0.9 part of graphene oxide and 0.05 part of polyvinyl alcohol, and performing 1600W ultrasonic irradiation for 15min to prepare a water phase;
(3) 5 parts of ferric nitrate is dissolved in 65 parts of deionized water to prepare a salt solution required by a receiving bath;
(4) and (4) mixing toluene and the salt solution prepared in the step (3) to prepare a two-phase receiving bath.
(5) And (3) loading the syringe filled with the dispersion liquid obtained in the step (2) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 5 kV.
(6) Placing the two-phase receiving bath obtained in the step (4) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 300rpm, and the length of the stirrer is 30mm, as shown in figure 1;
(7) filtering and washing the mixture obtained in the step (6) to obtain graphene oxide microspheres; rapidly freezing with liquid nitrogen to obtain graphene oxide ice microspheres, and freeze-drying (vacuum degree 20Pa, temperature-50 ℃) to obtain graphene oxide aerogel microspheres, as shown in FIG. 2.
(8) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 6 ℃/min under the atmosphere of Ar, and preserving heat for 3 h.
Observing the magnetic response two-dimensional material aerogel microspheres prepared in the example 1 by using a scanning electron microscope to obtain a morphology map of the microspheres; the results show that: the prepared magnetic response two-dimensional material aerogel microspheres are uniform in size and regular in shape, and have abundant network structures and pore structures. Scanning Electron microscopy asAs shown in fig. 3. The average grain diameter of the two-dimensional material aerogel microspheres is determined to be 247 mu m, and the density is determined to be 5.0kg/m3。
Example 2
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 120 parts of deionized water, 1.2 parts of black phosphorus and 0.1 part of polyvinylpyrrolidone, and performing 600W ultrasonic irradiation for 20min to prepare a water phase;
(2) 10 parts of nickel sulfate is dissolved in 85 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) mixing n-heptane and the salt solution prepared in step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 12 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 450rpm, and the length of the stirrer is 35 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain black phosphorus microspheres; and (3) quickly freezing the liquid nitrogen to obtain the black phosphorus ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the black phosphorus ice microspheres to obtain the black phosphorus aerogel microspheres. The average grain diameter of the black phosphorus microspheres is 450 mu m, and the density is 6.8kg/m3。
(7) Placing the black phosphorus aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 7 ℃/min under the Ar atmosphere, and keeping the temperature for 4 h.
Example 3
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 110 parts of deionized water, 0.8 part of boron nitride and 0.8 part of polyvinylpyrrolidone, and performing 800W ultrasonic irradiation for 25min to prepare a water phase;
(2) dissolving 20 parts of cobalt hydrochloride in 70 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) and (3) mixing n-octane and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 15 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 650rpm, and the length of the stirrer is 40 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain boron nitride microspheres; and (3) quickly freezing the liquid nitrogen to obtain boron nitride ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the boron nitride ice microspheres to obtain the boron nitride aerogel microspheres. The average particle diameter of the boron nitride microspheres is 550 mu m, and the density is 7.2kg/m3。
(7) Placing the boron nitride aerogel microspheres in a tube furnace, heating to 800 ℃ at a heating rate of 8 ℃/min under the atmosphere of Ar, and preserving heat for 5 h.
Example 4
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 105 parts of deionized water, 0.9 part of graphene oxide and 0.8 part of polyacrylamide, and performing ultrasonic irradiation at 500W for 35min to prepare a water phase;
(2) dissolving 25 parts of nickel hydrochloride in 75 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) and (3) mixing normal hexane and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 10 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 750rpm, and the length of the stirrer is 45 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain graphene oxide microspheres; and (3) quickly freezing liquid nitrogen to obtain graphene oxide ice microspheres, and freeze-drying (vacuum degree of 20Pa, temperature of-50 ℃) the graphene oxide ice microspheres to obtain the graphene oxide aerogel microspheres. The average grain diameter of the graphene oxide microspheres is 500 mu m, and the density is 8kg/m3。
(7) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 9 ℃/min under the atmosphere of Ar, and preserving heat for 4 h.
Example 5
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 130 parts of deionized water, 1.4 parts of black phosphorus and 2 parts of sodium polyacrylate, and performing 400W ultrasonic irradiation for 30min to prepare a water phase;
(2) dissolving 40 parts of cobalt hydrochloride in 60 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) and (3) mixing toluene and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 12 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 550rpm, and the length of the stirrer is 45 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain black phosphorus microspheres; and (3) quickly freezing the liquid nitrogen to obtain the black phosphorus ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the black phosphorus ice microspheres to obtain the black phosphorus aerogel microspheres. The average grain diameter of the black phosphorus microspheres is 650 mu m, and the density is 8.6kg/m3。
(7) Placing the black phosphorus aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 6 ℃/min under the Ar atmosphere, and keeping the temperature for 3 h.
