CN110205674A - A method of two-dimentional black phosphorus crystal is prepared by raw material of white phosphorus - Google Patents
A method of two-dimentional black phosphorus crystal is prepared by raw material of white phosphorus Download PDFInfo
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- CN110205674A CN110205674A CN201910518820.2A CN201910518820A CN110205674A CN 110205674 A CN110205674 A CN 110205674A CN 201910518820 A CN201910518820 A CN 201910518820A CN 110205674 A CN110205674 A CN 110205674A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000013078 crystal Substances 0.000 title claims abstract description 77
- 239000002994 raw material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims abstract description 30
- 239000010453 quartz Substances 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003708 ampul Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
Abstract
The invention discloses a kind of methods for preparing two-dimentional black phosphorus crystal as raw material using white phosphorus.Firstly, under an inert atmosphere, weighing white phosphorus, metal simple-substance tin and mineralizer tin tetraiodide in single head and sealing quartzy bottom of the tube, and reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system.Quartz ampoule is heated finally by the temperature programming and cooling of optimization, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.The present invention is using white phosphorus as raw material, added metal simple substance tin and mineralizer tin tetraiodide, and heating prepares two-dimentional black phosphorus crystal under vacuum conditions.Compared to the traditional preparation methods using red phosphorus as reaction raw materials, reaction temperature and reaction time in synthesis process is not only can be significantly reduced in this method, reduces energy consumption.And for synthesizing high-quality black phosphorus crystal, white phosphorus raw material is lower compared to high-purity red phosphorus cost of material, and the black phosphorus crystal volume synthesized is bigger, purity is higher, is more advantageous to the industrially scalable preparation for realizing black phosphorus crystal.
Description
Technical field
The invention belongs to two-dimensional material technical fields, and in particular to a kind of to prepare two-dimentional black phosphorus crystal by raw material of white phosphorus
Method.
Background technique
It is a kind of most stable of allotrope of phosphorus as a newcomer, black phosphorus in two-dimensional material family.It has class
Seemingly but different from the natural pleated structure of graphene film stratiform structure, this unique pleated structure imparts many uniquenesses of black phosphorus
Physico-chemical property.If black phosphorus has the unexistent semiconductor gap of graphene and is direct band gap, i.e. electronic conduction energy band (is led
Band) at the top of bottom and non-conductive energy band (valence band) in same position, realize that, from non-conductive to conduction, electronics only needs to absorb energy
Amount, without changing momentum.This means that black phosphorus can be used as variable semiconductor, it can include entire with direct-coupling, spectrum with light
Visible light is near infrared region.In field of electronic devices, there is graphene and transient metal sulfide (TMDs) not to have again for it
Standby characteristic, such as: tuneable band gap (0.3 ~ 2.0 eV), high carrier mobility (1000 cm2V-1s-1) and it is considerable
On-off ratio (105).Based on these characteristics, the FET device using black phosphorus preparation has superior electric property.This
Outside, phosphorus is as element indispensable in human body, but also black phosphorus has good biocompatibility.Therefore, black phosphorus is in photoelectricity
The numerous areas such as device, photoelectrocatalysis, chemistry and bio-sensing, solar battery, supercapacitor and biomedicine have
Wide application prospect.
The preparation of black phosphorus crystal also experienced a very long research process.1914, Bridgman et al. was 1.2
GPa, 200 oC high-temperature and high-pressure conditions under convert black phosphorus (Journal of the American for white phosphorus for the first time
Chemical Society, 1914,36 (7): 1344-1363).But the synthesis condition of this method is excessively harsh, is only limitted to reality
Test the scientific research under the conditions of room.1981, white phosphorus was dissolved in bismuth solution by Maruyama et al. using reaction kettle, 400
20 h are kept the temperature under the conditions of oC, then Slow cooling, obtained rodlike black phosphorus (Physica B+ C, 1981,105 (1):
99-102).However this method yield is lower and is more toxic, therefore, it is difficult to carry out industrial large-scale production.In order to
Simply, efficiently, it is nontoxic and black phosphorus is mass produced, Park in 2007 etc. synthesizes black phosphorus using high-energy mechanical ball milling method, but synthesizes
Pure phase black phosphorus crystallinity it is lower, and be unable to accurately control the pressure and temperature of inside reactor, process control is poor
(Advanced Materials, 2007,19 (18): 2465-2468.).
