CN113735554B - Functional two-dimensional material aerogel composite microsphere and macro preparation method thereof - Google Patents
Functional two-dimensional material aerogel composite microsphere and macro preparation method thereof Download PDFInfo
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Abstract
The invention provides a functional two-dimensional material aerogel composite microsphere and a macro preparation method thereof, wherein a two-dimensional material is dispersed in water, ultrasonically stirred, added with an organic ligand, blended and ultrasonically stirred to obtain a stable dispersion liquid, a corresponding functional salt is dissolved in deionized water to be used as a receiving bath, and then an organic solvent is added in a salt solution; filling the stable dispersion liquid into a spraying system, and placing a receiving bath right below the spraying system; and filtering the obtained solid microspheres through a screen, cleaning, freezing, and freeze-drying to obtain the two-dimensional material aerogel microspheres or the functional two-dimensional material aerogel composite microspheres. The invention uses the spray-gel method to prepare the two-dimensional material aerogel microspheres with industrialized magnetic response, the requirement of industrialized production equipment is reduced to extremely low, the production condition is simple, the production capacity is extremely high, the production efficiency can reach kilogram/day, and the obtained functional two-dimensional material aerogel composite microspheres have regular shapes and small volumes and are distributed in 1-200 um.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a functional two-dimensional material aerogel composite microsphere and a macro preparation method thereof.
Background
Taking graphene as an example, assembling two-dimensional graphene into a three-dimensional macrostructure is a common effective strategy that can utilize the performance and efficacy of graphene monolayers. Aerogels, hydrogels, organogels, etc. are common representations of these three-dimensional structures, where an aerogel is a 3D macroscopic solid network with multi-layered pore size and pore size distribution, as well as light density and high specific surface area, which can meet the demand for rapid mass transfer.
The graphene is prepared into aerogel microspheres, and the aerogel microspheres have potential application prospects in catalyst carriers, fillers, water treatment, high-efficiency adsorption, energy materials and the like.
If ions with specific functions are loaded on the two-dimensional material, the two-dimensional material microsphere is endowed with new functions while keeping the functions of the two-dimensional material microsphere, the effect that 1+1 is larger than 2 is realized, the application place of the two-dimensional material aerogel microsphere is greatly widened, if the graphene microsphere is loaded with magnesium ions, the dual biological activities of graphene and magnesium ions can greatly promote bone growth, and the application value in the biomedical direction is huge; if the graphene microspheres are loaded with cobalt ions and reduced into metal particles at high temperature, the metal graphene-based composite material is prepared at extremely low cost, and has great potential application in the military fields of electromagnetism, wave-absorbing materials and the like.
However, due to the structural characteristics (the porosity exceeds 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 reported production process for forming the two-dimensional material aerogel microspheres by electrostatic spinning jet freezing, a large amount of ethyl acetate, n-hexane and liquid nitrogen are needed, which causes environmental pollution and extremely consumes energy, on the basis, the problem group of the invention is that the two-dimensional material aerogel microspheres are endowed with magnetic response capability by using the electrostatic spinning technology in the previous work, which can greatly improve the application potential of the two-dimensional material in the fields of environment and energy catalysis and the like, although the gel-shaped aerogel microspheres prepared at normal temperature have better appearance, the production rate is slow, the problem of overlarge size is solved, the application in some fields is limited, only several grams can be prepared at most by one hundred thousand electrostatic spinning machines in one day, and the size is large, so that the size matching and dosage requirements of industrial production and practical application cannot be met.
Therefore, from the current production preparation and application prospects, the two-dimensional material aerogel microspheres are not diverse enough in functionality, not small in size control, not high in production efficiency and not wide in application occasions.
Therefore, a preparation method of the two-dimensional material aerogel microspheres with specific functions, which can be industrially produced in large scale under extremely simple production conditions, is urgently needed to be established.
Disclosure of Invention
The objects of the present invention include:
the functional two-dimensional material aerogel microspheres which can be prepared at room temperature simply are provided;
the preparation efficiency of the method is the fastest in all methods, the cost is the lowest, the obtained aerogel microspheres are regular in shape and size, can be screened, have a porous network structure and low in density, and can be prepared according to different load ions in different application occasions.
