CN111285339A - Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal - Google Patents
Sn (tin)3P4Preparation 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 125
- 238000000034 method Methods 0.000 title claims abstract description 80
- 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
- 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
- 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
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 24
- 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 7
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 claims description 7
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 7
- 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
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical compound [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 claims description 3
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L Tin(II) bromide Inorganic materials Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000005303 weighing Methods 0.000 abstract description 12
- 230000006911 nucleation Effects 0.000 abstract description 10
- 238000010899 nucleation Methods 0.000 abstract description 10
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005036 potential barrier Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- -1 Transition Metal Sulfides Chemical class 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 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
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 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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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses Sn3P4A 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 Sn3P4Compound and ground to a powder for use. Weighing red phosphorus raw material and Sn in inert atmosphere3P4Powder and a transport agent are arranged at the bottom of a 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 relates to a reaction systemIntermediate product Sn3P4As 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 Sn3P4A method for efficiently preparing two-dimensional black phosphorus crystals by induction.
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 photon and photoelectric device applications. First, black phosphorus has a flexible and tunable direct bandgap, which provides a wide-spectrum efficient optoelectronic response for optoelectronic devices 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, and the like, thereby providing an excellent platform for deeply exploring a novel photoelectric basic principle and realizing the application of new functions 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 developed various methods for the preparation of black phosphorus crystals in hundreds of years. 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 method for converting red phosphorus into black phosphorus under low pressure conditions by using gold and tin as catalysts (Inorganic chemistry, 2007, 46(10): 4028-4035), which lays a firm foundation for preparing black phosphorus crystals by the Chemical Vapor Transport (CVT) method which is most widely used at present, until 2007.
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, 21:4108-3P4The 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):2476-2Preparation of Sn by auxiliary high-temperature vacuum reaction and quenching treatment3P4The crystal structure and the thermoelectric property of the compound are researched systematically. However, this method requires not only SnCl2The 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 Sn3P4The 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 risk and poor controllability. And at present Sn3P4The method is only applied to the field of batteries, and researches on the catalysis of two-dimensional black phosphorus crystal growth are rarely reported. Thus, a method of forming Sn3P4The method for preparing the two-dimensional black phosphorus crystal by the catalyst in an efficient and controllable manner has important value for widening industrial-level 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 cooling3P4And 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)3P4As a catalyst, the nucleation barrier required in the red phosphorus-black phosphorus conversion process can be obviously reduced, and the nucleation and growth processes of the reaction are accelerated. 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 achieve the purpose, the invention adopts the technical scheme that:
sn (tin)3P4The 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) placing the sealed quartz tube in a tube furnace, setting a temperature rise and temperature reduction program to heat the quartz tube, and obtaining a block Sn after the reaction is finished3P4Taking out the compound, and grinding the compound into powder for later use;
(4) weighing red phosphorus raw material and Sn3P4The powder and the 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 standby;
(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 a temperature rise and temperature reduction program 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 scheme, the element molar ratio of the red phosphorus raw material to the metal simple substance tin is P: sn = 3.5~ 4.5: 3.
preferably, the molar ratio of the red phosphorus raw material to the metal simple substance tin is P: sn = 3.8~ 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 100-550 ℃/h; the programmed cooling rate is 1-550 ℃/min.
Preferably, the procedure of 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; and then cooling to room temperature after 1-120 min on the basis of heat preservation temperature. The temperature programming rate is 300-500 ℃/h; the programmed cooling rate is 5-520 ℃/min.
In the scheme, the transport agent is I2、SnI4、SnI2、PbI2、NH4I、BiI3、PI3、SnCl2、SnBr2Any one or a combination of at least two of them, and the purity is 95% or more.
Preferably, theThe delivery agent is I2、SnI4、SnI2、PbI2、NH4I、BiI3Any 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 Sn3P4The mass feeding ratio of the powder to the transport agent is 5-100: 5-10: 1.
preferably, the red phosphorus raw material and Sn3P4The 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, preserving the heat for 6-12 h; and then cooling to room temperature for 6-12 hours on the basis of the heat preservation temperature. The temperature programming rate is 50-500 ℃/h; the programmed cooling rate is 20-60 ℃/h.
Preferably, the procedure of 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; and then cooling to room temperature for 6-10 hours on the basis of the heat preservation temperature. The temperature programming rate is 300-500 ℃/h; the programmed cooling rate is 30-50 ℃/h.
The invention firstly prepares Sn through high-temperature vacuum reaction and rapid cooling3P4And 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 cooling3P4Two-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 reaction intermediate product Sn of the tin-phosphorus binary system3P4As a catalyst, the reaction conditions are limited to high temperature and high pressure, and direct characterization is difficult. So that the direct provision of "elemental metal Sn induced two-dimensional black under the same conditionsPhosphorus crystals "are 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 13P4X-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 representation of a quartz tube and a black phosphorus crystal obtained after 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 reaction in example 3 was completed.