Report in recent years, propose black phosphorus can it is at low pressure it is strong under be synthesized, mainly during vapor phase growth
Addition mineralizer is to promote black phosphorus to generate.Lange team is with red phosphorus, Au, Sn and Snl4It is reacted, is heated to for raw material
Room temperature is gradually cooling to after 600 oC.This method can prepare black phosphorus under nontoxic, lower pressure, can grow in ten days
The black phosphorus crystal of 1 ~ 2 mm of diameter, purity is up to 99.999 at%(Advanced Materials, 2007,19 (18):
2465-2468；Inorganic chemistry, 2007,46 (10): 4028-4035).Later, K pf was simplified,
Only with Sn, mineralizer Snl in the presence of not noble metal Au4Black phosphorus (the Journal of of high quality can equally be synthesized
Crystal Growth, 2014,405 (11): 6-10).Patent CN105133009A, CN105603517A and CN106087050A
Also disclose the improvement to this method, but they still have reaction unit requirement high (the above two require dual temperature area temperature control) and
The problems such as reaction temperature height (minimum temperature is at 500 DEG C or more).
In short, the preparation method of existing black phosphorus crystal is confined to substantially in above-mentioned several major class, and all there is reactions
Condition is harsh, reaction temperature is excessively high, the reaction time is too long, reaction unit is complicated, the reaction cost of raw material is excessively high, crystal growth ruler
A series of problems, such as very little smaller, crystal purity is lower.And it is black about being prepared using white phosphorus as raw material by chemical vapor transport method
The method of phosphorus crystal is also rarely reported.For this purpose, developing low-cost, simplicity and can quickly prepare high quality two dimension black phosphorus crystal material
The method of material is answered technical grade of the two-dimentional black phosphorus material in numerous areas such as photoelectric device, energy catalysis and biologic medicals is widened
With with important value.
Summary of the invention
The present invention is using white phosphorus as raw material, added metal simple substance tin and mineralizer tin tetraiodide, under vacuum conditions heating system
Standby two dimension black phosphorus crystal.Compared to the traditional preparation methods using red phosphorus as reaction raw materials, this method not only be can be significantly reduced
Reaction temperature and reaction time in synthesis process reduce energy consumption.And for synthesizing high-quality black phosphorus crystal, white phosphorus is former
Material is lower compared to high-purity red phosphorus cost of material, and the black phosphorus crystal volume synthesized is bigger, purity is higher, and it is black to be more advantageous to realization
It is prepared by the industrially scalable of phosphorus crystal.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A method of two-dimentional black phosphorus crystal being prepared by raw material of white phosphorus, it includes the following steps:
1) white phosphorus, metal simple-substance tin and mineralizer tin tetraiodide under an inert atmosphere, are weighed and seals quartzy bottom of the tube in single head, and
It is open with ParafilmTM spare；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets heating, cooling program and quartz ampoule is heated, to
After reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity is finally made.