The specific technical scheme is as follows:
the preparation method of the functional two-dimensional material aerogel composite microsphere comprises the following steps:
(1) preparing or preparing a two-dimensional material with the particle size of less than 400 meshes, dispersing the two-dimensional material in water, ultrasonically stirring for 5 hours, keeping the two-dimensional material stable and not settling for 2 hours, and then adding an organic ligand, blending and ultrasonically stirring for 2 hours;
(2) dissolving corresponding functional salt into a certain amount of deionized water as a receiving bath, then adding a certain amount of organic solvent into a salt solution, and stirring for 1 h;
(4) filling the stable dispersion liquid prepared in the step (1) into a spraying system, and controlling the spraying distance to be 2-5 m, wherein the power of the spraying system is 500w, and the particle size range of fog drops of the spraying system is 1-200 um; and placing the prepared receiving bath under a spraying system;
(5) and (4) filtering, cleaning and freezing the solid microspheres obtained in the step (4) through a screen, and freeze-drying the solid microspheres in a freeze dryer for two days to obtain the two-dimensional material aerogel microspheres or the functional two-dimensional material aerogel microspheres.
Further comprising:
(6) and (5) reducing the two-dimensional material aerogel microspheres obtained in the step (5) by using a high-temperature thermal reduction method to obtain the functionalized two-dimensional material aerogel microspheres.
Wherein, in the step (1), the two-dimensional material is Graphene (GN) type: single-layer graphene, multi-layer graphene, graphene oxide, reduced graphene oxide; topological Insulator (TI) class: bi2Se3、Bi2Te3(ii) a Transition Metal Sulfides (TMDCs) type: CapS3、CoPS3、FePS3、FeSe、GaS、GaSe、GaTe、GeS、SnS2、SnSe、TaS2、TaB2、TaS2、TaS3、TaS3、TaSe2、TiS2、Tl2S、WS2、WSe2、ZnPS3、InSe、MnPS3、MoS2、MoSe2ReS2、ReSe2Starting the process; MXene group: tin+1Cn、Nbn+1Cn、Vn+1Cn、Mon+1Cn(ii) a And VB2, MgB2、MoTe2、NbB2、PdTe2、PtTe、Sb2Te3One or more combinations thereof.
In the step (1), the organic ligand is selected from all small molecules or macromolecules which have carboxyl, phosphoryl, hydroxyl, sulfate, amino and amido and can be coordinated with metal ions: polyacrylamide, polyvinylpyrrolidone, sodium alginate, sodium carboxymethylcellulose, polyoxyethylene, sodium polyacrylate, polyvinyl alcohol, starch, polysaccharide, chitin and sodium acetate cellulose; or a combination of any one or more of polymers having a carboxyl group, a phosphoryl group, a hydroxyl group, a sulfate group, an amino group, and an amide group.
The mass ratio of the deionized water, the two-dimensional material and the organic ligand in the step (1) is as follows: 100-110 parts: 1-2 parts of: 1-2 parts; the mass ratio of the salt to the deionized water in the step (3) is as follows: 3-30 parts of: 70-97 parts.
The salt in the step (2) is calcium oxalate, calcium carbonate, calcium phosphate, calcium gluconate, calcium hydrogen phosphate, calcium lactate, calcium halide, calcium nitrate, calcium chlorate, calcium perchlorate, calcium bicarbonate and calcium dihydrogen phosphate; magnesium nitrate, magnesium chloride, magnesium sulfate; cobalt acetate, nickel acetate, iron acetate, cobalt hydrochloride, nickel hydrochloride, iron hydrochloride, cobalt nitrate, nickel nitrate, iron nitrate, cobalt sulfate, nickel sulfate, ferric sulfate.
The organic solvent in the step (2) is any one or more of acetic acid, acetone, acetonitrile, DMF, DMSO, dioxane, ethanol, methanol, isopropanol and tetrahydrofuran.