FIG. 6 is an enlarged 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 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 Sn3P4The difference of the method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst.
Example 1
Sn (tin)3P4The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) 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 under inert atmosphere (argon), 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 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 obtained3P4The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material and Sn3P4Powder 240 mg and delivery agent
I260 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for later use.
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 13P4X-ray diffraction pattern of (a). As can be seen from the figure, the sample exhibited typical Sn3P4Characteristic peaks and no other miscellaneous peaks appear, which indicates that Sn is prepared3P4Good crystallinity and high purity. Fig. 2 is an X-ray diffraction spectrum of the two-dimensional black phosphorus crystal obtained in example 1. 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 cluster and sheet shapes which are closely packed are presented.
Example 2
Sn (tin)3P4The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) 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 under inert atmosphere (argon), 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 obtained3P4The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material and Sn4P3Powder 240 mg and delivery agent
SnI260 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for later use.
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 cluster and sheet shapes which are closely packed are presented.
Example 3
Sn (tin)3P4The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) 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 under inert atmosphere (argon), 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) Placing the sealed quartz tube in the tubeAnd in the furnace, heating treatment is carried out on the quartz tube by setting temperature rising and reducing programs. 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 60min on the basis of the heat preservation temperature. After the reaction is finished, block Sn is obtained3P4The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (argon), weighing 3100 mg of red phosphorus raw material and Sn4P3Powder 240 mg and delivery agent
SnI460 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for later use.
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 after 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)3P4The 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 less than 1 Pa.
3) Placing the sealed quartz tube in a tube furnace, and setting the temperature to rise and fallThe temperature program heats 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 obtained3P4The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (nitrogen), weighing 3100 mg of red phosphorus raw material and Sn4P3Powder 240 mg and delivery agent
PbI260 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for later use.
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)3P4The method for efficiently preparing the induced two-dimensional black phosphorus crystal comprises the following specific preparation steps:
1) 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 under an inert atmosphere (helium gas), 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, preserving the heat for 240 h; then, the temperature is reduced, and the temperature is reduced to the room temperature after 360min on the basis of the heat preservation temperature. After the reaction is finished, block Sn is obtained3P4The compound is taken out and ground into powder for standby.
4) Under inert atmosphere (helium), weighing 3100 mg of red phosphorus raw material and Sn4P3Powder 240 mg and delivery agent
BiI360 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, and the opening is sealed by a sealing film for later use.
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 I260 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, 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 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 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 I260 mg of the mixture is placed at the bottom of a quartz tube with a single end sealed, 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 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 Sn3P4In 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 Sn3P4As a catalyst, 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.
As can be seen from comparison between examples 1-5 and comparative examples 1-2, the conventional method for preparing two-dimensional black phosphorus crystal by using elemental metallic Sn as catalyst needs to be carried out at a high temperature of 600 DEG CThe reaction is carried out for 37 hours, and then the black phosphorus crystal with better growth condition can be obtained (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 Sn3P4The 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 in the tube can also ensure the introduction of more red phosphorus raw materials, and is more favorable for carrying out amplification experiments.
Claims (9)
1. Sn (tin)3P4The preparation method of the induced two-dimensional black phosphorus crystal is characterized by comprising the following steps:
(1) under inert atmosphere, adding red phosphorus raw material and metal simple substance tin into a quartz tube, vacuumizing and sealing for later use;
(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 finished3P4Grinding into powder for later use;
(3) under inert atmosphere, red phosphorus raw material and Sn in the step (2)3P4Adding the powder and the transport agent into a quartz tube, vacuumizing and sealing for later use;
(4) and (4) placing the sealed quartz tube 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 has a purity of 98% or more.
4. The method according to claim 3, wherein the molar ratio of the red phosphorus raw material to the elemental tin metal in step (1) is P: sn = 3.5~ 4.5: 3.
5. the production method according to claim 4, wherein the pressure under vacuum in the quartz tube in the step (1) and the step (3) is 1 Pa or less.
6. The preparation method according to claim 5, wherein the programmed heating and cooling in step (2) is specifically: 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 100-550 ℃/h; the programmed cooling rate is 1-550 ℃/min.
7. The method of claim 6, wherein the delivery agent of step (3) is I2、SnI4、SnI2、PbI2、NH4I、BiI3、PI3、SnCl2、SnBr2Any one or a combination of at least two of them, and the purity is 95% or more.
8. The method according to claim 7, wherein the red phosphorus raw material, Sn, in the step (3)3P4The mass feeding ratio of the powder to the transport agent is 5-100: 5-10: 1.
9. the preparation method according to claim 8, 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, preserving the heat for 6-12 h; then, cooling, and cooling to room temperature for 6-12 hours on the basis of the heat preservation temperature; the temperature programming rate is 50-500 ℃/h; the programmed cooling rate is 20-60 ℃/h.
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