CN116022839A - Preparation method for preparing micro-nano structure at one time, micro-nano structure and application thereof - Google Patents
Preparation method for preparing micro-nano structure at one time, micro-nano structure and application thereof Download PDFInfo
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- CN116022839A CN116022839A CN202111248338.5A CN202111248338A CN116022839A CN 116022839 A CN116022839 A CN 116022839A CN 202111248338 A CN202111248338 A CN 202111248338A CN 116022839 A CN116022839 A CN 116022839A
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Abstract
The invention provides a preparation method for preparing a micro-nano structure, the micro-nano structure and application thereof. The preparation method of the invention comprises the following steps: 1) Placing liquid metal in micro pits of a micro pit array structure; 2) And (3) placing the micro-pit array structure with the liquid metal in the step (1) into a metal salt aqueous solution, and performing hydrothermal reaction to obtain solid particles with micro-nano structures. The preparation method can prepare the micro-nano structure at the same time in one step, can effectively improve the preparation speed of the micro-nano structure and reduce the preparation cost of the micro-nano material.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method for preparing a micro-nano structure at one time, the micro-nano structure and application thereof.
Background
The special structural effect of the micro-nano structure plays an irreplaceable role in a plurality of fields. For example, the self-cleaning function of the lotus leaf surface is mainly caused by the surface micro-nano structure. In the process of preparing micro-nano structures, many researches are performed by preparing micro-scale structures first and then designing nano structures, which increases the experimental steps and cost.
Disclosure of Invention
In order to simplify the experimental process and realize one-step preparation of the micro-nano structure, the invention provides a preparation method for preparing the micro-nano structure at one time, the micro-nano structure and application thereof. By this method, micro-nano structures can be rapidly prepared.
The invention provides a preparation method of a micro-nano structure, which comprises the following steps: 1) Placing liquid metal in micro pits of a micro pit array structure; 2) And (3) placing the micro-pit array structure with the liquid metal in the step (1) into a metal salt aqueous solution, and performing hydrothermal reaction to obtain solid particles with micro-nano structures.
According to an embodiment of the invention, in step 2), the liquid metal expands in situ in the micro-pits to obtain solid particles with micro-nano structures.
According to an embodiment of the present invention, when a liquid metal is heated in an aqueous metal salt solution to cause a hydrothermal reaction, the liquid metal reacts with hydrogen ions in the aqueous solution to form hydroxides and oxides of the metal, thereby producing a phase change from a liquid state to a solid state; during the phase change of the liquid metal, the hydrogen gas is generated, which also causes the inside to form porous. Both the phase change of the liquid metal and the generation of hydrogen gas cause the liquid metal to expand in volume during the hydrothermal reaction, thereby expanding out of the micropits. This expanded microsphere surface then provides a seed for nanostructure growth, thereby creating nanostructures on its surface.
Preferably, the microspheres have a hollow porous sphere structure.
According to an embodiment of the invention, the liquid metal is selected from gallium-based liquid metal alloys or bismuth-based liquid metal alloys. For example, the gallium-based liquid metal is selected from gallium-indium liquid metal alloys, wherein the mass ratio of gallium metal to indium metal is for example 10:1 to 3:1. for example, the gallium-based liquid metal may also be gallium indium tin, wherein the mass ratio of gallium metal, indium metal, and tin metal may be 10:1:0.1 to 10:1:1 or 75:25:0.1 to 75:25:1.
Illustratively, the gallium indium liquid metal alloy is GaIn10 or GaIn24.5, which has a melting point of 15 ℃ ± 2 ℃.
According to an embodiment of the present invention, the size of the micro-pits in the micro-pit array structure and the amount of liquid metal in the micro-pits may determine the particle size of the prepared solid particles having the micro-nano structure.
According to an embodiment of the present invention, the size of the micro-pits is not particularly limited, and a person skilled in the art may appropriately select the size of the micro-pits based on the size of the micro-nano particles to be prepared, for example, the average diameter of the micro-pits may be 1 μm to 8mm, such as 2 μm to 5mm, for example, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1mm.
Preferably, the average diameter of the micro pits is 5-200 μm.
According to an embodiment of the present invention, the pitch of the micro pits is not particularly limited, and may be, for example, 0.1 μm to 8mm, such as 0.5 μm to 5mm, such as 1 μm to 1mm. Preferably, the micro-pits have a pitch of 0.1-200 μm. The pitch of the micro-pits in the invention refers to the average distance between the center points of two adjacent micro-pits in the micro-pit array structure.
According to an embodiment of the present invention, the micro-pit array structure may be prepared by a method known in the art, for example, by a replica method, machining or 3D printing technique.