The high-temperature thermal reduction method in the step (6) comprises the following steps: and placing the obtained two-dimensional material aerogel microspheres in a high-temperature environment, and annealing for 2-5h at 800 ℃ in an inert gas atmosphere.
The functional two-dimensional material aerogel composite microsphere obtained by the invention is a porous aerogel microsphere taking a two-dimensional material as a matrix and taking organic (or high-molecular) ligands and calcium, magnesium, iron, cobalt and nickel ions as functional coordination ions; or, the functional two-dimensional material aerogel composite microsphere is a porous aerogel microsphere consisting of a two-dimensional material, a carbon material and metal ions or metal particles.
In the preparation method, the initial feeding mass ratio is 0.5-2 parts of two-dimensional material, 0.5-2 parts of polymer additive and 80-120 parts of deionized water, microspheres are formed by a spraying method, an organic solvent and a specific salt solution (containing calcium, magnesium, iron, cobalt and nickel) are used as a receiving bath, 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 calcium, magnesium, iron, cobalt and nickel are left. The aerogel is endowed with a general porous structure through freezing and drying (and the two-dimensional material is reduced through thermal annealing), so that the two-dimensional material, the high molecular additive and the two-dimensional material aerogel microspheres which are composed of calcium, magnesium, iron, cobalt and nickel and have functionality can be obtained. 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 10-20% while the two-dimensional material mass accounts for 80-90%.
The invention has the following advantages:
1. the invention firstly uses a spray-gel method to prepare a plurality of functional two-dimensional material aerogel microspheres in large batch.
2. The preparation method provided by the invention has the advantages that the requirement on industrial production equipment is reduced to be extremely low for the first time, the production conditions are simple, and the production capacity is extremely high.
3. The functional two-dimensional material aerogel obtained by the preparation method for the first time has a regular composite microspherical shape, a small volume and distribution of 1-200um, the characteristics of small size, industrialization and functionality are combined to the preparation of any two-dimensional material microsphere for the first time, and the production efficiency of one spraying device can reach kilogram per day.
Drawings
FIG. 1 is a process diagram of example 1 for preparing functional two-dimensional aerogel composite microspheres;
FIG. 2 is a scanning electron microscope image of the functional two-dimensional material aerogel composite microspheres prepared in example 1;
FIG. 3 is a scanning electron microscope image of the surface of a functional two-dimensional aerogel composite microsphere 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 macro preparation method of the functional two-dimensional material aerogel composite microspheres as shown in figure 1 comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 0.05 part of polyvinyl alcohol are ultrasonically stirred for 2 hours at a speed of 500 w;
(2) 5 parts of cobalt chloride was dissolved in 80 parts of deionized water, and then added with organic solvent acetic acid and mixed well for 1 hour as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing black solid in the receiving bath; freezing to obtain graphene oxide ice microspheres, and freeze-drying in a freeze dryer for 2 days to obtain a functional graphene oxide aerogel microsphere precursor, as shown in fig. 2.
(6) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, and annealing at 800 ℃ for 2 hours in an argon atmosphere to obtain the graphene aerogel microspheres loaded with cobalt metal particles.
Observing the functional two-dimensional material aerogel composite 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 functional two-dimensional material aerogel composite microspheres are uniform in size and regular in shape, and have abundant network structures and pore structures. The scanning electron micrograph is shown in FIG. 3. The average grain diameter of the functional two-dimensional material aerogel composite microspheres is only 50 μm.
Example 2
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) stirring 100 parts of deionized water, 1 part of graphene oxide and 1 part of sodium alginate for 2 hours by using 500w of ultrasonic waves;
(2) 5 parts of magnesium chloride is dissolved in 80 parts of deionized water, and then an organic solvent acetic acid is added and mixed well for 1 hour as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the magnesium ion loaded functional graphene oxide aerogel microspheres.
Example 3
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of polyvinylpyrrolidone are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of cobalt nitrate is dissolved in 80 parts of deionized water, and then an organic solvent ethanol is added to be fully mixed for 1 hour to serve as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the functional graphene oxide aerogel microsphere precursor.
