CN111439734A - By SnP3Method for efficiently preparing two-dimensional black phosphorus crystal for catalyst - Google Patents
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000013078 crystal Substances 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 238000007789 sealing Methods 0.000 claims abstract description 40
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000010453 quartz Substances 0.000 claims description 54
- 238000000498 ball milling Methods 0.000 claims description 50
- 229910052718 tin Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010963 304 stainless steel Substances 0.000 claims description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical compound [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L Tin(II) bromide Inorganic materials Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000376 reactant 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
- 229910000851 Alloy steel Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 8
- 238000010899 nucleation Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 238000005036 potential barrier Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229940124447 delivery agent Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical class [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000006854 communication Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 235000011178 triphosphate Nutrition 0.000 description 2
- 239000001226 triphosphate Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OZRUMCFJDUAWLN-UHFFFAOYSA-N [I].[Sn].[P] Chemical compound [I].[Sn].[P] OZRUMCFJDUAWLN-UHFFFAOYSA-N 0.000 description 1
- XCWCJGRYIMDVQP-UHFFFAOYSA-A [O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[Sn+4].[Sn+4].[Sn+4] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[Sn+4].[Sn+4].[Sn+4] XCWCJGRYIMDVQP-UHFFFAOYSA-A 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for using SnP3A method for efficiently preparing two-dimensional black phosphorus crystals for a catalyst. Firstly, weighing red phosphorus raw material and metal simple substance tin to carry out high-energy ball milling in inert atmosphere to obtain SnP3Taking out the powder for later use; weighing red phosphorus raw material and SnP under inert atmosphere3And heating the powder and the transport agent in a vacuum tube sealing system to finally prepare the high-purity and high-quality two-dimensional black phosphorus crystal. 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 intermediate product SnP of the reaction system3As 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 reaction timeEnergy consumption, and can also reduce intraductal pressure, prevent to explode the emergence of pipe. 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.
Description
Technical Field
The invention belongs to the technical field of two-dimensional materials, and particularly relates to a tin-phosphorus compound (SnP)3) A method for efficiently preparing two-dimensional black phosphorus crystals for a catalyst.
Background
Since 2014, black phosphorus has begun to gain wide attention due to its excellent properties, and is even considered to be a novel two-dimensional atomic material comparable to graphene. Two-dimensional black phosphorus is of most particular value in three different respects from other two-dimensional materials. (1) Optical properties. The band gap size of the thin-layer black phosphorus can be adjusted through the thickness (0.3-1.5 eV), and the band gap is just a bridge connecting the zero band gap of the graphene and the band gap defect between the wider band gap (1.5-2.5 eV) of the transition metal sulfide. Researches show that the thin-layer black phosphorus shows stronger light conduction efficiency in the wave band range of 1-5 mu m, which indicates that the black phosphorus has great application potential in the fields of near-infrared and intermediate-infrared optoelectronic devices, such as optical detectors, modems and light emitting diodes. In addition, when a single layer or a few layers of black phosphorus are subjected to a strain force such as compression or tension, the band structure of the black phosphorus can be changed significantly. Therefore, the single-layer black phosphorus photoresponse band can cover a wide range and can strongly interact with electromagnetic waves, and the single-layer black phosphorus photoresponse band has important application in the fields of medicine, national defense, communication, night vision, thermal imaging technology, near infrared, intermediate infrared and visible light region optical communication and the like. (2) Electrical properties. The black phosphorus has higher electron mobility and on-off ratio, so that the black phosphorus can be applied to field effect transistors beyond the strength of graphene. Currently, the first generation of high-speed black phosphorus transistors benefit from good current saturation performance due to the unique bandgap properties of black phosphorus, and exhibit superior electron emission frequency in terms of voltage and power gain. Future applications are expected to be greater in nanoelectronic devices. (3) In-plane anisotropy. The most unique property of black phosphorus is strong anisotropy in plane, and in the D2h dot group of the orthorhombic system, the effective carriers of the zigzag type along the longitudinal direction are ten times of those along the transverse direction. This property makes it possible to use black phosphorus for the design of new electronic and photonic devices. Researchers have begun exploring the unique polarization properties of black phosphorus plasma devices plus photoelectrons, and their application to thermoelectric devices. Therefore, the development of an efficient and controllable preparation method of the black phosphorus crystal is necessary for popularizing the practical application of the black phosphorus.
