CN110205674B - Method for preparing two-dimensional black phosphorus crystal by taking white phosphorus as raw material - Google Patents
Method for preparing two-dimensional black phosphorus crystal by taking white phosphorus as raw material Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000013078 crystal Substances 0.000 title claims abstract description 80
- 239000002994 raw material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000007789 sealing Methods 0.000 claims abstract description 46
- 239000010453 quartz Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 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
- -1 Transition Metal Sulfides Chemical class 0.000 description 1
- 238000000498 ball milling Methods 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
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
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- 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 method for preparing a two-dimensional black phosphorus crystal by taking white phosphorus as a raw material. Firstly, weighing white phosphorus, metal simple substance tin and mineralizer tin tetraiodide at the bottom of a single-head sealed quartz tube under inert atmosphere, and sealing reaction raw materials in the vacuum quartz tube by utilizing a vacuum tube sealing system. And finally, heating the quartz tube by means of the optimized procedure heating and cooling, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished. The invention takes white phosphorus as raw material, adds metal simple substance tin and mineralizer tin tetraiodide, and prepares two-dimensional black phosphorus crystal by heating under vacuum condition. Compared with the traditional preparation method using red phosphorus as a reaction raw material, the method can not only remarkably reduce the reaction temperature and the reaction time in the synthesis process, but also reduce the energy consumption. And for synthesizing high-quality black phosphorus crystals, the cost of the white phosphorus raw material is lower compared with that of the high-purity red phosphorus raw material, and the synthesized black phosphorus crystals are larger in volume and higher in purity, so that the industrial scale preparation of the black phosphorus crystals is realized.
Description
Technical Field
The invention belongs to the technical field of two-dimensional materials, and particularly relates to a method for preparing a two-dimensional black phosphorus crystal by taking white phosphorus as a raw material.
Background
Black phosphorus, a new member of the two-dimensional material family, is the most stable allotrope of phosphorus. It has a natural pleated structure similar to but different from the lamellar structure of graphene sheets, and the unique pleated structure imparts a number of unique physicochemical properties to black phosphorus. For example, the black phosphorus has a semiconductor gap which is not available in graphene and is a direct band gap, namely, the bottom of an electron conduction band (conduction band) and the top of a non-conduction band (valence band) are positioned at the same position, so that the situation from non-conduction to conduction is realized, and electrons only need to absorb energy without changing momentum. This means that black phosphorus can be used as a tunable semiconductor and can be directly coupled with light, the spectrum comprising the entire visible to near infrared region. In the field of electronic devices, it has properties not possessed by graphene and Transition Metal Sulfides (TMDs), such as: a tunable band gap (0.3-2.0 eV), a high carrier mobility (1000 cm) 2 V -1 s -1 ) And a considerable on-off ratio (10 5 ). Based on these characteristics, the field effect transistor device manufactured using black phosphorus has superior electrical properties. In addition, phosphorus is used as an indispensable element in human body, so that the black phosphorus has good biocompatibility. Thus, black phosphorus is useful in optoelectronic devices, photoelectrocatalysis, chemical and biological sensing, solar cells, supercapacitorsHas wide application prospect in various fields such as biomedicine and the like.
The preparation of black phosphorus crystals has also undergone a lengthy research process. Bridgman et al, 1914, converted white phosphorus to black phosphorus for the first time under high temperature and pressure conditions of 1.2 GPa at 200C (Journal of the American Chemical Society, 1914, 36 (7): 1344-1363). However, the synthesis conditions of this method are too severe and limited to scientific studies under laboratory conditions. In 1981, maruyama et al utilized a reaction kettle to dissolve white phosphorus in bismuth solution, incubated at 400℃for 20. 20 h, and then slowly cooled to give a rod-like black phosphorus (Physica B+C, 1981, 105 (1): 99-102). However, this method is low in yield and high in toxicity, and thus it is difficult to perform industrial mass production. In order to produce black phosphorus simply, efficiently, non-toxic and on a large scale, park et al in 2007 synthesized black phosphorus by a high-energy mechanical ball milling method, but the crystallinity of the synthesized pure-phase black phosphorus was low, and the pressure and temperature inside the reactor could not be controlled accurately, the process controllability was poor (Advanced Materials, 2007, 19 (18): 2465-2468).
