CN112340714A - Flower-shaped and chain-shaped black phosphorus material and preparation method thereof - Google Patents
Flower-shaped and chain-shaped black phosphorus material and preparation method thereof Download PDFInfo
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- CN112340714A CN112340714A CN202011271876.1A CN202011271876A CN112340714A CN 112340714 A CN112340714 A CN 112340714A CN 202011271876 A CN202011271876 A CN 202011271876A CN 112340714 A CN112340714 A CN 112340714A
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a flower-shaped and chain-shaped black phosphorus material and a preparation method thereof, belonging to the technical field of black phosphorus material preparation and comprising the following steps: s1, taking out black phosphorus in a protective gas atmosphere, grinding the black phosphorus in an air environment to obtain black phosphorus powder, and dispersing the black phosphorus powder into an organic dispersing agent to obtain a dispersion liquid; s2, performing microwave treatment on the dispersion liquid prepared in the S1 in an atmosphere of protective gas at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid; s3, centrifuging the mixed solution prepared in the S2, collecting the upper-layer liquid, and drying to obtain flower-shaped and chain-shaped black phosphorus powder; the surface of the flower-shaped and chain-shaped black phosphorus material provided by the invention is of a flower-shaped and chain-shaped structure, the flower-shaped size is smaller, and the chain-shaped size is larger; the invention has simple operation, high product quality and wide market prospect.
Description
Technical Field
The invention belongs to the technical field of black phosphorus material preparation, and particularly relates to a flower-shaped and chain-shaped black phosphorus material and a preparation method thereof.
Background
Two-dimensional layered materials, such as graphene and transition metal double-halogen compounds, have become a promising class of nanomaterials for basic research and potential application fields due to their interesting properties. Flower & chain as another form of nanomaterial, in addition to two-dimensional layered structure and one-dimensional quantum dot structure, exhibits excellent electronic and optical properties due to unique crystal structure. For example, graphene and molybdenum disulfide flower-like materials have been successfully prepared and are widely used in the fields of optoelectronic devices, catalysis, batteries, and the like.
The black phosphorus is a two-dimensional material, has excellent highly-oriented characteristics and a band gap depending on the number of layers of the material, and the black phosphorus nanosheets, the nanobelts and the quantum dots all have the flexibility, anisotropy, high specific surface area, electronic constraint and edge effect of the black phosphorus nanomaterial, and the flower-shaped and chain-shaped structure can cause abnormal control on the structure of the electronic band, so that a new phenomenon and unique structural application are generated, and the black phosphorus is a research hotspot. However, this study is still in its infancy and no black phosphorus flower & chain structures have been produced in the prior art.
Disclosure of Invention
In order to solve the problems, the invention provides a flower-shaped and chain-shaped black phosphorus material and a preparation method thereof, and lays a foundation for further researching the flower-shaped and chain-shaped structures of the black phosphorus.
The invention aims to provide a preparation method of a flower & chain black phosphorus material, which comprises the following steps:
s1, taking out black phosphorus in a protective gas atmosphere, grinding the black phosphorus in an air environment to obtain black phosphorus powder, and dispersing the black phosphorus powder into an organic dispersing agent to obtain a dispersion liquid;
grinding the block black phosphorus in the air, wherein oxygen and moisture in the air enter the black phosphorus layer in the grinding process, so that oxygen and moisture are carried between the black phosphorus layers, and covalent bonds between the black phosphorus layers are destroyed through oxidation, thereby promoting the generation of flower-shaped and chain-shaped structures
S2, performing microwave treatment on the dispersion liquid prepared in the S1 in an atmosphere of protective gas at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid; further destroying covalent bonds between the black phosphorus layers by microwave treatment;
s3, centrifuging the mixed solution prepared in the step S2, collecting upper-layer liquid (the lower-layer sediment is large in size, and black phosphorus materials with small sizes are dispersed in the upper-layer liquid, separating the materials with large sizes through centrifugation to obtain the black phosphorus materials with small sizes), and drying to obtain flower-shaped and chain-shaped black phosphorus powder.
Preferably, in S1, grinding is carried out for 20-30min in an air environment.
Preferably, in S1, the organic dispersant is N-methylpyrrolidone.
Preferably, in S1, the dosage ratio of the black phosphorus to the organic dispersant is 3-8 g: 1L of the compound.
Preferably, in S2, the microwave treatment time is 25-35 min.