According to embodiments of the invention, the replica process can replicate, for example, the structure of lotus leaves. For example, a replica material (such as silica gel and a curing agent) is spread on the surface of lotus leaves, and is cured to obtain the micro-pit array structure.
According to an embodiment of the invention, in step 1), the liquid metal is spread over the surface of the micro-pit array structure above its melting point, the liquid metal entering the micro-pits.
According to an embodiment of the invention, in step 2), the temperature of the hydrothermal reaction is, for example, 60-150 ℃, preferably 70-120 ℃, such as 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃.
According to an embodiment of the invention, in step 2), the time of the hydrothermal reaction is 1 to 20 hours, for example 1 to 10 hours. The pressure of the hydrothermal reaction is, for example, atmospheric pressure.
According to an embodiment of the invention, in step 2), the metal salt is selected from at least one of zinc salts, silver salts or copper salts, for example from at least one of zinc nitrate, silver nitrate or copper nitrate, preferably zinc nitrate.
According to an embodiment of the present invention, hexamethylenetetramine may be further contained in the aqueous metal salt solution.
According to an embodiment of the invention, the concentration of the aqueous metal salt solution is, for example, 0.001-0.016g/mL.
According to an exemplary embodiment of the present invention, the preparation method includes: placing the micro-pit array structure with the liquid metal in the step 1) into an aqueous solution containing zinc salt to perform hydrothermal reaction, and growing zinc oxide with petal-shaped structures on the surfaces of the solid microspheres formed by the liquid metal.
According to an embodiment of the present invention, the preparation method further comprises: and carrying out surface hydrophobic treatment on the solid particles with the micro-nano structures.
According to an embodiment of the present invention, the method of surface hydrophobic treatment includes, for example: and (3) treating the solid particles with the micro-nano structures by using fluorosilane to obtain the solid particles with the micro-nano structures, the surfaces of which are super-hydrophobic. Illustratively, the fluorosilane is selected from the group consisting of FAS-17.
Illustratively, the fluorosilane treatment specifically includes: and (3) placing FAS-17 fluorosilane and the solid particles with the micro-nano structure into a vacuum dryer, vacuumizing, and then heating in a vacuum state. For example, the vacuum dryer is 1-10L. For example, the evacuation time is 5-30 minutes. For example, the heating is carried out at 60-90℃for 3-9 hours.
The invention also provides the solid particles with the micro-nano structure prepared by the method.
According to an embodiment of the invention, the solid particles comprise a hollow porous sphere structure.
According to an embodiment of the present invention, the surface of the solid particles has a petal-shaped structure.
According to an embodiment of the invention, the average particle size of the solid particles is determined by the size of the micro-pits in the micro-pit array structure and the amount of liquid metal in the micro-pits, e.g. 1 μm-8mm, such as 2 μm-5mm, e.g. 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1mm. Illustratively, the solid particles have an average particle size of 10-500 μm.
The invention also provides application of the micro-nano structure in the super-hydrophobic field and the light absorption field.
Advantageous effects
The invention provides a preparation method for simultaneously preparing a micro-nano structure in one step, which can effectively improve the preparation speed of the micro-nano structure and reduce the preparation cost of a micro-nano material. And the size of the prepared solid particles with the micro-nano structure can be controlled.
Drawings
FIG. 1 is a schematic diagram of the present invention for preparing micro-nanospheres from liquid metal;
FIG. 2 is an electron microscope image of the micro-pore array structure of example 1;
FIG. 3 is an electron microscope image of the micro-nanospheres prepared in example 1;
fig. 4 is an electron microscope image of the micro-nano structure prepared in examples 2 and 3.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
(1) Firstly, preparing a micro-pit array structure and copying the lotus leaf structure. Silica gel and a curing agent are mixed according to the mass ratio of 10:1, uniformly stirring and spreading on the surface of lotus leaves. Curing at 70deg.C for 50 min, and removing lotus leaf to obtain micropore array surface as shown in figure 2;
(2) Spreading GaIn10 liquid metal alloy on the surface of the hole array at the temperature of above 15 ℃ of melting point, wherein the liquid metal enters the micro pits in the micro pit array;
(3) Placing the micro-pit array structure with the liquid metal obtained in the step (2) into a reaction kettle, adding a zinc nitrate aqueous solution with the concentration of 0.7g/100mL, heating to 90 ℃, and keeping the temperature for 4 hours, wherein the liquid metal expands inside the micro-pit array to obtain solid particles with micro-nano structures, and the surfaces of the solid particles are petal-shaped, as shown in figure 3; EDS tests show that the petal-shaped structure comprises zinc oxide;
(4) Surface hydrophobic treatment: and (3) treating the solid particles with the micro-nano structure obtained in the step (3) by using fluorosilane to obtain the solid particles with the micro-nano structure with the superhydrophobic surface, wherein the fluorosilane treatment specifically comprises:
placing 1-3 drops of FAS-17 fluorosilane and the micro-nano structure obtained in the step (3) into a vacuum dryer (1-10L), vacuumizing for 5-30 minutes, then placing the mixture into an oven to heat in a vacuum state, and keeping the temperature at 60-90 ℃ for 3-9 hours.
