CN105668530B - A kind of preparation method of two-dimension nano materials - Google Patents
A kind of preparation method of two-dimension nano materials Download PDFInfo
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- CN105668530B CN105668530B CN201610023583.9A CN201610023583A CN105668530B CN 105668530 B CN105668530 B CN 105668530B CN 201610023583 A CN201610023583 A CN 201610023583A CN 105668530 B CN105668530 B CN 105668530B
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
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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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
Abstract
The present invention discloses a kind of preparation method of two-dimension nano materials, and it comprises the following steps：The a certain amount of material with layer structure is mixed with lithium chloride and chlorination alumina particles; then melt and solidify repeatedly under certain condition by being incubated salt-mixture after being incubated and cooling after multiple heating; the material with layer structure is constantly by intercalation and stripping in the process; final sample obtains two-dimension nano materials by washing separation drying process.The preparation method cost of the present invention is cheap, and technique is simple, it is not necessary to complex device, and it is green；Because the present invention is that Physical is peeled off, so the sample being prepared has intact crystallinity, it is adapted to research application and industrialized production.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of preparation method of two-dimension nano materials.
Background technology
Graphene (Graphene) is the two-dimentional carbon material for having cellular atomic structure and individual layer atomic thickness.Its hair
The prophesy that two dimensional crystal can not be stabilized in nature is for a long time now not only broken, the excellent properties of its own also make
Graphene all great potential in basic and applied research.Up to the present, hundreds of existing two-dimensional material by it has been found that
This includes the 4th main group simple substance, the binary compound that the 3rd and the 5th main group is formed, metal chalcogenide compound, combined oxidation
Thing, etc..This kind of material is formed by the two-dimension single layer accumulation that thickness is only several atoms, is made between layers for van der Waals
With.In the traditional concept of people, during the number of plies of this kind of stratified material is progressively reduced until individual layer, its electronic structure
Very big change is tended to occur with physical property, for example band gap width significantly increases, indirect band gap changes to direct band gap, and
Change of crystal vibration energy etc..The presence of especially dirac cone (Dirac cone) imparts many novel things of graphene
Manage phenomenon and electronic property, such as half-integer, fraction and divide shape quantum hall effect, superelevation mobility etc..
But the method for preparing these two-dimensional materials now is difficult, and means are limited, are the milligram magnitude of laboratory level mostly, from
Laboratory applications are tested or production also has very remote distance.Therefore a kind of convenient, environmentally friendly, pervasive preparation means are developed not
Also particularly important to scientific research only to production, the present invention comes therefrom.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of convenient, environmentally friendly, pervasive convenient, environmentally friendly, pervasive two
The preparation method of dimension nano material.
In order to solve the above-mentioned technical problem, the preparation method of a kind of two-dimension nano materials provided by the invention, (1) will be certain
The material that measurer has layer structure mixes with lithium chloride and chlorination alumina particles,
(2) and then by being incubated the salt-mixture of lithium chloride and aluminium chloride one after being incubated and cooling after multiple heating
Determine to melt and solidify repeatedly under atmosphere, the material with layer structure is constantly by intercalation and stripping in the process,
(3) final sample obtains two-dimension nano materials by washing separation drying process.
The described a certain amount of material with layer structure accounts for lithium chloride and the salt-mixture mass ratio of chlorination alumina particles is
0.5%~10%, preferred mass ratio is 0.5%~5%.
The described material with layer structure refers to graphite, graphite oxide, expanded graphite, hexagonal boron nitride, curing
Molybdenum, tungsten disulfide, rhenium disulfide, black phosphorus, the 4th main group simple substance, the binary compound that the 3rd and the 5th main group is formed, metal sulphur
Compound, layered lithium manganate, stratiform cobalt acid lithium stratified material and with the above-mentioned doping vario-property material for main body material.
The molar ratio of the lithium chloride and aluminium chloride is 1:0.9~1.1.
Mixing in the step (1) refers to grind, stirs, shakes, rocking mode.
Repeatedly refer to 5~100 times, preferably 20~50 times in the step (2).
Insulation refers to that being warming up to 144 DEG C~200 DEG C starts to be incubated after heating in the step (2), heating rate 0.1
~100 DEG C/s, soaking time is 1~60 minute, is preferably warming up to 144 DEG C~180 DEG C and starts to be incubated, and preferably heating rate is 1
~10 DEG C/s, preferably soaking time is 10~30 minutes.
