CN112340714B - Flower-like and chain-like black phosphorus material and preparation method thereof - Google Patents
Flower-like and chain-like black phosphorus material and preparation method thereof Download PDFInfo
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- CN112340714B CN112340714B CN202011271876.1A CN202011271876A CN112340714B CN 112340714 B CN112340714 B CN 112340714B CN 202011271876 A CN202011271876 A CN 202011271876A CN 112340714 B CN112340714 B CN 112340714B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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-like and chain-like 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 into black phosphorus powder in an air environment, and dispersing the black phosphorus powder into an organic dispersing agent to prepare a dispersion liquid; s2, carrying out microwave treatment on the dispersion liquid prepared in the step S1 under the protection gas atmosphere at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid; s3, carrying out centrifugal treatment on the mixed solution prepared in the step S2, collecting upper-layer liquid, and drying to obtain flower-like and chain-like 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 extremely broad 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 dihalides, have become a promising class of nanomaterials for fundamental research and potential application fields due to their interesting properties. In addition to the two-dimensional layered structure and the one-dimensional quantum dot structure, the flower shape & chain shape as another form of nanomaterial exhibits excellent electronic and optical properties due to the unique crystal structure. For example, graphene and molybdenum disulfide flower-like materials have been successfully prepared and widely used in the fields of optoelectronic devices, catalysis, batteries, and the like.
Black phosphorus is a two-dimensional material with excellent high orientation characteristic and band gap depending on the number of layers of the material, and black phosphorus nanoplatelets, nanobelts and quantum dots all have flexibility, anisotropy, high specific surface area, electronic constraint and edge effect of the black phosphorus nanomaterial, and flower-like and chain-like structures can lead to abnormal control of the electronic belt structure and new phenomena and unique structural application, so that the black phosphorus nanoplatelets, nanobelts and quantum dots become research hot spots. However, to date, the study is still in the onset stage, and no black phospho-like & chain structure has been prepared 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, which lays a foundation for further researching the black phosphorus flower-shaped and chain-shaped structure.
The first object of the invention is to provide 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 into black phosphorus powder in an air environment, and dispersing the black phosphorus powder into an organic dispersing agent to prepare a dispersion liquid;
grinding the block black phosphorus in 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 broken through oxidization, thereby promoting the generation of flower-like and chain-like structures
S2, carrying out microwave treatment on the dispersion liquid prepared in the step S1 under the protection gas atmosphere at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid; further breaking covalent bonds between the black phosphorus layers by microwave treatment;
s3, carrying out centrifugal treatment on the mixed solution prepared in the step S2, collecting upper layer liquid (the size of the sediment of the lower layer is larger, and the black phosphorus material with smaller size is dispersed in the upper layer liquid), separating out the material with larger size through centrifugal treatment to obtain the black phosphorus material with smaller size, and drying to obtain the flower-shaped and chain-shaped black phosphorus powder.
Preferably, in S1, milling is performed in an air environment for 20-30min.
Preferably, in S1, the organic dispersant is N-methylpyrrolidone.
Preferably, in S1, the dosage ratio of the black phosphorus to the organic dispersing agent is 3-8g:1L.
Preferably, in S2, the microwave treatment time is 25-35min.
Preferably, in S3, the condition of the centrifugation is that the centrifugation is carried out for 15-25min at a rotation speed of 5000-7000rmp, the upper liquid is collected, and the upper liquid is centrifuged for 20min at a rotation speed of 14000 rmp.
A second object of the present invention is to provide a flower-like & chain-like black phosphorus material produced by the above-mentioned production 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) 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 broken through oxidation, thereby promoting the generation of a flower-like and chain-like structure;
(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 smaller (about 50 nm), and the chain size is larger (10 mu m); the preparation method is simple and convenient, has high product quality, and lays a foundation for further researching the black phosphorus flower-shaped and chain-shaped structure.
Drawings
FIG. 1 is a transmission electron micrograph and an electron diffraction pattern of the flower-shaped and chain-shaped black phosphorus material obtained in example 1.
Detailed Description
In order that those skilled in the art will better understand the technical scheme of the present invention and implement it, the following detailed description of the present invention will be given with reference to the accompanying drawings and detailed description, but the present invention is not limited to the following examples.
