CN109956494B - Few-layer-structure ZnO two-dimensional nanosheet and preparation method thereof - Google Patents
Few-layer-structure ZnO two-dimensional nanosheet and preparation method thereof Download PDFInfo
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Abstract
The invention provides a few-layer structure ZnO two-dimensional nanosheet and a preparation method thereof. The preparation method comprises the following steps: constructing an oil phase organic solution of a monomolecular layer on the surface of the ZnO precursor solution; and reacting at a preset temperature to generate the ZnO two-dimensional nanosheet with the few-layer structure at the oil interface of the oil-phase organic solution and the ZnO precursor solution. According to the invention, the ZnO two-dimensional nanosheet with a few-layer structure is epitaxially grown by utilizing the coupling effect between the oil-phase organic solution and the oily organic matter in the ZnO precursor solution. The method is very simple to operate, and the microstructure of the ZnO two-dimensional nanosheet obtained by the method has a corrugated shape similar to a graphene structure.
Description
Technical Field
The invention relates to a few-layer two-dimensional material and a preparation method thereof, in particular to a few-layer ZnO two-dimensional nanosheet and a preparation method thereof.
Background
The appearance of graphene has brought the attention of many researchers to few-layer two-dimensional materials. Many layers of two-dimensional materials exhibit excellent physicochemical properties such as extremely high room temperature carrier mobility, quantum hall effect, extremely large specific surface area, high young's modulus, excellent optical transmittance, and electrical and thermal conductivity, among others. However, the two-dimensional materials reported at present are mainly directed to material systems with a layered structure, such as transition metal sulfides, black phosphorus, layered oxides, and the like. In order to synthesize few layer materials, methods such as mechanical stripping, ion intercalation, CVD and the like are fully applied to prepare single-layer two-dimensional materials. However, non-layered oxides such as ZnO, CdS, and WO3 are difficult to prepare by the above method, and therefore, it is urgently needed to find a suitable method for constructing a non-layered few-layer structure (few-layered) two-dimensional nanosheet to investigate the physicochemical properties thereof.
Disclosure of Invention
The invention aims to provide a simple scheme for constructing a non-layered few-layer structure two-dimensional ZnO nano sheet.
According to one aspect of the invention, a preparation method of a few-layer structure ZnO two-dimensional nanosheet is provided, and comprises the following steps:
constructing an oil phase organic solution of a monomolecular layer on the surface of the ZnO precursor solution;
and reacting at a preset temperature to generate the ZnO two-dimensional nanosheet with the few-layer structure at the oil interface of the oil-phase organic solution and the ZnO precursor solution.
Optionally, the preset temperature is 60-65 ℃.
Optionally, the oil phase organic solution is a mixed solution of an oily organic substance and a volatile solvent.
Optionally, the volatile solvent is chloroform, ethanol or acetone.
Optionally, the volume ratio of the oily organic matter to the volatile solvent is 0.1-0.5%: 1.
optionally, the step of performing the reaction at a predetermined temperature, wherein the reaction time is 1.5-2 h.
Optionally, the ZnO precursor solution is a mixed solution of a zinc salt solution and a water-soluble organic base, and the chemical structure of the water-soluble organic base contains a methyl group.
Optionally, the zinc salt solution is zinc nitrate, zinc sulfate or zinc acetate, and the water-soluble organic base is hexamethylenetetramine or tetramethylammonium hydroxide.
According to another aspect of the invention, the few-layer structure ZnO two-dimensional nanosheet is prepared by the preparation method of any one of claims 1 to 8, and the structure of the few-layer structure ZnO two-dimensional nanosheet has a corrugated shape similar to a graphene structure.
Optionally, the thickness of the few-layer structure ZnO two-dimensional nanosheet is 1-3 nm.
According to the invention, the ZnO two-dimensional nanosheet with a few-layer structure is epitaxially grown by utilizing the coupling effect between the oil-phase organic solution and the oily organic matter in the ZnO precursor solution. The inventor has proved through a large amount of experiments and creatively proposed the scheme, and has obtained unexpected technical effect. The method is very simple to operate, and the microstructure of the ZnO two-dimensional nanosheet obtained by the method has a corrugated shape similar to a graphene structure.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
fig. 1 is a schematic flow chart of a method for preparing a few-layer structure ZnO two-dimensional nanosheet according to one embodiment of the present invention;
FIG. 2 is a transmission electron microscope image of a few-layer structure ZnO two-dimensional nanosheet in a first embodiment of the present invention;
FIG. 3 is a selected area electron diffraction pattern of a few-layer structure ZnO two-dimensional nanosheet in a first embodiment according to the present invention;
FIG. 4 is an AFM diagram of few-layer structure ZnO two-dimensional nanoplates according to a first embodiment of the present invention;
fig. 5 is a thickness map of ZnO two-dimensional nanoplates at the line region shown in fig. 4.