Insulation refers to that cooling to -60 DEG C~140 DEG C starts to be incubated after cooling in the step (2), rate of temperature fall 0.1
~100 DEG C/s, soaking time is 1~60 minute；Start to be incubated it is preferred that cooling to 0 DEG C~80 DEG C, preferably rate of temperature fall is 1~10
DEG C/s, preferably soaking time is 10~30 minutes.
Described atmosphere is selected from vacuum, air, oxygen, hydrogen, nitrogen, inert gas, oxidizing gas, reproducibility gas
Body, sour gas, the preferably one or more in alkaline gas, atmosphere are air, hydrogen, the one or more of nitrogen；Relatively
Pressure is 0~10MPa.
The second aspect of the present invention provides the two-dimension nano materials that a kind of above method is prepared.
Described two-dimension nano materials are that the number of plies is 1~20 layer, and thickness is 0~10nm.
The beneficial effects of the invention are as follows：Compared with prior art, the present invention is using low common by common inexpensive indifferent salt
Ionic liquid is obtained after fusing point melting, and lithium ion, aluminium ion, chlorion all has less ionic radius, be easily accessible stratiform
The formation intercalation between layers of structural material, make fuse salt crystallization and freezing by cooling afterwards, the ionic crystal life in intercalation
It is long big so as to which interlamellar spacing be supportted, this process is iteratively repeated so that interlamellar spacing constantly supports greatly, most stratified material is completely exfoliated at last,
And two-dimension nano materials are obtained by processing such as washings.The preparation method technique of the present invention is simple, and operation is easy, and cost is cheap,
Complex device is not needed, and it is green；Peeled off because the inventive method is Physical, the two-dimensional nano material being prepared
Material has intact crystallinity, is adapted to research application and industrialized production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene nanometer sheet prepared by the embodiment of the present invention 1.
The scanning electron microscope (SEM) photograph of hexagonal boron nitride nanosheet prepared by Fig. 2 positions embodiment of the present invention 3.
Embodiment：
To further understand the present invention, preferred scheme of the present invention is described with reference to specific embodiment, but should
Work as understanding, these descriptions are simply further explanation the features and advantages of the present invention, rather than the limit to the claims in the present invention
System.
Embodiment 1
5g graphite flakes are passed through into grinding and 100g lithium chlorides and aluminum chloride powder (mol ratio 1:1) mix, mixed sample
Product are heated to 200 DEG C under air normal pressure with 1 DEG C/s heating rate and being incubated 600 seconds melts mixture, afterwards with 1 DEG C/s
Rate of temperature fall be cooled to 80 DEG C and being incubated solidifies mixture in 1200 seconds, after repeating this melting and solidification process 50 times, pass through
Washing separation drying process, so as to obtain the thick graphene nanometer sheets of 3nm, as shown in Figure 1.
Embodiment 2
0.1g black phosphorus is passed through into stirring and 100g lithium chlorides and aluminum chloride powder (mol ratio 1:1) mix, mixed sample
Product are heated to 180 DEG C under vacuo with 80 DEG C/s heating rate and being incubated 600 seconds melts mixture, afterwards with 1 DEG C/s's
Rate of temperature fall is cooled to 100 DEG C and being incubated solidifies mixture in 600 seconds, after repeating this melting and solidification process 20 times, by washing
Separation drying process is washed, so as to obtain black phosphorus nanometer sheet.
Embodiment 3
2g hexagonal boron nitrides are passed through into concussion and 100g lithium chlorides and aluminum chloride powder (mol ratio 1:1) mix, after mixing
Sample be heated to 160 DEG C under air normal pressure with 10 DEG C/s heating rate and being incubated melts mixture in 3000 seconds, afterwards
20 DEG C are cooled to 10 DEG C/s rate of temperature fall and being incubated 3000 seconds solidifies mixture, repeat this melting and solidification process 20 times
Afterwards, drying process is separated by washing, so as to obtain the thick hexagonal boron nitride nanosheets of 5nm, as shown in Figure 2.
Embodiment 4
1g molybdenum disulfide is passed through into concussion and 100g lithium chlorides and aluminum chloride powder (mol ratio 1:1) mix, it is mixed
Sample is heated to 160 DEG C under nitrogen protection with 5 DEG C/s heating rate and being incubated 1800 seconds melts mixture, afterwards with 5
DEG C/s rate of temperature fall is cooled to 50 DEG C and being incubated 1800 seconds solidifies mixture, after repeating this melting and solidification process 20 times,
Drying process is separated by washing, so as to obtain molybdenum disulfide nano sheet.