In recent years, it has been proposed that black phosphorus can be synthesized at a lower pressure, mainly by adding mineralizers during vapor phase growth to promote black phosphorus production. Lange team with red phosphorus, au, sn and Snl 4 The raw materials react, and are gradually cooled to room temperature after being heated to 600 ℃. The method can prepare black phosphorus under nontoxic and low pressure conditions, and can grow black phosphorus crystals with the diameter of 1-2 mm within ten days, and the purity can reach 99.999-at% (Advanced Materials, 2007, 19 (18): 2465-2468;Inorganic chemistry, 2007, 46 (10): 4028-4035). Later, K is simplified, and Sn and mineralizer Snl are used alone without noble metal Au 4 High quality black phosphorus (Journal of Crystal Growth, 2014,405 (11): 6-10) can also be synthesized. Patents CN105133009A, CN105603517a and CN106087050a also disclose improvements to this method, but they still have problems of high reaction device requirements (the former two require dual temperature zone temperature control) and high reaction temperatures (the lowest temperatures are above 500 ℃), etc.
In summary, the existing preparation methods of black phosphorus crystals are basically limited to the above-mentioned several kinds of large-scale methods, and all have a series of problems of harsh reaction conditions, too high reaction temperature, too long reaction time, complex reaction devices, too high cost of reaction raw materials, smaller crystal growth size, lower crystal purity and the like. There are few reports on a method for preparing black phosphorus crystals by using white phosphorus as a raw material through a chemical vapor transport method. Therefore, the development of the method which is low in cost, simple, convenient and capable of rapidly preparing the high-quality two-dimensional black phosphorus crystal material has important value for widening industrial-grade application of the two-dimensional black phosphorus material in various fields such as photoelectric devices, energy catalysis, biomedical treatment and the like.
Disclosure of Invention
The invention takes white phosphorus as raw material, adds metal simple substance tin and mineralizer tin tetraiodide, and prepares two-dimensional black phosphorus crystal by heating under vacuum condition. Compared with the traditional preparation method using red phosphorus as a reaction raw material, the method can not only remarkably reduce the reaction temperature and the reaction time in the synthesis process, but also reduce the energy consumption. And for synthesizing high-quality black phosphorus crystals, the cost of the white phosphorus raw material is lower compared with that of the high-purity red phosphorus raw material, and the synthesized black phosphorus crystals are larger in volume and higher in purity, so that the industrial scale preparation of the black phosphorus crystals is realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing two-dimensional black phosphorus crystals by taking white phosphorus as a raw material comprises the following steps:
1) Weighing white phosphorus, metal simple substance tin and mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube in an inert atmosphere, and sealing an opening with a sealing film for standby;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
In the invention, white phosphorus with lower price is adopted to replace high-purity red phosphorus which is indispensable in the existing high-quality black phosphorus synthesis process. On one hand, the preparation cost of high-quality black phosphorus can be reduced better by taking white phosphorus as a raw material; on the other hand, the melting point (44.1 ℃) and boiling point (280.5 ℃) of white phosphorus are far lower than the sublimation temperature (416 ℃) of red phosphorus, so that the reaction temperature can be further reduced, and the temperature-rising program can be optimized. Compared with the prior art, the reaction process which is originally needed to be carried out at the temperature of more than 500 ℃ is changed into the reaction process which uses white phosphorus as the reaction raw material, and the reaction temperature can be reduced to below 500 ℃; the original reaction time is 5 d or even longer, and the preparation period is shortened to 1-2 d after white phosphorus is used as the reaction raw material. The black phosphorus crystal can be prepared at lower cost while the energy consumption is reduced and the efficiency is improved, and the preparation industrialization of the black phosphorus crystal is facilitated.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
In the scheme, the mass feeding ratio of the white phosphorus to the metal simple substance tin to the mineralizer tin tetraiodide is 10-200: 1 to 10:1.
preferably, the mass feed ratio of the white phosphorus, the metal simple substance tin and the mineralizer tin tetraiodide is 50-100: 2 to 8:1.
in the scheme, the purity of the tin simple substance is more than 98 percent; the purity of mineralizer tin tetraiodide is more than 95%.
