CN111285339B - Sn (tin) 3 P 4 Preparation method of induced two-dimensional black phosphorus crystal - Google Patents
Sn (tin) 3 P 4 Preparation method of induced two-dimensional black phosphorus crystal Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000013078 crystal Substances 0.000 title claims abstract description 69
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010453 quartz Substances 0.000 claims abstract description 93
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000007789 sealing Methods 0.000 claims abstract description 63
- 239000002994 raw material Substances 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229940124447 delivery agent Drugs 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- 239000002245 particle Substances 0.000 claims description 3
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- 230000008569 process Effects 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 17
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- 230000005693 optoelectronics Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
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- 239000012752 auxiliary agent Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical compound [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- 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
- C01B25/08—Other phosphides
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses Sn 3 P 4 A preparation method of an induced two-dimensional black phosphorus crystal. Under inert atmosphere, red phosphorus raw material and metal simple substance tin are sealed at the bottom of a quartz tube at a single end, reaction raw material is sealed in the quartz tube by utilizing a vacuum tube sealing system, and then the quartz tube is heated and cooled by optimized procedures to obtain block Sn 3 P 4 Compound and ground into powder for use. Weighing red phosphorus raw material and Sn in inert atmosphere 3 P 4 And powder and a transport agent are arranged at the bottom of the quartz tube with a single-end seal, a vacuum tube sealing system is utilized to seal reaction raw materials in the quartz tube, and then the quartz tube is heated and cooled through an optimized program to obtain the high-purity and high-quality two-dimensional black phosphorus crystal. The invention uses the intermediate product Sn of the reaction system 3 P 4 As a catalyst, the method can obviously reduce the nucleation potential barrier required in the red phosphorus-black phosphorus conversion process, accelerate the nucleation and growth process of the reaction, reduce the reaction temperature and the reaction time in the synthesis process and reduce the pressure in the tube.
Description
Technical Field
The invention belongs to the technical field of two-dimensional materials, and particularly relates to Sn 3 P 4 A method for efficiently preparing an induced two-dimensional black phosphorus crystal.
Background
Two-dimensional Black Phosphorus (BP) is a new semiconductor material that has emerged and received much attention in recent years. By virtue of excellent material characteristics of photonics and optoelectronics, black phosphorus has excellent potential in various applications of photons and photoelectric devices. First, black phosphorus has a flexible tunable direct bandgap, which provides optoelectronic devices with a broad spectrum of highly efficient optoelectronic responses from the visible to the mid-infrared. Secondly, considering from the two key performances of the mobility and the on-off ratio of the transistor device, the black phosphorus fills the gap between the Graphene (Graphene) and the Transition Metal Sulfides (TMDCs), and provides an ideal balance performance for the transistor device. Moreover, the in-plane anisotropy of the black phosphorus has great influence on the electrical, optical and mechanical properties of the material, so that an excellent platform is provided for the deep exploration of a novel photoelectric basic principle and the realization of new functional application of a photoelectric device.
The preparation of black phosphorus crystals has also undergone a lengthy research process. Since Bridgeman converted white phosphorus to black phosphorus in 1914 under high temperature and pressure conditions (Journal of the American Chemical Society, 1914, 36 (7): 1344-1363), researchers have developed various processes for the preparation of black phosphorus crystals in recent centuries. Such as mercury catalysis method, high-energy ball milling method, etc., but has no defects of harsh preparation conditions, complex reaction device, etc. Nilges reported a process for converting red phosphorus to black phosphorus using gold and tin as catalysts under low pressure conditions (Inorganic chemistry, 2007, 46 (10): 4028-4035), which has laid a firm foundation for the most widely used Chemical Vapor Transport (CVT) process for preparing black phosphorus crystals.