Example 6
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 135 parts of deionized water, 1.5 parts of boron nitride and 1.2 parts of sodium carboxymethylcellulose, and performing 600W ultrasonic irradiation for 55min to prepare a water phase;
(2) dissolving 20 parts of ferric hydrochloride in 80 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) and (3) mixing normal hexane and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) The syringe containing the dispersion obtained in step (1) was loaded on an electrostatic spraying apparatus, and a hollow needle was attached thereto with an applied voltage of 14 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 850rpm, and the length of the stirrer is 50 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain boron nitride microspheres; and (3) quickly freezing the liquid nitrogen to obtain boron nitride ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the boron nitride ice microspheres to obtain the boron nitride aerogel microspheres. The average grain diameter of the boron nitride microspheres is measured to be 350 mu m, and the density is measured to be 6.6kg/m3。
(7) Placing the boron nitride aerogel microspheres in a tube furnace, heating to 800 ℃ at a heating rate of 8 ℃/min under the atmosphere of Ar, and preserving heat for 4 h.
Example 7
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 140 parts of deionized water, 1.3 parts of TiC and 1.5 parts of sodium polyacrylate, and performing 550W ultrasonic irradiation for 45min to prepare a water phase;
(2) dissolving 25 parts of ferric sulfate in 75 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) mixing petroleum ether and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 17 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 950rpm, and the length of the stirrer is 40 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain TiC microspheres; rapidly freezing the liquid nitrogen to obtain TiC ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the TiC ice microspheres to obtain the TiC aerogel microspheres. The average grain diameter of the TiC microspheres is measured to be 450 mu m, and the density is measured to be 6.2kg/m3。
(7) Placing the TiC aerogel microspheres in a tube furnace, heating to 800 ℃ at a heating rate of 7 ℃/min under the atmosphere of Ar, and preserving heat for 3 h.
Example 8
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 125 parts of deionized water, 0.7 part of graphene oxide and 1.5 parts of polyacrylamide, and performing 650W ultrasonic irradiation for 55min to prepare a water phase;
(2) dissolving 15 parts of nickel sulfate in 85 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) and (3) mixing n-octane and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 17 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 850rpm, and the length of the stirrer is 45 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain graphene oxide microspheres; and (3) quickly freezing liquid nitrogen to obtain graphene oxide ice microspheres, and freeze-drying (vacuum degree of 20Pa, temperature of-50 ℃) the graphene oxide ice microspheres to obtain the graphene oxide aerogel microspheres. The average grain diameter of the graphene oxide microspheres is 650 mu m, and the density is 9.2kg/m3。
(7) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 6 ℃/min under the atmosphere of Ar, and preserving heat for 4 h.
Example 9
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 115 parts of deionized water, 0.9 part of black phosphorus and 1 part of starch, and performing 700W ultrasonic irradiation for 45min to prepare a water phase;
(2) dissolving 20 parts of cobalt acetate in 80 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) mixing petroleum ether and the salt solution prepared in the step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 17 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 800rpm, and the length of the stirrer is 35 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain black phosphorus microspheres; and (3) quickly freezing the liquid nitrogen to obtain the black phosphorus ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the black phosphorus ice microspheres to obtain the black phosphorus aerogel microspheres. The average grain diameter of the black phosphorus microspheres is 550 mu m, and the density is 8.4kg/m3。
(7) Placing the black phosphorus aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 7 ℃/min under the Ar atmosphere, and keeping the temperature for 3 h.
Example 10
The preparation method of the magnetic response two-dimensional material aerogel microspheres comprises the following steps:
(1) uniformly mixing 120 parts of deionized water, 1 part of TiC and 1 part of sodium alginate, and performing 750W ultrasonic irradiation for 25min to prepare a water phase;
(2) dissolving 30 parts of ferric acetate in 70 parts of deionized water to prepare a salt solution required by a receiving bath;
(3) mixing n-heptane and the salt solution prepared in step (2) to prepare a two-phase receiving bath.
(4) And (2) loading the syringe filled with the dispersion liquid obtained in the step (1) on an electrostatic spraying device, and installing a clip needle, wherein the applied voltage is 17 kV.