In the present invention, height indispensable in existing high-quality black phosphorus synthesis process is substituted using the lower white phosphorus of price
Pure red phosphorus.On the one hand, the preparation cost of high-quality black phosphorus can be preferably reduced using white phosphorus as raw material；On the other hand, white phosphorus
Fusing point (44.1 DEG C) and (280.5 DEG C) of boiling point are far below the sublimation temperature (416 DEG C) of red phosphorus, this allows for us can be into
The reduction reaction temperature of one step, Optimum Temperature Raising program.Compared with prior art, the reaction for needing to carry out at 500 DEG C or more originally
Process uses white phosphorus instead as after reaction raw materials, reaction temperature can be reduced to 500 DEG C or less；Need 5 d even longer originally
Reaction time uses white phosphorus instead as after reaction raw materials, manufacturing cycle shorten to 1 ~ 2 d.While reducing energy consumption, raising efficiency,
Also black phosphorus crystal can be prepared with lower cost, is more advantageous to black phosphorus crystal preparation industrialization.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
In above scheme, the quality feed ratio of the white phosphorus, metal simple-substance tin and mineralizer tin tetraiodide is 10~
200:1~10:1.
Preferably, the quality feed ratio of the white phosphorus, metal simple-substance tin and mineralizer tin tetraiodide be 50~100:2~
8:1.
In above scheme, the purity of the tin simple substance is 98% or more；The purity of mineralizer tin tetraiodide matter is 95%
More than.
Preferably, the purity of the tin simple substance is 99% or more；The purity of mineralizer tin tetraiodide matter is 99% or more.
In above scheme, the sample atmosphere is referred to as inert gas shielding atmosphere, and claims to need to be sealed with sealed membrane after sample
Firmly quartzy tube opening.
In above scheme, described is that reactant is sealed in quartz ampoule using vacuum sealing tube system, manages interior vacuum item
1 Pa or less of pressure of part.
In above scheme, the temperature control process is the temperature programming and cooling realized by Muffle furnace from tape controller.
In above scheme, the temperature programming and cooling specifically: under room temperature, temperature is raised to 350 through 1 ~ 2 h~
After 500 DEG C, 1~6 h is kept the temperature；Then start to cool down, on the basis of holding temperature, drop to 200~350 DEG C through 6~24 h,
50~200 DEG C are dropped to through 6~24 h again, is then down to room temperature through 1 ~ 6 h.
Preferably, the temperature programming and cooling specifically: under room temperature, temperature is raised to 400~480 through 1 ~ 2 h
After DEG C, 2~4 h are kept the temperature；Then start to cool down, on the basis of holding temperature, drop to 300~350 DEG C through 6~12 h, then pass through
6~12 h drop to 100~200 DEG C, are then down to room temperature through 2 ~ 4 h.
In above scheme, the programmed rate is 150 ~ 500 DEG C/min；Program rate of temperature fall be 10 ~ 50 DEG C/
min。
Preferably, the programmed rate is 300 ~ 500 DEG C/min；Program rate of temperature fall is 20 ~ 40 DEG C/min.
The two-dimentional black phosphorus crystal prepared according to above scheme, which is characterized in that the size of black phosphorus crystal is 2*2*2
Between mm ~ 10*10*10 mm.The lamellar structure of crystal is obvious, has typical crystal gloss.The test result of XRD shows brilliant
The crystallinity of body is good, black phosphorus purity is high.
The present invention is using white phosphorus as raw material, added metal simple substance tin and mineralizer tin tetraiodide, under vacuum conditions heating system
Standby two dimension black phosphorus crystal.Compared to the traditional preparation methods using red phosphorus as reaction raw materials, this method not only be can be significantly reduced
Reaction temperature and reaction time in synthesis process reduce energy consumption.And for synthesizing high-quality black phosphorus crystal, white phosphorus is former
Material is lower compared to high-purity red phosphorus cost of material, and the black phosphorus crystal volume synthesized is bigger, purity is higher, and it is black to be more advantageous to realization
It is prepared by the industrially scalable of phosphorus crystal.