Detailed Description
Fig. 1 shows a schematic flow chart of a preparation method of few-layer structure ZnO two-dimensional nanosheets according to one embodiment of the present invention. As shown in fig. 1, the preparation method comprises the following steps:
s100, constructing an oil phase organic solution of a monomolecular layer on the surface of the ZnO precursor solution;
s200, reacting at a preset temperature to generate a ZnO two-dimensional nanosheet at an oil interface of the oil-phase organic solution and the ZnO precursor solution.
In step S100, the ZnO precursor solution is a zinc salt solution and a water-soluble organic base, and the chemical structure of the water-soluble organic base includes a methyl group. The salt solution of zinc may be, for example, zinc nitrate, zinc sulfate or zinc acetate, but is not limited thereto. The water-soluble organic base may be, for example, hexamethylenetetramine or tetramethylammonium hydroxide, and is not limited thereto. The concentration of the zinc salt solution and the water-soluble organic base is any concentration in the range of 10-50 mmol/l. For example, the concentration of the zinc salt solution and the water-soluble organic base may be 10mmol/l, 20mmol/l, 30mmol/l, 40mmol/l or 50mmol/l, or may be any other concentration between 10 and 50 mmol/l.
The oil phase organic solution is a mixed solution of an oily organic substance and a volatile solvent. The volume ratio of the oily organic matter to the volatile solvent is within the range of 0.1-0.5%: 1, or any ratio therebetween. For example, the volume ratio of oily organic substance to volatile solvent may be 0.1%: 1. 0.2%: 1. 0.3%: 1. 0.4%: 1 or 0.5%: 1. when the volume ratio of the oily organic matter to the volatile solvent is less than 0.1%: 1, the concentration of the oily organic matters is too low, the oil-phase organic solution with a large volume needs to be measured to be dripped into the ZnO precursor solution, at the moment, the ZnO precursor solution is immersed in the oil-phase organic solution due to overlarge gravity of the liquid drops, and the monomolecular oil-phase organic solution is not easy to construct on the surface of the ZnO precursor solution. When the volume ratio of the oily organic matter to the volatile solvent is more than 0.5%: 1, the concentration of the oily organic matter is too high, the oil phase organic solution with small volume needs to be measured to be dropped into the ZnO precursor solution, and the smaller the volume is, the larger the measurement error is, so that the oil phase organic solution with a better monomolecular layer is not easy to construct.
The oily organic substance may be, for example, cyclohexane, octadecene or oleic acid, but is not limited thereto. The volatile solvent may be, for example, chloroform, ethanol or acetone, again without being limited thereto. The volatile solvent is selected to be capable of dissolving the oily organic substance and to be easily volatile at room temperature.
Specifically, in step S200, the preset temperature is any temperature in the range of 60 to 65 ℃. The predetermined temperature may be, for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃ or 65 ℃. When the preset temperature is lower than 60 ℃, no reaction occurs. When the preset temperature is higher than 65 ℃, the aqueous solution in the ZnO precursor solution is easy to evaporate, an oil interface with good dispersibility cannot be formed, and the structure of a product generated by the reaction is influenced finally. The reaction time may be, for example, 1.5 hours or 2 hours, or any of 1.5 to 2 hours. When the reaction time is less than 1.5h, ZnO two-dimensional nanosheets cannot be generated. When the reaction time is longer than 2h, the structure of the generated ZnO nanosheet changes, i.e., the obtained product is not the product expected to be obtained.
According to the invention, the ZnO two-dimensional nanosheet with a few-layer structure is epitaxially grown by utilizing the coupling effect between the oil-phase organic solution and the oily organic matter in the ZnO precursor solution. The inventor has proved through a large amount of experiments and creatively proposed the scheme, and has obtained unexpected technical effect. The method is very simple to operate, and the microstructure of the ZnO two-dimensional nanosheet obtained by the method has a corrugated shape similar to a graphene structure.
The following is a detailed description of specific embodiments.