However, the existing preparation method based on the chemical vapor transport method basically regulates, controls and improves the types of catalysts and transport agents and the temperature increasing and decreasing procedures of the reaction. And the research on the preparation of black phosphorus crystal by using the intermediate product tin-phosphorus compound of the reaction system is rarely reported. Rajesh Ganesan et al (Chemistry of Materials, 2009, 21 3 P 4 The compound, however, is difficult to synthesize in large quantities due to the high equipment requirements of the method. Julia V. Zaikina et al (Chemistry of Materials, 2008, 20 (7): 2476-2483.) use SnCl 2 Preparation of Sn by auxiliary high-temperature vacuum reaction and quenching treatment 3 P 4 Compounds, and their crystal structures and pyroelectricity properties were systematically studiedCan be used. However, this method requires not only SnCl 2 The method has the advantages that the reactor at high temperature needs to be instantly quenched in cold water, the operation difficulty and the danger coefficient are high, and the controllability of the reaction process is difficult to guarantee.
In summary, the current Sn 3 P 4 The preparation method mainly focuses on a chemical synthesis method and a high-temperature sintering method, wherein the former usually needs a complex chemical synthesis process, and the latter also needs introduction of an auxiliary agent and quenching treatment with high danger and poor controllability. And at present Sn 3 P 4 The method is only applied to the field of batteries, and researches on the catalysis of two-dimensional black phosphorus crystal growth are rarely reported. Therefore, a method of producing Sn 3 P 4 The method for preparing the two-dimensional black phosphorus crystal by the catalyst in an efficient and controllable manner has important value for widening industrial application of the black phosphorus material in various fields such as photoelectric devices, energy catalysis, biomedical treatment and the like.
Disclosure of Invention
The invention firstly prepares Sn through high-temperature vacuum reaction and rapid cooling 3 P 4 And the high-purity and high-quality two-dimensional black phosphorus crystal is prepared by taking the red phosphorus crystal as a catalyst and adding a red phosphorus raw material and a transport agent. Sn (tin) 3 P 4 As a catalyst, the method can obviously reduce the nucleation barrier required in the red phosphorus-black phosphorus conversion process and accelerate the nucleation and growth process of the reaction. The method can not only reduce the reaction temperature and the reaction time in the synthesis process and reduce the energy consumption, but also reduce the pressure intensity in the pipe and prevent the pipe explosion.
In order to realize the purpose, the invention adopts the technical scheme that:
sn (tin) 3 P 4 The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following steps:
(1) Weighing red phosphorus raw materials and metal simple substance tin at the bottom of a single-end sealed quartz tube, and sealing the opening for later use by using a sealing film;
(2) Removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system;
(3) The sealed quartz tube is placed in a tube furnace, and the temperature rising and reducing procedures are setHeating the quartz tube to obtain block Sn after the reaction is finished 3 P 4 Taking out the compound, and grinding the compound into powder for later use;
(4) Weighing red phosphorus raw material and Sn 3 P 4 Powder and a transport agent are arranged at the bottom of the quartz tube with a single-end seal, and the opening is sealed by a sealing film for later use;
(5) Removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system;
(6) And (3) placing the sealed quartz tube in a tube furnace, setting temperature rising and reducing programs to heat the quartz tube, and finally preparing the high-purity and high-quality two-dimensional black phosphorus crystal after the reaction is finished.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
In the scheme, the sample weighing atmosphere is inert gas protective atmosphere, and the opening of the quartz tube needs to be sealed by a sealing film after sample weighing is finished.
Preferably, the inert atmosphere comprises any one of argon, nitrogen and helium.
In the above scheme, the elemental metal tin is any one or a combination of at least two of tin powder, tin foil, tin particles, tin bars or tin blocks, and the purity is more than 98%.
Preferably, the metal simple substance tin is any one or a combination of at least two of tin powder, tin foil and tin particles, and the purity is more than 99%.
In the above scheme, the molar ratio of the red phosphorus raw material to the metal simple substance tin is P: sn = 3.5 to 4.5:3.
preferably, the molar ratio of the red phosphorus raw material to the metal simple substance tin is P: sn = 3.8 to 4.2:3.