Embodiment 5
0.5g tungsten disulfides are passed through into concussion and 100g lithium chlorides and aluminum chloride powder (mol ratio 1:1) mix, after mixing
Sample be heated to 160 DEG C under reducing atmosphere (5% hydrogen nitrogen blender) protection with 5 DEG C/s heating rate and be incubated
Melt mixture within 1800 seconds, be cooled to 50 DEG C with 5 DEG C/s rate of temperature fall afterwards and being incubated 1800 seconds solidifies mixture, weight
After multiple this melting and solidification process 20 times, drying process is separated by washing, so as to obtain tungsten disulfide nano slices.
The technology contents and technical characteristic of the present invention have revealed that as above, but those skilled in the art still may base
Make a variety of replacements and modification without departing substantially from spirit of the present invention, therefore, the scope of the present invention in teachings of the present invention and announcement
The content disclosed in embodiment should be not limited to, and various replacements and modification without departing substantially from the present invention should be included, and is this patent Shen
Please claim covered.
Claims (5)
1. a kind of preparation method of two-dimension nano materials, it is characterised in that its method comprises the following steps：
(1) a certain amount of material with layer structure is mixed with lithium chloride and chlorination alumina particles, there is the material of layer structure
Refer to graphite oxide, expanded graphite, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, rhenium disulfide, black phosphorus, layered lithium manganate,
Stratiform cobalt acid lithium material or more states the doping vario-property material for material of main part；
(2) and then by being incubated the salt-mixture of lithium chloride and aluminium chloride one after being incubated and cooling after the heating of 5~100 times
Determine to melt and solidify repeatedly under atmosphere, the material with layer structure is constantly by intercalation and stripping in the process,
Insulation refers to that being warming up to 144 DEG C~200 DEG C starts to be incubated after heating, and heating rate is 0.1~100 DEG C/s, soaking time
For 1~60 minute；
Insulation refers to that cooling to -60 DEG C~140 DEG C starts to be incubated after cooling, and rate of temperature fall is 0.1~100 DEG C/s, soaking time
For 1~60 minute；
(3) final sample obtains two-dimension nano materials by washing separation drying process.
2. the preparation method of two-dimension nano materials according to claim 1, it is characterised in that described with layer structure
It is 0.5%~10% that material, which accounts for lithium chloride and the salt-mixture mass ratio of chlorination alumina particles,.
3. the preparation method of two-dimension nano materials according to claim 1, it is characterised in that the lithium chloride and aluminium chloride
Molar ratio be 1:0.9~1.1.
4. the preparation method of two-dimension nano materials according to claim 1, it is characterised in that described atmosphere is selected from true
Sky, inert gas, oxidizing gas, reducibility gas, sour gas, the one or more in alkaline gas；Relative pressure is 0
~10MPa.
5. the preparation method of two-dimension nano materials according to claim 4, it is characterised in that the inert gas is selected from nitrogen
Gas；The reducibility gas is selected from hydrogen；The oxidizing gas is selected from air, oxygen.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082148B (en) * | 2016-06-21 | 2018-04-20 | 江苏大学 | A kind of method that two-dimentional hexagonal boron nitride nanosheet is prepared using liquid nitrogen gasification |
| CN106335927B (en) * | 2016-08-22 | 2018-03-06 | 河南师范大学 | A kind of preparation method of 2H phases individual layer tungsten disulfide nano slices |
| CN106841338B (en) * | 2017-01-25 | 2019-06-25 | 东南大学 | A kind of gas sensor and preparation method thereof |
| CN107039587A (en) * | 2017-03-31 | 2017-08-11 | 东南大学 | Negative differential resistance and preparation method based on black phosphorus/rhenium disulfide hetero-junctions |
| CN111151145B (en) * | 2018-11-08 | 2022-04-05 | 中国石油化工股份有限公司 | Super-hydrophobic separation membrane and preparation method and application thereof |
| CN109368703B (en) * | 2018-11-15 | 2020-01-07 | 厦门大学 | Preparation method of tungsten trioxide thin sheet |
| CN111547770B (en) * | 2020-06-05 | 2021-05-07 | 中国科学技术大学 | Preparation method of functionalized modified molybdenum disulfide nanosheet |
| CN116169012B (en) * | 2023-04-26 | 2023-08-08 | 南京理工大学 | Preparation method of two-dimensional layered semiconductor material with room-temperature ferromagnetism and ferroelectricity |
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