Preferably, the purity of the tin simple substance is more than 99%; the purity of mineralizer tin tetraiodide is above 99%.
In the above scheme, the sample-weighing atmosphere is inert gas protective atmosphere, and the quartz tube opening is required to be sealed by a sealing film after the sample weighing is finished.
In the scheme, the reactant is sealed in the quartz tube by using a vacuum tube sealing system, and the pressure of the vacuum condition in the tube is less than 1 Pa.
In the scheme, the temperature control process is temperature programming and cooling realized by the muffle furnace with a controller.
In the above scheme, the program heating and cooling specifically comprises: under the condition of room temperature, after the temperature is raised to 350-500 ℃ for 1-2 h, preserving heat for 1-6 h; then cooling is started, the temperature is reduced to 200-350 ℃ through 6-24 h, then reduced to 50-200 ℃ through 6-24 h, and then cooled to room temperature through 1-6 h on the basis of heat preservation temperature.
Preferably, the program heating and cooling specifically comprises the following steps: under the condition of room temperature, after the temperature is raised to 400-480 ℃ for 1-2 h, preserving heat for 2-4 h; then cooling is started, the temperature is reduced to 300-350 ℃ through 6-12 h, then is reduced to 100-200 ℃ through 6-12 h, and then is reduced to room temperature through 2-4 h on the basis of heat preservation temperature.
In the scheme, the temperature programming rate is 150-500 ℃/min; the program cooling rate is 10-50 ℃/min.
Preferably, the temperature programming rate is 300-500 ℃/min; the program cooling rate is 20-40 ℃/min.
The two-dimensional black phosphorus crystal prepared according to the scheme is characterized in that the size of the black phosphorus crystal is 2-10 mm and is 2-2 mm. The lamellar structure of the crystals is evident, and typical crystal gloss is provided. The XRD test results show that the crystal has good crystallinity and high purity of black phosphorus.
The invention takes white phosphorus as raw material, adds metal simple substance tin and mineralizer tin tetraiodide, and prepares two-dimensional black phosphorus crystal by heating under vacuum condition. Compared with the traditional preparation method using red phosphorus as a reaction raw material, the method can not only remarkably reduce the reaction temperature and the reaction time in the synthesis process, but also reduce the energy consumption. And for synthesizing high-quality black phosphorus crystals, the cost of the white phosphorus raw material is lower compared with that of the high-purity red phosphorus raw material, and the synthesized black phosphorus crystals are larger in volume and higher in purity, so that the industrial scale preparation of the black phosphorus crystals is realized.
Compared with the prior art, the invention has the beneficial effects that:
1) In the invention, white phosphorus with lower price is adopted to replace high-purity red phosphorus which is indispensable in the existing high-quality black phosphorus synthesis process. On one hand, the preparation cost of high-quality black phosphorus can be reduced better by taking white phosphorus as a raw material; on the other hand, the melting point (44.1 ℃) and boiling point (280.5 ℃) of white phosphorus are far lower than the sublimation temperature (416 ℃) of red phosphorus, so that the reaction temperature can be further reduced, and the temperature-rising program can be optimized. Compared with the existing preparation technology using red phosphorus as raw material, the reaction process which needs to be carried out at the temperature of more than 500 ℃ originally changes white phosphorus as the raw material for reaction, and the reaction temperature can be reduced to below 500 ℃; the original reaction time is 5 d or even longer, and the preparation period is shortened to 1-2 d after white phosphorus is used as the reaction raw material. The black phosphorus crystal can be prepared at lower cost while the energy consumption is reduced and the efficiency is improved, and the preparation industrialization of the black phosphorus crystal is facilitated.