Compared with prior art, the invention has the benefit that
1) it in the present invention, is substituted using the lower white phosphorus of price indispensable high-purity in existing high-quality black phosphorus synthesis process
Red phosphorus.On the one hand, the preparation cost of high-quality black phosphorus can be preferably reduced using white phosphorus as raw material；On the other hand, white phosphorus is molten
Point (44.1 DEG C) and (280.5 DEG C) of the boiling point sublimation temperatures (416 DEG C) far below red phosphorus, this allows for us can be into one
The reduction reaction temperature of step, Optimum Temperature Raising program.With it is existing using red phosphorus compared with the technology of preparing of raw material, originally need exist
500 DEG C or more the reaction process carried out use white phosphorus instead as after reaction raw materials, reaction temperature can be reduced to 500 DEG C or less；It is former
5 d of this needs even longer reaction time uses white phosphorus instead as after reaction raw materials, manufacturing cycle shorten to 1 ~ 2 d.Reducing energy
While consumption, raising efficiency, also black phosphorus crystal can be prepared with lower cost, be more advantageous to black phosphorus crystal preparation industry
Change.
2) raw material of the present invention are simple and easy to get, synthesis condition is mild and is easy to regulate and control, and operating process is simple, is convenient for
It repeats, can largely synthesize.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram of two dimension black phosphorus crystal obtained in embodiment 1；
Fig. 2 is the picture of two dimension black phosphorus crystal obtained in embodiment 1；
Fig. 3 is the picture of two dimension black phosphorus crystal obtained in embodiment 2；
Fig. 4 is the scanning electron microscope (SEM) photograph of two dimension black phosphorus crystal obtained in embodiment 3；
Fig. 5 is product photo obtained in embodiment 1 and comparative example 1；
Fig. 6 is the picture of two dimension black phosphorus crystal obtained in comparative example 1.
Specific embodiment
In order to better understand the present invention, combined with specific embodiments below with the attached drawing content that the present invention is furture elucidated,
But the contents of the present invention are not limited solely to the following examples.Wherein, comparative example 1 and comparative example 2 are using red phosphorus as raw material system
The traditional preparation methods of standby two dimension black phosphorus crystal prepare the difference of two-dimentional black phosphorus crystal to compare using white phosphorus as raw material.
Embodiment 1
A method of two-dimentional black phosphorus crystal being prepared by raw material of white phosphorus, specific preparation process is as follows:
1) white phosphorus, 12 mg metal simple-substance tin and 6 mg mineralizer tin tetraiodides of 300 mg under an inert atmosphere, are weighed in single head
Quartzy bottom of the tube is sealed, and spare with ParafilmTM opening；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets certain heating, cooling program and quartz ampoule is heated
Processing, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
4) quartz ampoule being sealed is placed in Muffle furnace, under room temperature, temperature is after 1 h is raised to 500 DEG C, heat preservation 2
h；Then start to cool down, on the basis of holding temperature, 350 DEG C are dropped to through 12 h, then drop to 50 DEG C through 6 h, then through 1 h
It is down to room temperature.To after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
Fig. 1 is the X-ray diffraction spectrogram of two dimension black phosphorus crystal obtained in embodiment 1.It can be seen from the figure that sample is in
Reveal typical black phosphorus characteristic peak, and occur without other miscellaneous peaks, the prepared black phosphorus crystal crystallinity of this explanation is good, and black phosphorus is pure
It spends higher.Three strong characteristic peak is respectively to (020) of black phosphorus crystal, (040), (060) crystal face.Fig. 2 is gained in embodiment 1
Two-dimentional black phosphorus crystal picture, it can be seen from the figure that prepared two-dimentional black phosphorus crystal lamellar structure is obvious, size
About 0.7*0.6*0.5 mm.