The following experimental methods and detection methods, if not specified, are all conventional methods; the raw materials and reagents, unless otherwise specified, are commercially available.
The invention provides a preparation method of a flower-like and chain-like black phosphorus material, which comprises the following steps:
s1, taking out black phosphorus in a protective gas atmosphere, grinding the black phosphorus into black phosphorus powder in an air environment, and dispersing the black phosphorus powder into an organic dispersing agent to prepare a dispersion liquid;
s2, carrying out microwave treatment on the dispersion liquid prepared in the step S1 under the protection gas atmosphere 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, carrying out centrifugal treatment on the mixed solution prepared in the step S2, collecting upper-layer liquid, and drying to obtain flower-like and chain-like 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 broken through oxidization, thereby promoting the generation of a flower-like and chain-like structure.
Example 1
The preparation method of the flower-like and chain-like 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, dispersing the black phosphorus powder into 20mL of N-methylpyrrolidone (NMP), and sealing and shaking to obtain black phosphorus-NMP dispersion liquid;
(2) Adding the black phosphorus-NMP dispersion liquid obtained in the step (1) into a three-necked flask, carrying out microwave reaction for 25min at 100 ℃ under the 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 liquid, centrifuging the upper liquid at 14000rmp for 20min at high speed, collecting upper liquid (brilliant yellow), and drying to obtain flower-like and chain-like black phosphorus powder.
Example 2
The preparation method of the flower-like and chain-like 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-necked flask, reacting for 35min at 130 ℃ under the microwave power of 700W in the argon environment, and cooling the solution to room temperature;
(3) Centrifuging the mixed solution obtained in the step (2) at 7000rmp for 25min, collecting upper liquid, centrifuging the upper liquid at 14000rmp for 20min at high speed, collecting upper liquid (brilliant yellow), and drying to obtain flower-like and chain-like black phosphorus powder.
Example 3
The preparation method of the flower-like and chain-like 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-necked flask, carrying out microwave 600W power under an argon environment, reacting for 25min at 120 ℃, and cooling the solution to room temperature;
(3) Centrifuging the mixed solution obtained in the step (2) for 20min at 6000rmp, collecting upper liquid, centrifuging the upper liquid at 14000rmp for 20min at high speed, collecting upper liquid (brilliant yellow), and drying to obtain flower-like and chain-like black phosphorus powder.
The properties of the flower-like and chain-like black phosphorus materials obtained in examples 1 to 3 are similar to each other, and the following description will be made by taking example 1 alone as an example.
Fig. 1 is a transmission electron micrograph and an electron diffraction pattern of the flower-like & chain-like black phosphorus material obtained in example 1, and it is seen from fig. 1 that a large amount of chain-like structural substances (about 10 μm in size) are present in the low-power transmission electron micrograph (upper left image), indicating that the chain-like black phosphorus material was successfully obtained, and when the magnification is applied (upper right image), it is evident that the chain-like structure is composed of flower-like structures (about 50nm in flower-like size), and when the magnification is applied, it is evident that the lattice fringes are evident (lower left image), and that single crystal diffraction is evident in the electron diffraction pattern (lower right image), indicating that the quality of the synthesized black phosphorus flower-like & chain-like structure is excellent.
Therefore, the invention can successfully prepare the black phosphorus material with flower-like and chain-like structures, the surface of the black phosphorus material is distributed in the chain-like structure, the chain-like structure is composed of the flower-like structures, the flower-like size is smaller (50 nm), the chain-like size is larger (10 mu m), the preparation method is simple and convenient, the product quality is high, and a foundation is laid for further researching the black phosphorus flower-like and chain-like structures.
It should be noted that, when reference is made to a numerical range in the claims of the present invention, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and since the adopted steps are the same as those of the embodiments, the present invention describes the preferred embodiments and effects thereof for preventing redundancy, but once the basic inventive concept is known to those skilled in the art, additional variations and modifications can be made to these embodiments. It is therefore intended that the following claims be interpreted as including the 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 spirit or scope of the invention, and such modifications and variations are within the scope of the invention.