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 realized by temperature programming and temperature reduction through a controller of the muffle furnace or the tube furnace.
In the above scheme, the procedure of heating and cooling in step (3) specifically comprises: under the condition of room temperature, after the temperature is raised to 420-550 ℃ for 1-6 h, the temperature is kept for 120-240 h; then cooling to room temperature after 1-360 min on the basis of heat preservation temperature. The temperature programming rate is 100 to 550 ℃/h; the programmed cooling rate is 1 to 550 ℃/min.
Preferably, the programmed heating and cooling specifically comprises: under the condition of room temperature, after the temperature is raised to 450-520 ℃ for 1-2 h, the temperature is kept for 144-192 h; then cooling to room temperature after 1-120 min on the basis of heat preservation temperature. The temperature programming rate is 300 to 500 ℃/h; the programmed cooling rate is 5 to 520 ℃/min.
In the scheme, the transport agent is I 2 、SnI 4 、SnI 2 、PbI 2 、NH 4 I、BiI 3 、PI 3 、SnCl 2 、SnBr 2 Any one or a combination of at least two of them, and the purity is 95% or more.
Preferably, the delivery agent is I 2 、SnI 4 、SnI 2 、PbI 2 、NH 4 I、BiI 3 Any one or a combination of at least two of them, and the purity is 98% or more.
In the above scheme, the red phosphorus raw material and Sn 3 P 4 The mass feeding ratio of the powder to the transport agent is 5-100: 5 to 10:1.
preferably, the red phosphorus raw material and Sn 3 P 4 The mass feeding ratio of the powder to the transport agent is 50-100: 8-10: 1.
in the above scheme, the procedure of heating and cooling in step 6) specifically includes: under the condition of room temperature, after the temperature is raised to 440-550 ℃ for 1-6 h, the temperature is kept for 6-12 h; then the temperature is reduced, and the temperature is reduced to the room temperature for 6 to 12 hours on the basis of the heat preservation temperature. The temperature programming rate is 50 to 500 ℃/h; the programmed cooling rate is 20 to 60 ℃/h.
Preferably, the programmed heating and cooling specifically comprises: under the condition of room temperature, after the temperature is raised to 460-520 ℃ for 1-2 h, the temperature is kept for 6-10 h; then cooling to room temperature after 6-10 h on the basis of heat preservation temperature. The temperature programming rate is 300 to 500 ℃/h; the programmed cooling rate is 30 to 50 ℃/h.
The invention firstly prepares Sn through high-temperature vacuum reaction and rapid cooling 3 P 4 And the high-purity and high-quality two-dimensional black phosphorus crystal is prepared by taking the red phosphorus crystal as a catalyst and adding a red phosphorus raw material and a transport agent. The black phosphorus crystal synthesized by the method has less impurities, high purity and good quality, and is more favorable for realizing the industrial scale preparation of the black phosphorus crystal.
Compared with the prior art, the invention has the beneficial effects that: 1) In the invention, sn is prepared by high-temperature vacuum reaction and rapid cooling 3 P 4 Two-dimensional black phosphorus crystals were prepared for the catalyst. Compared with the traditional method for preparing the two-dimensional black phosphorus crystal by taking the metallic simple substance Sn as the catalyst, the method takes the Sn as the reaction intermediate product of the tin-phosphorus binary system 3 P 4 As a catalyst, the reaction conditions are limited to high temperature and high pressure, and direct characterization is difficult. Therefore, a reaction rate contrast chart of "elemental metal Sn induces two-dimensional black phosphorus crystals" under the same conditions is directly provided, as shown in FIG. 8.