(6) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, and annealing for 3 hours at 800 ℃ in an argon atmosphere to obtain the graphene aerogel microspheres loaded with cobalt metal particles.
Example 4
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of polyvinylpyrrolidone by weight are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of nickel nitrate is dissolved in 80 parts of deionized water, and then an organic solvent ethanol is added to be fully mixed for 1 hour to serve as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the functional graphene oxide aerogel microsphere precursor.
(6) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, and annealing for 2.5 hours at 800 ℃ in an argon atmosphere to obtain the graphene aerogel microspheres loaded with nickel metal particles.
Example 5
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of sodium alginate are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of nickel nitrate is dissolved in 80 parts of deionized water, and then an organic solvent ethanol is added to be fully mixed for 1 hour to serve as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the functional graphene oxide aerogel microsphere precursor.
(6) And (3) placing the graphene oxide aerogel microspheres in a tube furnace, and annealing for 3 hours at 800 ℃ in an argon atmosphere to obtain the graphene aerogel microspheres loaded with nickel metal particles.
Example 6
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of polyvinylpyrrolidone are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of calcium chloride is dissolved in 80 parts of deionized water, and then an organic solvent ethanol is added to be fully mixed for 1 hour to serve as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the calcium ion loaded functional graphene oxide aerogel microspheres.
Example 7
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of sodium alginate by weight are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of calcium oxalate was dissolved in 80 parts of deionized water, and then added to an organic solvent ethanol and mixed well for 1 hour as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the calcium ion loaded functional graphene oxide aerogel microspheres.
Example 8
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of polyvinylpyrrolidone are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of magnesium sulfate was dissolved in 80 parts of deionized water, and then added to an organic solvent ethanol and mixed well for 1 hour as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing black solid in the receiving bath; and freezing to obtain graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the magnesium ion loaded functional graphene oxide aerogel microspheres.
Example 9
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of polyvinylpyrrolidone are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of ferric chloride is dissolved in 80 parts of deionized water, and then an organic solvent ethanol is added to be fully mixed for 1 hour to serve as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the functional graphene oxide aerogel microsphere precursor.
(6) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, and annealing for 3 hours at 800 ℃ in an argon atmosphere to obtain the graphene aerogel microspheres loaded with iron metal particles.
Example 10
The macro preparation method of the functional two-dimensional material aerogel composite microspheres comprises the following steps:
(1) 100 parts of deionized water, 1 part of graphene oxide and 1 part of sodium alginate by weight are ultrasonically stirred for 2 hours at 500 w;
(2) 5 parts of cobalt acetate tetrahydrate are dissolved in 80 parts of deionized water, and then an organic solvent ethanol is added to be fully mixed for 1 hour to serve as a receiving bath.
(3) The dispersion obtained in step (1) was charged into a spray apparatus, and the applied power was 500 w.
(4) Placing the receiving bath obtained in the step (2) under a spraying device, and controlling the distance between a spray head and a receiving bath interface to be 2 m;
(5) filtering and washing the black solid in the receiving bath; and freezing to obtain the graphene oxide ice microspheres, and freeze-drying for 2 days in a freeze dryer to obtain the functional graphene oxide aerogel microsphere precursor.
(6) And (3) placing the graphene oxide aerogel microspheres in a tubular furnace, and annealing for 5 hours at 800 ℃ in an argon atmosphere to obtain the graphene aerogel microspheres loaded with cobalt metal particles.
Claims (9)
1. The macro preparation method of the functional two-dimensional material aerogel composite microspheres is characterized by comprising the following steps of:
(1) preparing or preparing a two-dimensional material with the particle size of less than 400 meshes, dispersing the two-dimensional material in water, ultrasonically stirring for 5 hours, keeping the two-dimensional material stable and not settling for 2 hours, and then adding an organic ligand, blending and ultrasonically stirring for 2 hours;
(2) dissolving corresponding functional salt into a certain amount of deionized water as a receiving bath, then adding a certain amount of organic solvent into a salt solution, and stirring for 1 h;
(4) filling the stable dispersion liquid prepared in the step (1) into a spraying system, and controlling the spraying distance to be 2-5 m, wherein the power of the spraying system is 500w, and the particle size range of fog drops of the spraying system is 1-200 um; and placing the receiving bath under the spraying system;
(5) and (4) filtering, cleaning and freezing the solid microspheres obtained in the step (4) through a screen, and freeze-drying the solid microspheres in a freeze dryer for two days to obtain the two-dimensional material aerogel microspheres or the functional two-dimensional material aerogel microspheres.