Example 2
The preparation method of the micro-nano structured solid particles of the present embodiment is different from that of example 1 in that a micro-pit array structure is prepared by 3D printing technology, the diameter of the micro-pits is 5 μm, and the average pitch of the micro-pits is 5 μm.
Example 3
(1) And preparing a micro-pit array structure with different micro-pit diameters through machining, wherein the micro-pit diameters are respectively as follows: 200 μm, 120 μm, 80 μm, 50 μm; the average pitch of the corresponding micropits was 500 μm.
(2) Spreading GaIn24.5 liquid metal alloy on the surface of the prepared micro-pit array at the temperature above the melting point of 15 ℃ respectively, wherein liquid metal enters the micro-pits in the micro-pit array;
(3) Placing the micro-pit array structure with the liquid metal obtained in the step (2) into a reaction kettle, adding zinc nitrate aqueous solution with the concentration of 0.7g/100mL and 0.3g hexamethylenetetramine, heating to 100 ℃, and keeping for 2 hours to obtain solid particles with a micro-nano structure;
(4) Surface hydrophobic treatment: and (3) treating the solid particles with the micro-nano structure obtained in the step (3) by using fluorosilane to obtain the micro-nano structure with the super-hydrophobic surface, wherein the fluorosilane treatment step is the same as that of the embodiment 1.
Fig. 4 shows the solid particles with micro-nano structure prepared in examples 2-3, wherein the micro-pits in fig. 4a-e have diameters of 200 μm, 120 μm, 80 μm, 50 μm, 5 μm, respectively, and fig. 4f is a partial enlarged view of fig. e.
The above description has been given of exemplary embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing a micro-nanostructure, the method comprising: 1) Placing liquid metal in micro pits of a micro pit array structure; 2) And (3) placing the micro-pit array structure with the liquid metal in the step (1) into a metal salt aqueous solution, and performing hydrothermal reaction to obtain solid particles with micro-nano structures.
2. The method of manufacturing according to claim 1, wherein the liquid metal is selected from gallium-based liquid metal alloys or bismuth-based liquid metal alloys;
preferably, the gallium-based liquid metal is selected from gallium indium liquid metal alloys.
3. The method of claim 1, wherein the average diameter of the micro-pits is 1 μm to 8mm. Preferably, the micro-pits may have a pitch of 0.1 μm to 8mm.
4. The method of claim 1, wherein in step 1), the liquid metal is spread over the surface of the micro-pit array structure above its melting point, and the liquid metal enters the micro-pits.
Preferably, in step 2), the temperature of the hydrothermal reaction is 60-150 ℃.
Preferably, the hydrothermal reaction time is 1 to 20 hours.
Preferably, the pressure of the hydrothermal reaction is atmospheric pressure.
5. The method according to claim 1, wherein in step 2) the metal salt is selected from at least one of zinc salts, silver salts or copper salts, such as at least one of zinc nitrate, silver nitrate or copper nitrate.
Preferably, the concentration of the aqueous metal salt solution is 0.001-0.016g/mL.
6. The method of any one of claims 1-5, further comprising: and carrying out surface hydrophobic treatment on the solid particles with the micro-nano structures.
Preferably, the method for surface hydrophobic treatment comprises: and (3) treating the solid particles with the micro-nano structures by using fluorosilane to obtain the solid particles with the micro-nano structures, the surfaces of which are super-hydrophobic.
7. The method of any one of claims 1-6, wherein the method of preparation comprises: placing the micro-pit array structure with the liquid metal in the step 1) into an aqueous solution containing zinc salt to perform hydrothermal reaction, and growing zinc oxide with petal-shaped structures on the surfaces of the solid microspheres formed by the liquid metal.
8. A solid particle having a micro-nanostructure, prepared by the method of any one of claims 1-7.
9. The micro-nano structure according to claim 8, wherein the solid particles comprise a hollow porous sphere structure; preferably, the surface of the solid particles has a petal-shaped structure.
10. Use of the micro-nano structure according to claim 8 or 9 in the field of superhydrophobicity and light absorption.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111248338.5A CN116022839A (en) | 2021-10-26 | 2021-10-26 | Preparation method for preparing micro-nano structure at one time, micro-nano structure and application thereof |
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| CN202111248338.5A CN116022839A (en) | 2021-10-26 | 2021-10-26 | Preparation method for preparing micro-nano structure at one time, micro-nano structure and application thereof |
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