Preferably, in S3, the centrifugation treatment is performed under the conditions of firstly centrifuging at 5000-7000rmp for 15-25min, collecting the supernatant liquid, and then centrifuging the supernatant liquid at 14000rmp for 20 min.
The second purpose of the invention is to provide the flower-shaped & chain-shaped black phosphorus material prepared by the preparation method.
Preferably, the black phosphorus material is distributed in a chain structure, and the chain structure is composed of a flower-like structure.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method comprises the following steps of grinding the block black phosphorus in the air, wherein oxygen and moisture in the air enter the black phosphorus layer in the grinding process, so that oxygen and moisture are carried between the black phosphorus layers, and covalent bonds between the black phosphorus layers are destroyed through oxidation, so that the generation of flower-shaped and chain-shaped structures is promoted;
(2) the surface of the black phosphorus material provided by the invention is distributed in a chain structure, the chain structure is formed by a flower-shaped structure, the flower-shaped size is small (about 50nm), and the chain size is large (10 mu m); the preparation method is simple and convenient, has high product quality, and lays a foundation for further researching black phosphorus flower-shaped and chain-shaped structures.
Drawings
Fig. 1 is a transmission electron micrograph and an electron diffraction pattern of the flower & chain black phosphorus material prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and practical for those skilled in the art, the present invention will be described in detail below with reference to the accompanying drawings and the detailed description, but the present invention is not limited to the following examples.
The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the raw materials and reagents, if not specifically mentioned, are commercially available.
The invention provides a preparation method of a flower-shaped and chain-shaped black phosphorus material, which comprises the following steps:
s1, taking out black phosphorus in a protective gas atmosphere, grinding the black phosphorus in an air environment to obtain black phosphorus powder, and dispersing the black phosphorus powder into an organic dispersing agent to obtain a dispersion liquid;
s2, performing microwave treatment on the dispersion liquid prepared in the S1 in an atmosphere of protective gas at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid;
and S3, centrifuging the mixed solution prepared in the S2, collecting the upper-layer liquid, and drying to obtain the flower-shaped and chain-shaped black phosphorus powder.
According to the invention, the block black phosphorus is ground in the air, oxygen and moisture in the air enter the black phosphorus layer in the grinding process, so that oxygen and moisture are carried between the black phosphorus layers, and covalent bonds between the black phosphorus layers are destroyed through oxidation, thereby promoting the generation of flower-shaped and chain-shaped structures.
Example 1
A preparation method of a flower-shaped and chain-shaped black phosphorus material comprises the following steps:
(1) taking out the block black phosphorus in a glove box filled with nitrogen, grinding the block black phosphorus into black phosphorus powder in an air environment, weighing 60mg of black phosphorus powder, dispersing the black phosphorus powder into 20mL of N-methylpyrrolidone (NMP), and sealing and shaking the mixture to obtain a black phosphorus-NMP dispersion liquid;
(2) adding the black phosphorus-NMP dispersion liquid obtained in the step (1) into a three-neck flask, reacting for 25min at 100 ℃ under the microwave power of 500W in an argon environment, and cooling the solution to room temperature;
(3) and (3) centrifuging the mixed solution obtained in the step (2) at 5000rmp for 15min, collecting upper-layer liquid, centrifuging the upper-layer liquid at 14000rmp for 20min at a high speed, collecting the upper-layer liquid (bright yellow), and drying to obtain flower-shaped and chain-shaped black phosphorus powder.
Example 2
A preparation method of a flower-shaped and chain-shaped black phosphorus material comprises the following steps:
(1) taking out the block black phosphorus in a glove box filled with nitrogen, grinding the block black phosphorus into black phosphorus powder in an air environment, weighing 80mg of black phosphorus powder, dispersing the black phosphorus powder into 10mL of NMP, and sealing and shaking the mixture to obtain black phosphorus-NMP dispersion liquid;
(2) adding the black phosphorus-NMP dispersion liquid obtained in the step (1) into a three-neck flask, reacting for 35min at 130 ℃ under the microwave power of 700W in an argon environment, and cooling the solution to room temperature;
(3) and (3) centrifuging the mixed solution obtained in the step (2) at 7000rmp for 25min, collecting upper-layer liquid, centrifuging the upper-layer liquid at 14000rmp for 20min at a high speed, collecting the upper-layer liquid (bright yellow), and drying to obtain the flower-shaped and chain-shaped black phosphorus powder.
