CN107188141B - A kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material - Google Patents
A kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material Download PDFInfo
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- CN107188141B CN107188141B CN201710557192.XA CN201710557192A CN107188141B CN 107188141 B CN107188141 B CN 107188141B CN 201710557192 A CN201710557192 A CN 201710557192A CN 107188141 B CN107188141 B CN 107188141B
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- nanometer sheet
- black phosphorus
- phosphorus nanometer
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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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention discloses a kind of direct, liquid phase, low temperature synthesis black phosphorus nanometer sheet methods, belong to black phosphorus two-dimensional material technical field.This method is packed into white phosphorus in a kettle and ethylenediamine seals reaction kettle after white phosphorus is completely dissolved, be placed in baking oven and be heated to 60-140 DEG C by the method for solvent heat, 12 hours of constant temperature.After reacting stopping, the black phosphorus nanometer sheet of pure phase can be obtained.Operation of the present invention is simple, low in cost, is convenient for industrial mass production, and prepared black phosphorus nanometer sheet has many advantages, such as purity is high, and yield 70% can be widely applied to the fields such as photoelectric device, catalysis.
Description
Technical field
The invention belongs to black phosphorus two-dimensional material technical fields, are related to a kind of side of low temperature batch synthesis black phosphorus nanometer sheet material
Method.
Background technique
Black phosphorus with orthohormbic structure, unit cell units are a hexatomic ring to interlink, are that phosphorus is most under normal temperature and pressure
Stable isomer.The optical band gap that there is black phosphorus thickness to rely on, it is adjustable within the scope of 0.5-2eV, and show non-
Often the advantages that high carrier mobility rate, thus black phosphorus nanometer sheet in opto-electronic device, the energy, biomedicine etc. using having
Great application potential, performance is considerably beyond grapheme material, it is considered to be a kind of very potential two-dimensional material.But
It is that the synthesis of black phosphorus nanometer sheet is extremely difficult.The body phase black phosphorus of mechanical or liquid phase removing at present is the master for preparing black phosphorus nanometer sheet
Want method.In this approach, it is necessary first to prepare the black phosphorus block of high quality, this is equally a biggish problem, is needed
It is completed under high-temperature and high-pressure conditions.In addition during removing, black phosphorus nanometer sheet is very easy to be oxidized, so that it be made to lose
The characteristic of semiconductor, and this method is extremely time-consuming, higher cost, is unfavorable for large-scale industrial production.To limit
The extensive use and development of black phosphorus nanometer sheet.
Summary of the invention
The present invention is oxidized easily when preparing black phosphorus nanometer sheet there are product for the prior art and time-consuming, higher cost
The technical issues of, a kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material is provided.
The technical solution adopted by the invention is as follows: a kind of method of direct liquid phase low temperature synthesis black phosphorus nanometer sheet, including with
White phosphorus: being added in ethylenediamine solvent by lower step in a kettle, and stirring is completely dissolved to it, then tightens reaction kettle cover,
And reaction kettle is placed in baking oven, it is heated to 60-140 DEG C, 12 hours of constant temperature；It, can after centrifugation, washing, drying after cooling
To obtain black phosphorus nanometer sheet.
In entire black phosphorus nanometer sheet preparation process, the selection of solvent be it is crucial, only ethylenediamine be effectively synthesize it is black
The solvent of phosphorus nanometer sheet.This is because ethylenediamine polarity is stronger, the solubility of white phosphorus can be increased, and in ethylenediamine environment
In, white phosphorus reactivity is stronger, can directly react to form intermediate with ethylenediamine, so that reducing white phosphorus is transformed into black phosphorus institute
The energy barrier for needing to overcome is conducive to the formation of black phosphorus.In addition reaction temperature is also one of key factor.(it is lower than under lower temperature
60 DEG C), no product is formed；And when reaction temperature is higher than 140 DEG C, product is mainly white phosphate crystal.In the present invention most
The good temperature range for forming black phosphorus is 60-140 DEG C.
The present invention provides a kind of direct, liquid phase, low-temperature synthetic method preparation high-purity black phosphorus nanometer sheet, this methods
Not only low in cost, technique simplifies, but also yield is higher, is convenient for industrialized mass production.
The invention has the advantages that
(1) preparation method it is simple and convenient, it is low in cost, can be realized and be prepared on a large scale.The black phosphorus that Fig. 1 show 2g is in kind
Photo by increase reaction vessel volume, and increases and feeds intake, can further increase the yield of product.
(2) the black phosphorus nanometer sheet purity prepared by the present invention is higher.As shown in Fig. 2, it is not observed in XRD result
The diffraction maximum of its impurity, chemical property are stablized, and yield is up to 70%, and prepared nanometer sheet thickness is 1-10nm, size
It is 200-1000nm(as shown in attached drawing 3,4), it is suitably applied the fields such as opto-electronic device, the energy and biomedicine.
(3) preparation process is not limited by material rate.
Detailed description of the invention
Fig. 1: black phosphorus material object picture.
Fig. 2: the XRD of black phosphorus nanometer sheet.
Fig. 3: the transmission electron microscope picture of black phosphorus nanometer sheet.
Fig. 4: the atomic force microscope images of black phosphorus nanometer sheet.
Fig. 5: the Raman spectrogram of black phosphorus nanometer sheet.