2) The invention has the advantages of simple and easily obtained raw materials, mild synthesis conditions, easy regulation and control, simple operation process, convenient repetition and large-scale synthesis.
Drawings
FIG. 1 is an X-ray diffraction chart of a two-dimensional black phosphorus crystal obtained in example 1;
FIG. 2 is a picture of a two-dimensional black phosphorus crystal obtained in example 1;
FIG. 3 is a picture of the two-dimensional black phosphorus crystal obtained in example 2;
FIG. 4 is a scanning electron microscope image of the two-dimensional black phosphorus crystal obtained in example 3;
FIG. 5 is a photograph of the product obtained in example 1 and comparative example 1;
fig. 6 is a picture of the two-dimensional black phosphorus crystal obtained in comparative example 1.
Detailed Description
For a better understanding of the present invention, the content of the present invention will be further elucidated with reference to the specific embodiments and the drawings, but the content of the present invention is not limited to the following embodiments. Among them, comparative examples 1 and 2 are conventional preparation methods for preparing two-dimensional black phosphorus crystals from red phosphorus, and are distinguished from preparing two-dimensional black phosphorus crystals from white phosphorus.
Example 1
A method for preparing two-dimensional black phosphorus crystals by taking white phosphorus as a raw material comprises the following specific preparation steps:
1) Under inert atmosphere, weighing 300 mg white phosphorus, 12 mg metal simple substance tin and 6 mg mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube, and sealing the opening with a sealing film for standby;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a certain heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
4) Placing the sealed quartz tube in a muffle furnace, and keeping the temperature at 2h after the temperature is 1 h to 500 ℃ under the room temperature condition; then starts to cool down, and on the basis of the heat preservation temperature, the temperature is reduced to 350 ℃ through 12 h, then is reduced to 50 ℃ through 6h, and then is reduced to room temperature through 1 h. After the reaction is finished, the high-quality two-dimensional black phosphorus crystal with large volume and high purity is finally prepared.
FIG. 1 is an X-ray diffraction chart of the two-dimensional black phosphorus crystal obtained in example 1. As can be seen from the graph, the sample shows typical black phosphorus characteristic peaks, and no other impurity peaks appear, which indicates that the prepared black phosphorus crystal has good crystallinity and higher purity. The three strong characteristic peaks are respectively for the (020), (040) and (060) crystal faces of the black phosphorus crystal. Fig. 2 is a picture of the two-dimensional black phosphorus crystal obtained in example 1, and it can be seen from the picture that the prepared two-dimensional black phosphorus crystal has a remarkable lamellar structure and a size of about 0.7×0.6×0.5 mm.
Example 2
A method for preparing two-dimensional black phosphorus crystals by taking white phosphorus as a raw material comprises the following specific preparation steps:
1) Under inert atmosphere, weighing 300 mg white phosphorus, 24 mg metal simple substance tin and 12 mg mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube, and sealing the opening with a sealing film for later use;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a certain heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
4) Placing the sealed quartz tube in a muffle furnace, and keeping the temperature at 2h after the temperature is 1 h to 500 ℃ under the room temperature condition; then starts to cool down, and on the basis of the heat preservation temperature, the temperature is reduced to 350 ℃ through 12 h, then is reduced to 50 ℃ through 6h, and then is reduced to room temperature through 1 h. After the reaction is finished, the high-quality two-dimensional black phosphorus crystal with large volume and high purity is finally prepared.
Fig. 3 is a picture of the two-dimensional black phosphorus crystal obtained in example 2, and it can be seen from the picture that the prepared two-dimensional black phosphorus crystal has a remarkable lamellar structure and a size of about 0.6×0.5×0.5 mm.