(5) Placing the two-phase receiving bath obtained in the step (3) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 700rpm, and the length of the stirrer is 30 mm;
(6) filtering and washing the mixture obtained in the step (5) to obtain TiC microspheres; rapidly freezing the liquid nitrogen to obtain TiC ice microspheres, and freeze-drying (the vacuum degree is 20Pa, and the temperature is-50 ℃) the TiC ice microspheres to obtain the TiC aerogel microspheres. The average grain diameter of the TiC microspheres is measured to be 450 mu m, and the density is measured to be 6.8kg/m3。
(7) Placing the TiC aerogel microspheres in a tube furnace, heating to 800 ℃ at a heating rate of 7 ℃/min under the atmosphere of Ar, and preserving heat for 3 h.
Claims (8)
1. The preparation method of the magnetic response two-dimensional material aerogel microspheres is characterized by comprising the following steps of:
(1) preparing or preparing a bulk two-dimensional material;
(2) uniformly mixing deionized water, a bulk two-dimensional material and a polymer additive, and then performing ultrasonic irradiation for 15-360min to prepare a water phase, wherein the bulk two-dimensional material is peeled into a two-dimensional material in the ultrasonic process and is uniformly mixed with the polymer additive;
(3) dissolving salt of a magnetic element in deionized water to prepare a salt solution required by a receiving bath;
(4) mixing an organic solvent and the salt solution prepared in the step (3) to prepare a two-phase receiving bath;
(5) loading the injector filled with the dispersion liquid obtained in the step (2) on electrostatic spraying equipment, and installing a clip needle head, wherein the applied voltage is 5-20 kV;
(6) placing the two-phase receiving bath obtained in the step (4) under a needle head, and adding a stirrer for stirring, wherein the stirring speed is 200 and 1200rpm, and the length of the stirrer is 30-50 mm;
(7) filtering and washing the mixture obtained in the step (6) to obtain hydrogel microspheres; quickly freezing by using liquid nitrogen to obtain hydrogel ice microspheres, and freeze-drying the hydrogel ice microspheres to obtain two-dimensional material aerogel microspheres;
(8) and (5) reducing the two-dimensional material aerogel microspheres obtained in the step (7) by using a high-temperature thermal reduction method to obtain the magnetic response two-dimensional material aerogel microspheres.
2. The method for preparing aerogel microspheres of magnetically responsive two-dimensional material as claimed in claim 1, wherein the bulk two-dimensional material in step (1) is Bi2Se3、Bi2Te3Black phosphorus, boron nitride, CaPS3、CoPS3、FePS3FeSe, GaS, GaSe, GaTe, GeS, graphite, graphene oxide, InSe, MgB2、MnPS3、MoS2、MoSe2、MoTe2、NbB2、PdTe2、PtTe、ReS2、ReSe2、Sb2Te3、SnS2、SnSe、TaS2、TaB2、TaS2、TaS3、TaS3、TaSe2、TiS2、Tl2S、VB2、WS2、WSe2、ZnPS3、Ti2C3And TiC.
3. The preparation method of the magnetic-response two-dimensional material aerogel microspheres according to claim 1, wherein the polymer additive in the step (2) is selected from one or more of polyacrylamide, polyvinylpyrrolidone, sodium alginate, sodium carboxymethylcellulose, polyoxyethylene, sodium polyacrylate, polyvinyl alcohol, starch, chitin, and sodium acetate.
4. The preparation method of the magnetic response two-dimensional material aerogel microspheres according to claim 1, wherein the deionized water, the bulk phase two-dimensional material and the polymer additive in the step (2) are mixed according to the following mass parts: 90-150 parts of: 0.05-2 parts of: 0.05-2 parts of a stabilizer;
in the step (3), the salt of the magnetic element and the deionized water are mixed according to the mass part: 5-40 parts of: 60-95 parts.
5. The preparation method of the magnetic-response two-dimensional material aerogel microspheres according to claim 1, wherein the salt of the magnetic element in the step (3) is one or more of cobalt acetate, nickel acetate, iron acetate, cobalt hydrochloride, nickel hydrochloride, iron hydrochloride, cobalt nitrate, nickel nitrate, iron nitrate, cobalt sulfate, nickel sulfate, and iron sulfate.
6. The preparation method of the magnetic-response two-dimensional material aerogel microspheres according to claim 1, wherein the organic solvent in the step (4) is any one or more of n-heptane, petroleum ether, toluene, n-hexane and n-octane.
7. The preparation method of the magnetic response two-dimensional material aerogel microspheres according to claim 1, wherein the high-temperature thermal reduction method comprises the following steps: and (3) placing the two-dimensional material aerogel microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 5-10 ℃/min under the Ar atmosphere, and preserving heat for 2-5 h.
8. Magnetically responsive two-dimensional material aerogel microspheres, characterized by being obtained by the preparation method of any one of claims 1 to 7.
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