The nucleation barrier required in the red phosphorus-black phosphorus conversion process can be obviously reduced, so that the rapid generation of black phosphorus crystal nucleus is promoted, and the nucleation and growth process of the whole reaction is accelerated. In one aspect, the process is capable of reducing the maximum temperature required for the reaction to below 500 ℃ and as low as 440 ℃. The reaction time is shortened to be within 18 hours, and the minimum time can be 13 hours. On the other hand, the acceleration of the red phosphorus-black phosphorus conversion process can promote the consumption of red phosphorus steam, so that v (the volatilization rate of the red phosphorus steam) is less than v (the consumption rate of the red phosphorus steam), is limited by the reaction conditions of high temperature and high pressure, and is difficult to directly represent. The method is also directly observed according to experimental phenomena, v (volatilization) is equal to v (consumption) under normal reaction balance, and if v (volatilization) is greater than v (consumption), the pressure in the tube is overlarge and tube explosion can occur. In the invention, the reaction time can be reduced, and v (volatilization) is smaller than v (consumption), so that the raw materials are accelerated to volatilize to reach balance, and the reaction time is reduced.
Further reducing the pressure in the pipe and preventing the pipe from being burst. Meanwhile, the reduction of the pressure in the tube can also ensure the introduction of more red phosphorus raw materials, and is more favorable for carrying out amplification experiments.
2) The method 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 shows Sn obtained in example 1 3 P 4 X-ray diffraction pattern of (a).
Fig. 2 is an X-ray diffraction spectrum of the two-dimensional black phosphorus crystal obtained in example 1.
FIG. 3 is an enlarged schematic representation of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in example 1.
FIG. 4 is an enlarged schematic view of a quartz tube and a black phosphorus crystal obtained after the completion of the reaction in example 2.
FIG. 5 is an enlarged schematic view of a quartz tube and a black phosphorus crystal obtained after the completion of the reaction in example 3.
FIG. 6 is an enlarged schematic view of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in comparative example 1.
FIG. 7 is an enlarged schematic view of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in comparative example 2.
FIG. 8 is a graph showing a comparison of the reaction rates of the red phosphorus raw materials in the reaction processes of example 1 and comparative example 1.
Detailed Description
For a better understanding of the present invention, the following further illustrates the present invention with reference to specific examples and drawings, but the present invention is not limited to the following examples. Wherein, comparative examples 1 and 2 are the traditional method for preparing two-dimensional black phosphorus crystal by taking metallic simple substance Sn as catalyst, so as to compare with Sn 3 P 4 The difference of the method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst.
Example 1
Sn (tin) 3 P 4 The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) Under inert atmosphere (argon), 117.69 mg of red phosphorus raw material and 356.1 mg of tin powder are weighed at the bottom of a quartz tube with a single-end seal, and the opening is sealed by a sealing film for standby.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is less than 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 450 ℃ for 1 h, the temperature is kept for 144 h; and then, cooling, stopping the heating program on the basis of the heat preservation temperature, and opening the tube furnace to cool the tube furnace to the room temperature within 1 min. After the reaction is finished, block Sn is obtained 3 P 4 The compound is taken out and ground into powder for standby.
4) Weighing 3100 mg of red phosphorus raw material and Sn under inert atmosphere (argon) 3 P 4 Powder 240 mg and delivery agent
I 2 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
5) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
6) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 460 ℃ for 1 h, the temperature is kept for 6 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 6 hours on the basis of the heat preservation temperature. And finally preparing the high-purity and high-quality two-dimensional black phosphorus crystal after the reaction is finished.