Example 3
A method for preparing two-dimensional black phosphorus crystals by taking white phosphorus as a raw material comprises the following specific preparation steps:
1) Under inert atmosphere, weighing 1200 mg white phosphorus, 60 mg metal simple substance tin and 6 mg mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube, and sealing the opening with a sealing film for later use;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a certain heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
4) Placing the sealed quartz tube in a muffle furnace, and keeping the temperature at 2h after the temperature is increased to 480 ℃ through 1 h under the condition of room temperature; then starts to cool down, and on the basis of the heat preservation temperature, the temperature is reduced to 350 ℃ through 12 h, then is reduced to 50 ℃ through 6h, and then is reduced to room temperature through 1 h. After the reaction is finished, the high-quality two-dimensional black phosphorus crystal with large volume and high purity is finally prepared.
FIG. 4 is a scanning electron microscope image of the two-dimensional black phosphorus crystal obtained in example 3, and it can be seen from the image that the prepared two-dimensional black phosphorus crystal has an obvious lamellar structure.
Example 4
A method for preparing two-dimensional black phosphorus crystals by taking white phosphorus as a raw material comprises the following specific preparation steps:
1) Under inert atmosphere, weighing 60 mg white phosphorus, 6 mg metal simple substance tin and 6 mg mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube, and sealing the opening with a sealing film for later use;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a certain heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
4) Placing the sealed quartz tube in a muffle furnace, and keeping the temperature at 2h after the temperature is increased to 480 ℃ through 1 h under the condition of room temperature; then starts to cool down, and on the basis of the heat preservation temperature, the temperature is lowered to 380 ℃ through 12 h, then is lowered to 50 ℃ through 18 h, and then is lowered to room temperature through 1 h. After the reaction is finished, the high-quality two-dimensional black phosphorus crystal with large volume and high purity is finally prepared.
Comparative example 1
A method for preparing two-dimensional black phosphorus crystals by taking red phosphorus as a raw material comprises the following specific preparation steps:
1) Under inert atmosphere, weighing 300 mg red phosphorus, 12 mg metal simple substance tin and 6 mg mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube, and sealing the opening with a sealing film for later use;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a certain heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
4) Placing the sealed quartz tube in a muffle furnace, and keeping the temperature at 2h after the temperature is 1 h to 500 ℃ under the room temperature condition; then starts to cool down, and on the basis of the heat preservation temperature, the temperature is reduced to 350 ℃ through 12 h, then is reduced to 50 ℃ through 6h, and then is reduced to room temperature through 1 h. . After the reaction is finished, the red phosphorus raw material has incomplete reaction, and two-dimensional black phosphorus crystals are not obtained. This temperature-raising program was the same as that in comparative example 1 to compare the difference between the two production methods under the same temperature-raising program.
FIG. 5 is a photograph of the product obtained in example 1 and comparative example 1, and it can be seen from the figure that the reaction was performed by the same temperature increasing program, and that in example 1 (using white phosphorus as a raw material), the sample reaction was complete, no obvious red phosphorus was adhered to the pipe wall, and the black phosphorus crystal was grown well. In contrast, the sample of comparative example 1 (with red phosphorus as the starting material) was not completely reacted, a large amount of red phosphorus was adhered to the tube wall, and no significant black phosphorus crystals were formed.
Comparative example 2
A method for preparing two-dimensional black phosphorus crystals by taking red phosphorus as a raw material comprises the following specific preparation steps:
1) Under inert atmosphere, weighing 300 mg red phosphorus, 12 mg metal simple substance tin and 6 mg mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube, and sealing the opening with a sealing film for later use;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) And placing the sealed quartz tube in a muffle furnace, setting a certain heating and cooling program to heat the quartz tube, and finally preparing the high-quality two-dimensional black phosphorus crystal with large volume and high purity after the reaction is finished.