Example 1:
the preparation method of the few-layer structure ZnO two-dimensional nanosheet comprises the following steps:
s1, preparing precursor solutions of zinc nitrate and hexamethylenetetramine with the concentrations of 25mmol/l, measuring 14ml of the precursor solution, and placing the precursor solution into a volumetric flask;
s2, cyclohexane and chloroform according to the volume ratio of 0.1%: 1 preparing a solution to form an oil-phase organic solution;
s3, dripping 3 mu l of oil phase organic solution on the liquid surface of the precursor solution, and forming a monomolecular oil phase layer on the liquid surface of the precursor solution along with the evaporation of chloroform;
s4, reacting the solution in the step S3 at 60 ℃ for 1.5h to obtain the ZnO two-dimensional nanosheet with the few-layer structure.
Fig. 2 shows a transmission electron microscope image of a few-layer structure ZnO two-dimensional nanosheet in a first embodiment of the present invention. As can be seen from fig. 2, the ZnO nanosheet with the few-layer structure has a graphene-like wrinkled shape, and is thinner and more transparent than carbon.
Fig. 3 shows a selected-region electron diffraction pattern of a few-layer structure ZnO two-dimensional nanosheet in a first embodiment of the present invention. As can be seen from fig. 3, the crystal structure of the few-layer structured ZnO nanosheet is a hexagonal phase structure typical of ZnO. With reference to fig. 4 and 5, the thickness of the few-layer structure ZnO nanosheet is 2.2 nm.
Example 2:
the preparation method of the few-layer structure ZnO two-dimensional nanosheet comprises the following steps:
s1, preparing precursor solutions of zinc nitrate and hexamethylenetetramine with the concentrations of 35mmol/l, measuring 12ml of the precursor solutions, and placing the precursor solutions into a volumetric flask;
s2, cyclohexane and chloroform according to the volume ratio of 0.2%: 1 preparing a solution to form an oil-phase organic solution;
s3, dripping 5 mu l of oil phase organic solution on the liquid surface of the precursor solution, and forming a monomolecular oil phase layer on the liquid surface of the precursor solution along with the evaporation of chloroform;
s4, reacting the solution in the step S3 at 62 ℃ for 2h to obtain the ZnO two-dimensional nanosheet with the few-layer structure.
Example 3:
the preparation method of the few-layer structure ZnO two-dimensional nanosheet comprises the following steps:
s1, preparing precursor solutions of zinc nitrate and hexamethylenetetramine with the concentrations of 45mmol/l, measuring 10ml of the precursor solution, and placing the precursor solution into a volumetric flask;
s2, cyclohexane and chloroform, wherein the volume ratio is 0.35%: 1 preparing a solution to form an oil-phase organic solution;
s3, dropping 6 μ l of oil phase organic solution on the liquid surface of the precursor solution, and forming a monomolecular oil phase layer on the liquid surface of the precursor solution along with the evaporation of chloroform;
s4, reacting the solution in the step S3 at 65 ℃ for 1.5h to obtain the ZnO two-dimensional nanosheet with the few-layer structure.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (6)
1. A preparation method of a few-layer ZnO two-dimensional nanosheet comprises the following steps:
constructing an oil phase organic solution of a monomolecular layer on the surface of the ZnO precursor solution;
reacting at a preset temperature to generate a ZnO two-dimensional nanosheet with a few-layer structure at an oil interface of the oil-phase organic solution and the ZnO precursor solution;
the oil phase organic solution is a mixed solution of an oily organic matter and a volatile solvent;
the volume ratio of the oily organic matter to the volatile solvent is 0.1-0.5%: 1;
the preset temperature is 60-65 ℃;
in the step of carrying out the reaction at a preset temperature, the reaction time is 1.5-2 h.
2. The production method according to claim 1, wherein the volatile solvent is chloroform, ethanol or acetone.
3. The production method according to claim 1 or 2, wherein the ZnO precursor solution is a mixed solution of a zinc salt solution and a water-soluble organic base, and the chemical structure of the water-soluble organic base contains a methyl group.
4. The production method according to claim 3, wherein the salt solution of zinc is zinc nitrate, zinc sulfate or zinc acetate, and the water-soluble organic base is hexamethylenetetramine or tetramethylammonium hydroxide.
5. A few-layer structure ZnO two-dimensional nanosheet prepared by the preparation method of any one of claims 1-4, wherein the structure of the few-layer structure ZnO two-dimensional nanosheet is corrugated like a graphene structure.
6. The few-layer structure ZnO two-dimensional nanosheet of claim 5, wherein the few-layer structure ZnO two-dimensional nanosheet has a thickness of from 1 to 3 nm.
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