Example 3
A preparation method of a flower-shaped and chain-shaped black phosphorus material comprises the following steps:
(1) taking out the block black phosphorus in a glove box filled with nitrogen, grinding the block black phosphorus into black phosphorus powder in an air environment, weighing 80mg of black phosphorus powder, dispersing the black phosphorus powder into 20mL of NMP, and sealing and shaking the mixture to obtain black phosphorus-NMP dispersion liquid;
(2) adding the black phosphorus-NMP dispersion liquid obtained in the step (1) into a three-neck flask, reacting for 25min at 120 ℃ under the microwave power of 600W in an argon environment, and cooling the solution to room temperature;
(3) and (3) centrifuging the mixed solution obtained in the step (2) at 6000rmp for 20min, collecting upper-layer liquid, centrifuging the upper-layer liquid at 14000rmp for 20min at a high speed, collecting the upper-layer liquid (bright yellow), and drying to obtain flower-shaped and chain-shaped black phosphorus powder.
The flower-like and chain-like black phosphorus materials obtained in the above examples 1 to 3 have similar performances, and the following description will be given only by taking example 1 as an example.
Fig. 1 is a transmission electron micrograph and an electron diffraction pattern of the flower & chain black phosphorus material prepared in example 1, and from fig. 1, it can be seen that a large amount of chain structure substances (the size is about 10 μm) exist in a low-power transmission electron micrograph (the upper left picture), which indicates that the chain black phosphorus material is successfully prepared, and after magnification (the upper right picture), it can be clearly seen that the chain structure is composed of a flower structure (the flower size is about 50nm), and after continuous magnification, it can be seen that a clear lattice fringe (the lower left picture) is evident, and at the same time, single crystal diffraction in an electron diffraction pattern (the lower right picture) is evident, which indicates that the synthesized black phosphorus flower & chain structure has excellent quality.
Therefore, the black phosphorus material with the flower-shaped and chain-shaped structure is successfully prepared, the surface of the black phosphorus material is distributed in the chain-shaped structure, the chain-shaped structure is formed by the flower-shaped structure, the flower-shaped size is small (50nm), the chain-shaped size is large (10 mu m), the preparation method is simple and convenient, the product quality is high, and a foundation is laid for further researching the flower-shaped and chain-shaped structure of the black phosphorus.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any value between the two ends can be selected, and since the steps and methods used are the same as those of the embodiments, the preferred embodiments and effects thereof are described in the present invention for the sake of avoiding redundancy, but once the basic inventive concept is known, those skilled in the art may make other changes and modifications to the embodiments. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the principles and spirit thereof, and these modifications and variations also fall within the scope of the invention.
Claims (8)
1. A preparation method of a flower-shaped and chain-shaped black phosphorus material is characterized by comprising the following steps:
s1, taking out black phosphorus in a protective gas atmosphere, grinding the black phosphorus in an air environment to obtain black phosphorus powder, and dispersing the black phosphorus powder into an organic dispersing agent to obtain a dispersion liquid;
s2, performing microwave treatment on the dispersion liquid prepared in the S1 in an atmosphere of protective gas at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid;
and S3, centrifuging the mixed solution prepared in the S2, collecting the upper-layer liquid, and drying to obtain the flower-shaped and chain-shaped black phosphorus powder.
2. The method for preparing flower & chain black phosphorus material according to claim 1, wherein in S1, grinding is performed in air environment for 20-30 min.
3. The method for preparing a flower & chain black phosphorus material according to claim 1, wherein the organic dispersant is N-methylpyrrolidone in S1.
4. The method for preparing a flower & chain black phosphorus material as claimed in claim 3, wherein in S1, the dosage ratio of black phosphorus to organic dispersant is 3-8 g: 1L of the compound.
5. The method for preparing flower & chain black phosphorus material according to claim 1, wherein in S2, the microwave treatment time is 25-35 min.
6. The method as claimed in claim 1, wherein the centrifugation step S3 comprises centrifuging at 5000-7000rmp for 15-25min, collecting the upper liquid, and centrifuging at 14000rmp for 20 min.
7. The flower & chain black phosphorus material prepared by the preparation method according to any one of claims 1 to 6.
8. The flower & chain black phosphorus material as claimed in claim 7, wherein the black phosphorus material is distributed in a chain structure, and the chain structure is composed of flower structures.
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