FIG. 1 shows Sn obtained in example 1 3 P 4 X-ray diffraction pattern of (a). As can be seen from the figure, the sample exhibited typical Sn 3 P 4 Characteristic peaks and no other miscellaneous peaks appear, which indicates that Sn is prepared 3 P 4 Good crystallinity and high purity. FIG. 2 is a diagram of the embodiment 1And obtaining an X-ray diffraction spectrum of the two-dimensional black phosphorus crystal. As can be seen from the figure, the sample presents typical black phosphorus characteristic peak, and no other miscellaneous peak appears, which indicates that the prepared black phosphorus crystal has good crystallinity and high black phosphorus purity. The three strong characteristic peaks respectively correspond to the (020), (040) and (060) crystal faces of the black phosphorus crystal. FIG. 3 is an enlarged schematic representation of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in example 1. As can be seen from the figure, the red phosphorus raw material in the quartz tube reacts completely, the black phosphorus crystal grows well, and the compact-packed cluster-shaped and sheet-shaped appearances are presented.
Example 2
Sn (tin) 3 P 4 The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) Under inert atmosphere (argon), 130.07 mg of red phosphorus raw material and 356.1 mg of tin bar are weighed at the bottom of a quartz tube with a single-end seal, and the opening is sealed by a sealing film for standby.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is less than 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 520 ℃ for 2 h, the temperature is kept for 192 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 120 min on the basis of the heat preservation temperature. After the reaction is finished, block Sn is obtained 3 P 4 The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material and Sn 4 P 3 Powder 240 mg and delivery agent
SnI 2 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
5) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
6) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 520 ℃ for 2 h, preserving for 10 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 10 hours on the basis of the heat preservation temperature. And finally preparing the high-purity and high-quality two-dimensional black phosphorus crystal after the reaction is finished.
FIG. 4 is an enlarged schematic representation of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in example 2. As can be seen from the figure, the red phosphorus raw material in the quartz tube reacts completely, the black phosphorus crystal grows well, and the compact-packed cluster-shaped and sheet-shaped appearances are presented.
Example 3
Sn (tin) 3 P 4 The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) Under inert atmosphere (argon), 123.88 mg of red phosphorus raw material and 356.1 mg of tin foil are weighed at the bottom of a quartz tube with a single-end seal, and the opening is sealed by a sealing film for later use.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is less than 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 500 ℃ for 1 h, preserving the heat for 168 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 60 min on the basis of the heat preservation temperature. After the reaction is finished, block Sn is obtained 3 P 4 The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material and Sn 4 P 3 Powder 240 mg and delivery agent
SnI 4 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
5) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
6) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is increased to 480 ℃ for 1 h, the temperature is kept for 8 h; then the temperature is reduced, and the temperature is reduced to the room temperature for 8 hours on the basis of the heat preservation temperature. And finally preparing the high-purity and high-quality two-dimensional black phosphorus crystal after the reaction is finished.
FIG. 5 is an enlarged schematic view of a quartz tube and a black phosphorus crystal obtained after the reaction in example 3 was completed. As can be seen from the figure, the red phosphorus raw material in the quartz tube reacts completely, the black phosphorus crystal grows well, and the cluster and sheet shapes which are closely packed are presented.
Example 4
Sn (tin) 3 P 4 The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) Under inert atmosphere (nitrogen), 108.4 mg of red phosphorus raw material and 356.1 mg of tin powder are weighed at the bottom of a quartz tube with a single-end seal, and the opening is sealed by a sealing film for later use.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is below 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 420 ℃ for 1 h, the temperature is kept for 120 h; and then, cooling, stopping the heating program on the basis of the heat preservation temperature, and opening the tube furnace to cool the tube furnace to the room temperature within 1 min. After the reaction is finished, block Sn is obtained 3 P 4 The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (nitrogen), weighing 3100 mg of red phosphorus raw material and Sn 4 P 3 Powder 240 mg and delivery agent
PbI 2 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
5) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
6) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 440 ℃ for 1 h, the temperature is kept for 6 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 6 hours on the basis of the heat preservation temperature. And finally preparing the high-purity and high-quality two-dimensional black phosphorus crystal after the reaction is finished.