2. The macro preparation method of the functional two-dimensional material aerogel composite microspheres according to claim 1, further comprising:
(6) and (5) reducing the two-dimensional material aerogel microspheres obtained in the step (5) by using a high-temperature thermal reduction method to obtain the functionalized two-dimensional material aerogel microspheres.
3. The macro preparation method of the functional two-dimensional material aerogel composite microspheres of claim 1, wherein the two-dimensional material in step (1) is one or more of the following materials:
graphene GN type: single-layer graphene, multi-layer graphene, graphene oxide, reduced graphene oxide;
topological insulator TI class: bi2Se3、Bi2Te3；
Transition metal sulfides TMDCs type: CaPS3、CoPS3、FePS3、FeSe、GaS、GaSe、GaTe、GeS、SnS2、SnSe、TaS2、TaB2、TaS3、TaSe2、TiS2、Tl2S、WS2、WSe2、ZnPS3、InSe、MnPS3、MoS2、MoSe2ReS2、ReSe2；
MXene group: tin+1Cn、Nbn+1Cn、Vn+1Cn、Mon+1Cn(ii) a And VB2, MgB2、MoTe2、NbB2、PdTe2、PtTe、Sb2Te3。
4. The macro preparation method of the functional two-dimensional material aerogel composite microspheres of claim 1, wherein the organic ligand in step (1) is selected from small molecules or macromolecules with carboxyl, phosphoryl, hydroxyl, sulfate, amino and amide groups capable of coordinating with metal ions: polyacrylamide, polyvinylpyrrolidone, sodium alginate, sodium carboxymethylcellulose, polyoxyethylene, sodium polyacrylate, polyvinyl alcohol, starch, polysaccharide, chitin and sodium cellulose acetate.
5. The macro preparation method of the functional two-dimensional material aerogel composite microspheres according to claim 1, wherein the mass ratio of the deionized water, the two-dimensional material and the organic ligand in the step (1) is as follows: 100-110 parts: 1-2 parts of: 1-2 parts; the mass ratio of the salt to the deionized water in the step (3) is as follows: 3-30 parts of: 70-97 parts.
6. The macro-preparation method of the functional two-dimensional material aerogel composite microspheres according to claim 1, wherein the corresponding functional salt in step (2) is calcium oxalate, calcium carbonate, calcium phosphate, calcium gluconate, calcium hydrogen phosphate, calcium lactate, calcium chloride, calcium halide, calcium nitrate, calcium chlorate, calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate; magnesium nitrate, magnesium chloride, magnesium sulfate; cobalt acetate, nickel acetate, iron acetate, cobalt hydrochloride, nickel hydrochloride, iron hydrochloride, cobalt nitrate, nickel nitrate, iron nitrate, cobalt sulfate, nickel sulfate, ferric sulfate.
7. The macro preparation method of the functional two-dimensional material aerogel composite microspheres according to claim 1, wherein the organic solvent in step (2) is any one or more of acetic acid, acetone, acetonitrile, DMF, DMSO, dioxane, ethanol, methanol, isopropanol, and tetrahydrofuran.
8. The macro preparation method of the functional two-dimensional material aerogel composite microspheres according to claim 2, wherein the high temperature thermal reduction method in the step (6) is: and placing the obtained two-dimensional material aerogel microspheres in a high-temperature environment, and annealing for 2-5h at 800 ℃ in an inert gas atmosphere.
9. Functional two-dimensional material aerogel composite microspheres, characterized by being obtained by the preparation method of any one of claims 1 to 8.
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