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 methods based on the chemical vapor transport method basically adjust, control and improve the types of catalysts and transport agents (CN106498492A, CN106087050) and the reaction temperature raising and lowering procedures (CN105133009A, CN105603517A, CN108059138A), and the catalysts commonly used at present, such as Sn, Bi, In, Pb, Cd, etc., are usually toxic or easily generate toxic by-products, and the catalytic efficiency is low. For example, in the patents CN105133009B, CN106087050A and CN109913942A, the formation process of the intermediate product is completely uncontrollable by using pure tin as a catalyst, so the catalytic efficiency is low. 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. Park J W et al (Scientific Reports,2016,6:35980.) use a high energy ball milling method to prepare SnP from tin powder and phosphorus powder3Adding amorphous carbon powder to the compound, further ball milling to obtain SnP3The novel positive electrode material has the characteristics of high volume capacity, high initial coulombic efficiency, stable performance circulation, high rapid rate capability and the like, and can be used for rechargeable lithium ionThe application of the pool has wide prospect. Patent CN109841820A discloses a preparation method of amorphous tetratin triphosphate/phosphorus/few-layer graphene negative electrode material for lithium ion battery. Firstly, mixing tin powder and phosphorus powder, and ball-milling to obtain tin triphosphate (SnP)3) And mixing the product with expanded graphite and further ball-milling to obtain the amorphous tetratin triphosphate/phosphorus/few-layer graphene composite material. The cathode material is matched with a lithium iron phosphate cathode material, and the assembled lithium ion battery shows excellent performance. In addition, as in patent CN109305661A, a tin-iodine-phosphorus ternary compound is used as a catalyst, although the catalytic efficiency is high, since it is necessary to introduce iodine or iodide which is very volatile during the synthesis process, the purity of the product and the controllability of the synthesis process are poor, which is far less than the stability of the tin-phosphorus compound.
The current state of research, tin phosphorus compounds (SnP)3) 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 tin phosphorus compound (SnP) was developed3) 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-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 the tin-phosphorus compound (SnP) by high-energy ball milling3) 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. Not only can reduce the reaction temperature and the reaction time in the synthesis process and reduce the energy consumption, but also can reduce the pressure intensity in the pipe and prevent the pipe explosion. 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.
In order to achieve the purpose, the invention adopts the technical scheme that:
tin phosphorus compound (SnP)3) The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst comprises the following steps:
1) weighing red phosphorus raw material and metal simple substance tinAnd (4) performing high-energy ball milling in a ball milling tank under inert atmosphere. After the ball milling is finished, SnP is obtained3And taking the powder out for later use.
2) Weighing red phosphorus raw material and SnP under inert atmosphere3The powder and the conveying 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.
3) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
4) 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-quality two-dimensional black phosphorus crystal with large volume 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 ball milling atmosphere and the sample weighing atmosphere are inert gas protective atmosphere, and the opening of the quartz tube needs to be sealed by a sealing film after sample weighing is finished.
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 is 2.5-3.5: 1.
preferably, the molar ratio of the red phosphorus raw material to the metal simple substance tin is P: sn is 2.8-3.2: 1.
in the above scheme, the ball-milling material (including the ball-milling pot and the milling balls) is any one or a combination of at least two of agate, zirconia, corundum, silicon nitride, polytetrafluoroethylene, nylon, polyurethane, cemented carbide and 304 stainless steel. The particle size of the grinding ball is 0.1-1 cm, the ball material ratio is 80-100: 1, the ball milling time is 24-72 h, and the ball milling rotating speed is 200-600 r/min.
Preferably, the ball milling material (including the ball milling pot and the milling balls) is any one or a combination of at least two of agate, zirconium dioxide, corundum, silicon nitride, cemented carbide and 304 stainless steel. The particle size of the grinding ball is 0.5-1 cm, the ball material ratio is 90-100: 1, the ball milling time is 36-60 h, and the ball milling speed is 300-500 r/min.
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 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, the 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 scheme, the red phosphorus raw material and SnP3The mass feeding ratio of the powder to the transport agent is 5-100: 5-10: 1.
preferably, the red phosphorus raw material and SnP3The 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 specifically comprises: 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 the tin-phosphorus compound (SnP) by high-energy ball milling3) 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, tin-phosphorus compound (SnP) is prepared by high-energy ball milling3) 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 reaction intermediate product SnP of the tin-phosphorus binary system3As 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. 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 (red phosphorus steam volatilization) is less than v (red phosphorus steam consumption), the pressure intensity 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.
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 a tin-phosphorus compound (SnP) obtained in example 13) 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 view of a quartz tube and a black phosphorus crystal obtained after the reaction in example 1;
FIG. 4 is an enlarged view of a quartz tube and a black phosphorus crystal obtained after the reaction in example 2;
FIG. 5 is an enlarged view of a quartz tube and a black phosphorus crystal obtained after the reaction in example 3;
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. Among them, comparative example 1 is a conventional method for preparing two-dimensional black phosphorus crystal using metallic simple substance Sn as catalyst, to compare tin phosphorus compound (SnP)3) The difference of the method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst.