Example 5
Sn (tin) 3 P 4 The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) Under inert atmosphere (helium), 139.37 mg of red phosphorus raw material and 356.1 mg of tin bar are weighed at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is less than 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 550 ℃ for 1 h, the temperature is kept for 240 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 360 min on the basis of the heat preservation temperature. After the reaction is finished, block Sn is obtained 3 P 4 The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (helium), weighing 3100 mg of red phosphorus raw material and Sn 4 P 3 Powder 240 mg and delivery agent
BiI 3 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
5) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
6) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is increased to 550 ℃ for 6 h, the temperature is kept for 12 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 12 hours on the basis of the heat preservation temperature. And finally preparing the high-purity and high-quality two-dimensional black phosphorus crystal after the reaction is finished.
Comparative example 1
A method for preparing a two-dimensional black phosphorus crystal induced by a metal simple substance Sn comprises the following specific preparation steps:
1) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material, 120 mg of tin powder and transport agent I 2 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is below 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 460 ℃ for 1 h, the temperature is kept for 6 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 6 hours on the basis of the heat preservation temperature. After the reaction is finished, partial incomplete reaction of the red phosphorus raw material exists, and only a small amount of two-dimensional black phosphorus crystals are obtained.
FIG. 6 is an enlarged schematic view of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in comparative example 1. As can be seen from the figure, most of the red phosphorus raw material in the quartz tube is not completely reacted, and a large amount of red phosphide is adhered to the tube wall.
Comparative example 2
A method for preparing a two-dimensional black phosphorus crystal induced by a metal simple substance Sn comprises the following specific preparation steps:
1) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material, 120 mg of tin powder and transport agent I 2 60 mg is arranged at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for standby.
2) Removing the sealing film, and rapidly sealing the reaction raw materials in a quartz tube by using a vacuum tube sealing system, wherein the pressure of the vacuum condition in the quartz tube is below 1 Pa.
3) And (3) placing the sealed quartz tube in a tube furnace, and setting a temperature rise and temperature reduction program to heat the quartz tube. The specific procedures are as follows: under the condition of room temperature, after the temperature is raised to 600 ℃ for 1 h, the temperature is kept for 24 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 12 hours on the basis of the heat preservation temperature. And finally preparing the two-dimensional black phosphorus crystal after the reaction is finished.
FIG. 7 is an enlarged view of a quartz tube and a black phosphorus crystal obtained after completion of the reaction in comparative example 2. As can be seen from the figure, the red phosphorus raw material in the quartz tube reacts completely, the black phosphorus crystal grows well, and the cluster and sheet shapes which are closely packed are presented. FIG. 8 is a graph showing a comparison of the reaction rates of the red phosphorus raw materials in the reaction processes of example 1 and comparative example 1. As can be seen from the figure, compared with the traditional method for preparing the two-dimensional black phosphorus crystal by taking metallic elementary Sn as the catalyst, the method takes Sn 3 P 4 In order to more efficiently promote the volatilization of the red phosphorus raw material by the method for preparing the two-dimensional black phosphorus crystal by the catalyst, the red phosphorus raw material in the example 1 is basically completely volatilized and reacted within 6 hours, while the red phosphorus raw material in the comparative example 1 is not basically volatilized and reacted within 6 hours. This is due to the reaction intermediate Sn 3 P 4 As a catalyst, the method can obviously reduce the nucleation barrier required in the red phosphorus-black phosphorus conversion process, thereby promoting the rapid generation of black phosphorus crystal nucleus and accelerating the nucleation and growth process of the whole reaction.