4) Placing the sealed quartz tube in a muffle furnace, and keeping the temperature at 2h after the temperature is increased to 600 ℃ through 1 h under the room temperature condition; then starts to cool down, on the basis of the heat preservation temperature, the temperature is reduced to 350 ℃ through 48 and h, then is reduced to 50 ℃ through 18 and h, and then is reduced to room temperature through 1 and h. And after the reaction is finished, finally preparing the two-dimensional black phosphorus crystal.
Fig. 6 is a picture of the two-dimensional black phosphorus crystal obtained in comparative example 2, from which it can be seen that the conventional preparation method using red phosphorus as a raw material can prepare black phosphorus crystal only under a high-temperature and long-time reaction condition. The prepared two-dimensional black phosphorus crystal also has a lamellar structure, and the size is about 0.5 mm by 0.4 mm by 0.3 mm.
Claims (8)
1. A method for preparing two-dimensional black phosphorus crystals by taking white phosphorus as a raw material comprises the following steps:
1) Weighing white phosphorus, metal simple substance tin and mineralizer tin tetraiodide at the bottom of a single-end sealed quartz tube in an inert atmosphere, and sealing an opening with a sealing film for standby;
2) Removing the sealing film, and rapidly sealing the reaction raw materials in the vacuum quartz tube by using a vacuum tube sealing system;
3) Placing the sealed quartz tube in a muffle furnace, setting a heating and cooling program to heat the quartz tube, and finally preparing a large-volume high-purity high-quality two-dimensional black phosphorus crystal after the reaction is finished;
the program heating and cooling specifically comprises the following steps: under the condition of room temperature, the temperature is raised to 350-500 ℃ for 1-2 hours, and then the heat is preserved for 1-6 hours; then cooling is started, the temperature is reduced to 200-350 ℃ through 6-24 h, then 50-200 ℃ through 6-24 h, and then the room temperature is reduced through 1-6 h on the basis of the heat preservation temperature.
2. The method according to claim 1, wherein the mass feed ratio of white phosphorus, elemental metal tin and mineralizer tin tetraiodide in step 1) is 10-200: 1 to 10:1.
3. the method according to claim 1, wherein the elemental tin in step 1) has a purity of 98% or more; the purity of mineralizer tin tetraiodide is above 95%.
4. The method according to claim 1, wherein the sample atmosphere in step 1) is an inert gas atmosphere, and the quartz tube opening is sealed with a sealing film after the sample is ended.
5. The method of claim 1, wherein in step 2) the reactant is sealed in a quartz tube using a vacuum tube sealing system, and the pressure of the vacuum condition in the tube is less than 1 Pa.
6. The method of claim 1, wherein the temperature control process in step 3) is a programmed temperature increase and decrease by a muffle or tube furnace self-contained controller.
7. The method according to claim 1, wherein the temperature programming rate in step 3) is 150 to 500 ℃/min; the program cooling rate is 10-50 ℃/min.
8. The two-dimensional black phosphorus crystal prepared by the method according to any one of claims 1 to 7, wherein the size of the black phosphorus crystal is between 2 x 2mm and 10 x 10 mm.
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| CN201910518820.2A CN110205674B (en) | 2019-06-16 | 2019-06-16 | Method for preparing two-dimensional black phosphorus crystal by taking white phosphorus as raw material |
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| CN111020697A (en) * | 2019-12-06 | 2020-04-17 | 深圳市中科墨磷科技有限公司 | Sn-doped tin4P3Method for efficiently preparing two-dimensional black phosphorus crystal for catalyst |
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Effective date of registration: 20231206 Address after: 443007 No. 66-2 Ting Ting Road, Ting Ting District, Yichang, Hubei Patentee after: HUBEI MOPHOS TECHNOLOGY Co.,Ltd. Address before: 518111 602-4, 6th floor, building B, Baoneng zhichuanggu, no.6, Fukang Road, Pinghu street, Longgang District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN ZHONGKE MOPHOS TECHNOLOGY Co.,Ltd. |