Example 1
Tin phosphorus compound (SnP)3) The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst comprises the following specific preparation steps:
1) 86.7mg of red phosphorus raw material and 118.7mg of metal simple substance tin are weighed in a ball milling tank and are subjected to high-energy ball milling in an inert atmosphere. The specific parameters are as follows: the ball milling material (including a ball milling tank and grinding balls) is agate, the particle size of the grinding balls is 0.5cm, and the ball-to-material ratio is 90: 1, the ball milling time is 36h, and the ball milling rotating speed is 300 r/min. After the ball milling is finished, SnP is obtained3And taking the powder out for later use.
2) Weighing 3100mg of red phosphorus raw material and SnP under inert atmosphere3Powder 210mg and delivery agent I260 mg were placed on the bottom of a single-ended quartz tube, and the opening was sealed with a sealing film for use.
3) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
4) 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 1h, 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 a tin-phosphorus compound (SnP) obtained in example 13) X-ray diffraction pattern of (a). As can be seen from the figure, the sample exhibited a typical SnP3Characteristic peak and no other miscellaneous peak appear, which indicates that the SnP is prepared3Good crystallinity and high purity. FIG. 2 is an X-ray diffraction pattern 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
Tin phosphorus compound (SnP)3) The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst comprises the following specific preparation steps:
1) 99.1mg of red phosphorus raw material and 118.7mg of metal simple substance tin are weighed in a ball milling tank and are subjected to high-energy ball milling in an inert atmosphere. The specific parameters are as follows: the ball milling material (including a ball milling tank and grinding balls) is zirconium dioxide, the particle size of the grinding balls is 1cm, and the ball material ratio is 100: 1, the ball milling time is 60 hours, and the ball milling rotating speed is 500 r/min. After the ball milling is finished, SnP is obtained3And taking the powder out for later use.
2) Weighing 3100mg of red phosphorus raw material and SnP under inert atmosphere3Powder 210mg and delivery agent SnI260mg 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.
3) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
4) 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 2h, the temperature is kept 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
Tin phosphorus compound (SnP)3) The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst comprises the following specific preparation steps:
1) 92.9mg of red phosphorus raw material and 118.7mg of metal simple substance tin are weighed in a ball milling tank and are subjected to high-energy ball milling in an inert atmosphere. The specific parameters are as follows: the ball milling material (including the ball milling tank and the grinding balls) is zirconium dioxide, the particle size of the grinding balls is 0.8cm, and the ball-to-material ratio is 95: 1, the ball milling time is 48h, and the ball milling rotating speed is 400 r/min. After the ball milling is finished, SnP is obtained3And taking the powder out for later use.
2) Weighing 3100mg of red phosphorus raw material and SnP under inert atmosphere3Powder 210mg and delivery agent SnI460mg 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.
3) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
4) 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 1h, 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
Tin phosphorus compound (SnP)3) The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst comprises the following specific preparation steps:
1) 77.4mg of red phosphorus raw material and 118.7mg of metal simple substance tin are weighed in a ball milling tank and are subjected to high-energy ball milling in an inert atmosphere. The specific parameters are as follows: the ball milling material (including a ball milling tank and grinding balls) is agate, the particle size of the grinding balls is 0.1cm, and the ball-to-material ratio is 80: 1, the ball milling time is 24 hours, and the ball milling rotating speed is 200 r/min. After the ball milling is finished, SnP is obtained3And taking the powder out for later use.
2) Weighing 3100mg of red phosphorus raw material and SnP under inert atmosphere3Powder 210mg and delivery agent PbI260mg 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.
3) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
4) 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 1h, 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
Tin phosphorus compound (SnP)3) The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst comprises the following specific preparation steps:
1) 108.4mg of red phosphorus raw material and 118.7mg of metal simple substance tin are weighed in a ball milling tank and are subjected to high-energy ball milling in an inert atmosphere. The specific parameters are as follows: the ball milling material (including ball milling pot and milling ball) is agate, the particle size of the milling ball is 1cm, and the ball-to-material ratio is 100:1, the ball milling time is 72 hours, and the ball milling rotating speed is 600 r/min. After the ball milling is finished, SnP is obtained3And taking the powder out for later use.
2) Weighing 3100mg of red phosphorus raw material and SnP under inert atmosphere3Powder 210mg and delivery agent BiI360mg 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.
3) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
4) 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 6h, 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 two-dimensional black phosphorus crystals by taking a metal simple substance Sn as a catalyst comprises the following specific preparation steps:
1) weighing 3100mg of red phosphorus raw material, 120mg of metallic simple substance tin and a transport agent I in inert atmosphere260mg 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) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
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 1h, 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 two-dimensional black phosphorus crystals by taking a metal simple substance Sn as a catalyst comprises the following specific preparation steps:
1) weighing 3100mg of red phosphorus raw material, 120mg of metallic simple substance tin and a transport agent I in inert atmosphere260mg 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) And removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system.
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 1h, 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 two-dimensional black phosphorus crystal by taking metallic simple substance Sn as a catalyst, the method takes tin phosphorus compound (SnP)3) 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 facilitated by the reaction intermediate SnP3As 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 1-3 and comparative examples 1-2, the conventional method for preparing the two-dimensional black phosphorus crystal by using the elemental metal Sn as the catalyst needs to react for 37 hours at a high temperature of 600 ℃ to obtain the black phosphorus crystal with a good growth condition (comparative example 2). If the reaction temperature is lowered, shrinkageShort reaction time, the red phosphorus raw material can not completely react, and black phosphorus crystals with good growth condition are difficult to obtain. In contrast, with tin-phosphorus compounds (SnP)3) 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 reaction time is shortened to be within 18h, and the minimum time can be 13h (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 (red phosphorus steam volatilization) is less than v (red phosphorus steam consumption), the pressure intensity 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 (10)
1. By SnP3The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized by comprising the following steps of:
1) weighing red phosphorus raw materials and metal simple substance tin in a ball milling tank, and carrying out high-energy ball milling in an inert atmosphere; after the ball milling is finished, SnP is obtained3Taking out the powder for later use;
2) weighing red phosphorus raw material and SnP under inert atmosphere3The 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;
3) removing the sealing film, and quickly sealing the reaction raw materials in the quartz tube by using a vacuum tube sealing system;
4) 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-quality two-dimensional black phosphorus crystal with large volume after the reaction is finished.
2. The SnP of claim 13Method for efficiently preparing two-dimensional black phosphorus crystals for catalyst, characterized in that the atmosphere described in step 1) and step 2)The atmosphere is inert gas protective atmosphere.
3. The SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that the metal simple substance tin in the step 1) is any one or the combination of at least two of tin powder, tin foil, tin particles, tin strips or tin blocks, and the purity is more than 98%.
4. The SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that the element molar ratio of the red phosphorus raw material and the metal simple substance tin in the step 1) is P: sn is 2.5-3.5: 1.
5. the SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that the ball-milling material in the step 1) comprises a ball-milling tank and milling balls, and is any one or combination of at least two of agate, zirconium dioxide, corundum, silicon nitride, polytetrafluoroethylene, nylon, polyurethane, hard alloy and 304 stainless steel; the particle size of the grinding ball is 0.1-1 cm, the ball material ratio is 80-100: 1, the ball milling time is 24-72 h, and the ball milling rotating speed is 200-600 r/min.
6. The SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that in the step 2), the reactant is sealed in a quartz tube by using a vacuum tube sealing system, and the pressure of the vacuum condition in the tube is less than 1 Pa.
7. The SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that the temperature control process in the step 3) is temperature programming and temperature reduction realized by a muffle furnace or a tube furnace with a controller.
8. The SnP of claim 13Efficient preparation of II for catalystThe method for preparing the Vigreux phosphorus crystal is characterized in that the transport agent in the step 4) 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.
9. The SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that the red phosphorus raw material and SnP in the step 5)3The mass feeding ratio of the powder to the transport agent is 5-100: 5-10: 1.
10. the SnP of claim 13The method for efficiently preparing the two-dimensional black phosphorus crystal for the catalyst is characterized in that the procedure of heating and cooling in the step 6) is as follows: 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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| CN111892027A (en) * | 2020-08-24 | 2020-11-06 | 昆明理工大学 | Method for preparing nano black phosphorus by one-step method |
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| CN111892027A (en) * | 2020-08-24 | 2020-11-06 | 昆明理工大学 | Method for preparing nano black phosphorus by one-step method |
| CN112939065A (en) * | 2021-03-12 | 2021-06-11 | 昆明理工大学 | Preparation method of black phosphorus catalyst |
| CN115739136A (en) * | 2022-12-16 | 2023-03-07 | 中国科学院深圳理工大学(筹) | Black phosphorus and purple phosphorus composite material, preparation method thereof, photocatalyst and application |
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