As can be seen from the comparison between examples 1 to 5 and comparative examples 1 to 2, the conventional method for preparing the two-dimensional black phosphorus crystal by using the metallic simple substance Sn as the catalyst needs to react for 37 hours at a high temperature of 600 ℃ to obtain the black phosphorus crystal with a better growth condition (comparative example 2). If the reaction temperature is lowered and the reaction time is shortened, the red phosphorus raw material cannot be completely reacted, and it is difficult to obtain a black phosphorus crystal with a good growth condition. In contrast, with Sn 3 P 4 The method for preparing the two-dimensional black phosphorus crystal by the catalyst can obviously reduce the nucleation potential barrier required in the red phosphorus-black phosphorus conversion process, thereby promoting the rapid generation of black phosphorus crystal nucleus and accelerating the nucleation and growth process of the whole reaction. In one aspect, the process is capable of reducing the maximum temperature required for the reaction to below 500 ℃ and as low as 440 ℃ (example 4). The time required for the reaction is shortened to be within 18 hours, and the minimum time can be 13 hours (example 1). On the other hand, the acceleration of the red phosphorus-black phosphorus conversion process can promote the consumption of red phosphorus steam, so that v (the volatilization rate of the red phosphorus steam) is less than v (the consumption rate of the red phosphorus steam), the pressure in the pipe is further reduced, and the pipe explosion phenomenon is prevented. Meanwhile, the reduction of the pressure intensity in the pipe can also be ensuredThe introduction of more red phosphorus raw materials is proved, and the method is more favorable for carrying out amplification experiments.
Claims (7)
1. Sn (tin) 3 P 4 The preparation method of the induced two-dimensional black phosphorus crystal is characterized by comprising the following steps:
(1) Under inert atmosphere, adding a red phosphorus raw material and metallic simple substance tin into a quartz tube, vacuumizing, and sealing for later use, wherein the molar ratio of the red phosphorus raw material to the metallic simple substance tin is P: sn = 3.5 to 4.5:3;
(2) Placing the sealed quartz tube obtained in the step (1) into a tube furnace, setting a temperature rising and reducing program to heat the quartz tube, and obtaining a block Sn after the reaction is finished 3 P 4 Grinding into powder for later use, wherein the procedure of heating and cooling comprises the following steps: under the condition of room temperature, after the temperature is raised to 420-550 ℃ for 1-6 h, the temperature is kept for 120-240 h; then cooling to room temperature after 1-360 min on the basis of heat preservation temperature; the temperature programming rate is 100 to 550 ℃/h; the programmed cooling rate is 1 to 550 ℃/min;
(3) Under inert atmosphere, red phosphorus raw material and Sn in the step (2) 3 P 4 Adding the powder and the transport agent into a quartz tube, vacuumizing and sealing for later use;
(4) And (4) placing the quartz tube sealed in the step (3) into a tube furnace, setting a temperature rising and reducing program to heat the quartz tube, and obtaining the two-dimensional black phosphorus crystal after the reaction is finished.
2. The method according to claim 1, wherein the inert gas atmosphere in the steps (1) and (3) comprises any one of argon, nitrogen and helium.
3. The method according to claim 2, wherein the elemental tin metal in step (1) comprises any one or a combination of at least two of tin powder, tin foil, tin particles, tin bars and tin blocks, and the purity is more than 98%.
4. The production method according to claim 1, wherein the pressure of the vacuum condition in the quartz tube in the step (1) and the step (3) is 1 Pa or less.
5. The method of claim 1, wherein the delivery agent of step (3) is I 2 、SnI 4 、SnI 2 、PbI 2 、NH 4 I、BiI 3 、PI 3 、SnCl 2 、SnBr 2 Any one or a combination of at least two of them, and the purity is 95% or more.
6. The method according to claim 5, wherein the red phosphorus raw material, sn, in the step (3) 3 P 4 The mass feeding ratio of the powder to the transport agent is 5-100: 5 to 10:1.
7. the preparation method according to claim 6, wherein the programmed heating and cooling in step (4) is specifically: under the condition of room temperature, after the temperature is raised to 440-550 ℃ for 1-6 h, the temperature is kept for 6-12 h; then cooling to room temperature for 6-12 h on the basis of heat preservation temperature; the temperature programming rate is 50 to 500 ℃/h; the programmed cooling rate is 20 to 60 ℃/h.
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