Embodiment 2
A method of two-dimentional black phosphorus crystal being prepared by raw material of white phosphorus, specific preparation process is as follows:
1) white phosphorus, 24 mg metal simple-substance tin and 12 mg mineralizer tin tetraiodides of 300 mg under an inert atmosphere, are weighed in list
Head seals quartzy bottom of the tube, and spare with ParafilmTM opening；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets certain heating, cooling program and quartz ampoule is heated
Processing, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
4) quartz ampoule being sealed is placed in Muffle furnace, under room temperature, temperature is after 1 h is raised to 500 DEG C, heat preservation 2
h；Then start to cool down, on the basis of holding temperature, 350 DEG C are dropped to through 12 h, then drop to 50 DEG C through 6 h, then through 1 h
It is down to room temperature.To after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
Fig. 3 is the picture of two dimension black phosphorus crystal obtained in embodiment 2, it can be seen from the figure that prepared two dimension is black
Phosphorus crystalline lamellae structure is obvious, and size is about 0.6*0.5*0.5 mm.
Embodiment 3
A method of two-dimentional black phosphorus crystal being prepared by raw material of white phosphorus, specific preparation process is as follows:
1) white phosphorus, 60 mg metal simple-substance tin and 6 mg mineralizer tin tetraiodides of 1200 mg under an inert atmosphere, are weighed in list
Head seals quartzy bottom of the tube, and spare with ParafilmTM opening；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets certain heating, cooling program and quartz ampoule is heated
Processing, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
4) quartz ampoule being sealed is placed in Muffle furnace, under room temperature, temperature is after 1 h is raised to 480 DEG C, heat preservation 2
h；Then start to cool down, on the basis of holding temperature, 350 DEG C are dropped to through 12 h, then drop to 50 DEG C through 6 h, then through 1 h
It is down to room temperature.To after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
Fig. 4 is the scanning electron microscope (SEM) photograph of two dimension black phosphorus crystal obtained in embodiment 3, it can be seen from the figure that prepared
Two-dimentional black phosphorus crystal has apparent lamellar structure.
Embodiment 4
A method of two-dimentional black phosphorus crystal being prepared by raw material of white phosphorus, specific preparation process is as follows:
1) white phosphorus, 6 mg metal simple-substance tin and 6 mg mineralizer tin tetraiodides under an inert atmosphere, weighing 60 mg are sealed in single head
The quartzy bottom of the tube of mouth, and it is spare with ParafilmTM opening；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets certain heating, cooling program and quartz ampoule is heated
Processing, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
4) quartz ampoule being sealed is placed in Muffle furnace, under room temperature, temperature is after 1 h is raised to 480 DEG C, heat preservation 2
h；Then start to cool down, on the basis of holding temperature, 380 DEG C are dropped to through 12 h, then drop to 50 DEG C through 18 h, then through 1
H is down to room temperature.To after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
Comparative example 1
A method of two-dimentional black phosphorus crystal being prepared by raw material of red phosphorus, specific preparation process is as follows:
1) red phosphorus, 12 mg metal simple-substance tin and 6 mg mineralizer tin tetraiodides of 300 mg under an inert atmosphere, are weighed in single head
Quartzy bottom of the tube is sealed, and spare with ParafilmTM opening；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets certain heating, cooling program and quartz ampoule is heated
Processing, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
4) quartz ampoule being sealed is placed in Muffle furnace, under room temperature, temperature is after 1 h is raised to 500 DEG C, heat preservation 2
h；Then start to cool down, on the basis of holding temperature, 350 DEG C are dropped to through 12 h, then drop to 50 DEG C through 6 h, then through 1 h
It is down to room temperature.To after reaction, the incomplete phenomenon of reaction occurs in red phosphorus raw material, two-dimentional black phosphorus crystal is not obtained.
This temperature program is identical as temperature program in comparative example 1, to compare the difference of two kinds of preparation methods under identical temperature program.
Fig. 5 is product photo obtained in embodiment 1 and comparative example 1, it can be seen from the figure that with identical temperature program
It is reacted, the example reaction (using white phosphorus as raw material) is complete in embodiment 1, adheres on tube wall without apparent red phosphorus, black phosphorus
Crystal growth is good.And the sample in comparative example 1 (with the non-raw material of red phosphorus) then reacts not exclusively, a large amount of red phosphorus is attached to tube wall
On, and generated without apparent black phosphorus crystal.