Specific embodiment
Embodiment 1
(1) it weighs 3g white phosphorus and adds it in the reaction kettle equipped with 70mL ethylenediamine, magnetic agitation keeps white phosphorus complete
Dissolution；
(2) reaction kettle cover is tightened, and places it in baking oven and is heated to 140 DEG C, 12 hours of constant temperature；
(3) after reaction kettle is spontaneous be cooled to room temperature after, products therefrom is centrifuged, and is washed with benzene, ethyl alcohol and deionized water；
(4) gained black precipitate is placed in a vacuum drying oven, drying 12 hours at room temperature is to obtain black phosphorus nanometer sheet
Material.
Embodiment 2
It weighs 2g white phosphorus and adds it in the reaction kettle equipped with 60mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution, remaining condition obtain black phosphorus nanometer sheet material with embodiment 1, through detection.
Embodiment 3
It weighs 3g white phosphorus and adds it in the reaction kettle equipped with 70mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution；Reaction kettle cover is tightened, and places it in baking oven and is heated to 120 DEG C, 12 hours of constant temperature；Remaining condition with embodiment 1,
Black phosphorus nanometer sheet material is obtained through detection.
Embodiment 4
It weighs 3g white phosphorus and adds it in the reaction kettle equipped with 70mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution；Reaction kettle cover is tightened, and places it in baking oven and is heated to 100 DEG C, 12 hours of constant temperature；Remaining condition with embodiment 1,
Black phosphorus nanometer sheet material is obtained through detection.
Embodiment 5
It weighs 3g white phosphorus and adds it in the reaction kettle equipped with 70mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution；Reaction kettle cover is tightened, and places it in baking oven and is heated to 80 DEG C, 12 hours of constant temperature；Remaining condition is the same as embodiment 1, warp
Detection obtains black phosphorus nanometer sheet material.
Embodiment 6
It weighs 3g white phosphorus and adds it in the reaction kettle equipped with 70mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution；Reaction kettle cover is tightened, and places it in baking oven and is heated to 60 DEG C, 12 hours of constant temperature；Remaining condition is the same as embodiment 1, warp
Detection obtains black phosphorus nanometer sheet material.
Embodiment 7
It weighs 3g white phosphorus and adds it in the reaction kettle equipped with 60mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution；Reaction kettle cover is tightened, and places it in baking oven and is heated to 120 DEG C, 12 hours of constant temperature；Remaining condition with embodiment 1,
Black phosphorus nanometer sheet material is obtained through detection.
Embodiment 8
It weighs 2g white phosphorus and adds it in the reaction kettle equipped with 70mL ethylenediamine, magnetic agitation keeps white phosphorus completely molten
Solution；Reaction kettle cover is tightened, and places it in baking oven and is heated to 120 DEG C, 12 hours of constant temperature；Remaining condition with embodiment 1,
Black phosphorus nanometer sheet material is obtained through detection.
Claims (3)
1. a kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material, which comprises the following steps: in a kettle
White phosphorus is added in ethylenediamine solvent, stirring is completely dissolved to it, then tightens reaction kettle cover, and reaction kettle is placed in baking oven
In, it is heated to 60-140 DEG C, 12 hours of constant temperature；After cooling, the available black phosphorus nanometer sheet after centrifugation, washing, drying.
2. a kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material according to claim 1, which is characterized in that anti-
After answering kettle is spontaneous to be cooled to room temperature, products therefrom is centrifuged, and is successively washed with benzene, ethyl alcohol and deionized water, then by gained
Black precipitate is placed in a vacuum drying oven, and drying 12 hours at room temperature is to obtain black phosphorus nanometer sheet.
3. a kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material according to claim 1 or 2, which is characterized in that
After white phosphorus is added in ethylenediamine solvent, it is completely dissolved using magnetic agitation to white phosphorus.
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| CN201710557192.XA CN107188141B (en) | 2017-07-10 | 2017-07-10 | A kind of method that low temperature batch synthesizes black phosphorus nanometer sheet material |
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| CN107188141B true CN107188141B (en) | 2019-03-08 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107777674B (en) * | 2017-09-26 | 2019-11-29 | 深圳先进技术研究院 | A method of two-dimensional material is prepared using atmospheric plasma |
| CN108538707B (en) * | 2018-03-05 | 2020-04-24 | 南京航空航天大学 | Preparation method of two-dimensional black phosphorus crystal |
| CN111483990A (en) * | 2020-04-22 | 2020-08-04 | 昆明理工大学 | Low-cost high-crystallinity black phosphorus and preparation method thereof |
| WO2022047780A1 (en) * | 2020-09-07 | 2022-03-10 | 深圳先进技术研究院 | Phosphorene material, and preparation method therefor and application thereof |
| CN112174103B (en) * | 2020-09-17 | 2024-05-24 | 昆明理工大学 | Superlattice material of black phosphorus and preparation method thereof |
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| JPS638292A (en) * | 1986-06-27 | 1988-01-14 | Nippon Chem Ind Co Ltd:The | Production of black phosphorus single crystal |
| US6110438A (en) * | 1999-03-17 | 2000-08-29 | Lucent Technologies Inc. | Method of making black phosphorus from red phosphorus |
| CN102491294A (en) * | 2011-12-01 | 2012-06-13 | 东北师范大学 | Method for preparing black phosphorus of negative electrode materials of high-capacity lithium-ion battery |
| CN104630879A (en) * | 2015-02-28 | 2015-05-20 | 安庆美晶新材料有限公司 | Method for preparing black phosphorus monocrystal from high-purity red phosphorus under atmospheric pressure |
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Granted publication date: 20190308 Termination date: 20190710 |