Claims (5)
1. The preparation method of the flower-like and chain-like black phosphorus material is characterized by comprising the following steps of:
s1, taking out black phosphorus in a protective gas atmosphere, grinding the black phosphorus into black phosphorus powder in an air environment, and dispersing the black phosphorus powder into an organic dispersing agent to prepare a dispersion liquid;
grinding in air for 20-30min;
s2, carrying out microwave treatment on the dispersion liquid prepared in the step S1 under the protection gas atmosphere at the power of 500-700W and the temperature of 100-130 ℃, and then cooling to room temperature to prepare a mixed liquid;
the microwave treatment time is 25-35min;
s3, carrying out centrifugal treatment on the mixed solution prepared in the step S2, collecting upper-layer liquid, and drying to obtain flower-like and chain-like black phosphorus powder; the flower-like and chain-like black phosphorus powder is distributed in a chain-like structure, and the chain-like structure is formed by a flower-like structure;
the condition of the centrifugal treatment is that the upper liquid is firstly centrifuged for 15-25min at the rotation speed of 5000-7000rmp, and then the upper liquid is centrifuged for 20min at the rotation speed of 14000 rmp.
2. The method for preparing a flower-like and chain-like black phosphorus material according to claim 1, wherein in S1, the organic dispersant is N-methylpyrrolidone.
3. The method for preparing the flower-like and chain-like black phosphorus material according to claim 2, wherein in S1, the dosage ratio of the black phosphorus to the organic dispersant is 3-8g:1L.
4. A flower-like & chain-like black phosphorus material produced by the production method according to any one of claims 1 to 3.
5. The flower-like and chain-like black phosphorus material according to claim 4, wherein the black phosphorus material is distributed in a chain-like structure, and the chain-like structure is constituted by a flower-like structure.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| CN105565289A (en) * | 2016-01-29 | 2016-05-11 | 西北大学 | Black phosphorus and phosphinidene preparing methods |
| CN105600760A (en) * | 2015-12-25 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Small-sized black phosphorus flakes and preparation method thereof |
| CN106711408A (en) * | 2015-11-13 | 2017-05-24 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanosheet-graphene composite film anode, and preparation thereof |
| CN108772079A (en) * | 2018-04-26 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of nanometer of black phosphorus/graphene composite material |
| CN110229667A (en) * | 2019-05-29 | 2019-09-13 | 商丘师范学院 | A kind of black phosphorus quantum dot, titanium dioxide black phosphorus quantum dot composite material and its preparation method and application |
| CN111517295A (en) * | 2020-06-02 | 2020-08-11 | 陕西科技大学 | Two-dimensional mesh black phosphorus material and controllable and adjustable preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107658475A (en) * | 2017-09-25 | 2018-02-02 | 青岛大学 | A kind of platinum/black phosphorus@carbon ball methanol fuel cell anode catalyzers and preparation method thereof |
| US10858253B2 (en) * | 2018-12-26 | 2020-12-08 | United States Of America As Represented By The Secretary Of The Air Force | Method and apparatus for producing a nanometer thick film of black phosphorus |
-
2020
- 2020-11-13 CN CN202011271876.1A patent/CN112340714B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| CN106711408A (en) * | 2015-11-13 | 2017-05-24 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanosheet-graphene composite film anode, and preparation thereof |
| CN105600760A (en) * | 2015-12-25 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Small-sized black phosphorus flakes and preparation method thereof |
| CN105565289A (en) * | 2016-01-29 | 2016-05-11 | 西北大学 | Black phosphorus and phosphinidene preparing methods |
| CN108772079A (en) * | 2018-04-26 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of nanometer of black phosphorus/graphene composite material |
| CN110229667A (en) * | 2019-05-29 | 2019-09-13 | 商丘师范学院 | A kind of black phosphorus quantum dot, titanium dioxide black phosphorus quantum dot composite material and its preparation method and application |
| CN111517295A (en) * | 2020-06-02 | 2020-08-11 | 陕西科技大学 | Two-dimensional mesh black phosphorus material and controllable and adjustable preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黑磷烯稳定性增强研究进展;刘艳奇;何路东;廉培超;陈鑫智;梅毅;;《化工学报》(第03期);第936-944页 * |
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