Comparative example 2
A method of two-dimentional black phosphorus crystal being prepared by raw material of red phosphorus, specific preparation process is as follows:
1) red phosphorus, 12 mg metal simple-substance tin and 6 mg mineralizer tin tetraiodides of 300 mg under an inert atmosphere, are weighed in single head
Quartzy bottom of the tube is sealed, and spare with ParafilmTM opening；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets certain heating, cooling program and quartz ampoule is heated
Processing, to after reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity finally be made.
4) quartz ampoule being sealed is placed in Muffle furnace, under room temperature, temperature is after 1 h is raised to 600 DEG C, heat preservation 2
h；Then start to cool down, on the basis of holding temperature, 350 DEG C are dropped to through 48 h, then drop to 50 DEG C through 18 h, then through 1
H is down to room temperature.To after reaction, two-dimentional black phosphorus crystal finally be made.
Fig. 6 is the picture of two dimension black phosphorus crystal obtained in comparative example 2, it can be seen from the figure that using red phosphorus as raw material
Traditional preparation methods are only capable of that black phosphorus crystal is prepared under high temperature, prolonged reaction condition.Prepared two-dimentional black phosphorus is brilliant
Body is likewise supplied with lamellar structure, and size is about 0.5*0.4*0.3 mm.
Claims (9)
1. a kind of method for preparing two-dimentional black phosphorus crystal as raw material using white phosphorus, it includes the following steps:
1) white phosphorus, metal simple-substance tin and mineralizer tin tetraiodide under an inert atmosphere, are weighed and seals quartzy bottom of the tube in single head, and
It is open with ParafilmTM spare；
2) remove sealed membrane, reaction raw materials are sealed in inside vitreosil pipe using vacuum sealing tube system rapidly；
3) quartz ampoule being sealed is placed in Muffle furnace, and sets heating, cooling program and quartz ampoule is heated, to
After reaction, the high quality two dimension black phosphorus crystal of large volume, high-purity is finally made.
2. the method according to claim 1, wherein white phosphorus described in step 1), metal simple-substance tin and mineralising
The quality feed ratio of agent tin tetraiodide is 10~200:1~10:1.
3. the method according to claim 1, wherein the purity of tin simple substance described in step 1) be 98% with
On；The purity of mineralizer tin tetraiodide matter is 95% or more.
4. the method according to claim 1, wherein sample atmosphere described in step 1) is referred to as inert gas shielding
Atmosphere, and claim to be needed after sample with ParafilmTM quartz tube opening.
5. preparation method according to claim 1, which is characterized in that be to utilize vacuum sealing tube system described in step 2
Reactant is sealed in quartz ampoule, 1 Pa or less of pressure of interior vacuum condition is managed.
6. the method according to claim 1, wherein temperature control process described in step 3) be by Muffle furnace from
The temperature programming and cooling that tape controller is realized.
7. the method according to claim 1, wherein temperature programming described in step 3) and cooling specifically:
Under room temperature, temperature keeps the temperature 1~6 h after 1 ~ 2 h is raised to 350~500 DEG C；Then start to cool down, in holding temperature
On the basis of, 200~350 DEG C are dropped to through 6~24 h, then drop to 50~200 DEG C through 6~24 h, is then down to room through 1 ~ 6 h
Temperature.
8. the method according to claim 1, wherein programmed rate described in step 3) is 150 ~ 500
℃/min；Program rate of temperature fall is 10 ~ 50 DEG C/min.
9. the two-dimentional black phosphorus crystal of any one of claim 1 ~ 8 the method preparation, which is characterized in that the size of black phosphorus crystal is big
It is small between 2*2*2 mm ~ 10*10*10 mm.
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| CN112645295A (en) * | 2021-01-05 | 2021-04-13 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
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