CN109305661A - A method of preparing rhombic system black phosphorus monocrystalline - Google Patents
A method of preparing rhombic system black phosphorus monocrystalline Download PDFInfo
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- CN109305661A CN109305661A CN201710644806.8A CN201710644806A CN109305661A CN 109305661 A CN109305661 A CN 109305661A CN 201710644806 A CN201710644806 A CN 201710644806A CN 109305661 A CN109305661 A CN 109305661A
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- Prior art keywords
- black phosphorus
- iodine
- preparation
- phosphorus
- tin
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 21
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- OZRUMCFJDUAWLN-UHFFFAOYSA-N [I].[Sn].[P] Chemical compound [I].[Sn].[P] OZRUMCFJDUAWLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims description 60
- 238000010792 warming Methods 0.000 claims description 23
- 229910052718 tin Inorganic materials 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 3
- 238000000859 sublimation Methods 0.000 claims description 3
- 230000008022 sublimation Effects 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 2
- 238000007789 sealing Methods 0.000 claims 2
- YQNSMGUFZYPDOO-UHFFFAOYSA-N [P].[I] Chemical compound [P].[I] YQNSMGUFZYPDOO-UHFFFAOYSA-N 0.000 claims 1
- 230000007717 exclusion Effects 0.000 claims 1
- 238000003306 harvesting Methods 0.000 claims 1
- HKOSYZIBCKCKET-UHFFFAOYSA-M iodotin Chemical compound I[Sn] HKOSYZIBCKCKET-UHFFFAOYSA-M 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims 1
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical group [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 136
- 239000010453 quartz Substances 0.000 description 117
- 239000003708 ampul Substances 0.000 description 78
- 238000005538 encapsulation Methods 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000227 grinding Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000011135 tin Substances 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- QPBYLOWPSRZOFX-UHFFFAOYSA-J Tin(IV) iodide Inorganic materials I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite alkenes Chemical class 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 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
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to rhombic system black phosphorus method for preparing single crystal, specifically: ternary phosphor tin iodine catalyst and red phosphorus are mixed, it is placed in reactor, exclude by temperature programming and cooling to prepare black phosphorus after air is tamping, wherein ternary phosphor tin iodine catalyst can preparatory mass production, and it is good as the black phosphorus crystal property of catalyst acquisition using it, purity is high, yield is up to 99%, and catalyst can be reused, and provides great convenience for subsequent black phosphorus application development.
Description
Technical field
The invention belongs to optoelectronic semiconductor two-dimensional material fields, and in particular to a kind of side of preparation of rhombic system black phosphorus material
Method.
Background technique
More stringent requirements are proposed for development of the rapid development of semiconductor electronic industry to material.Graphene has started two dimension
The epoch of material, the carrier mobility (15000cm of superelevation2/ V*s) and other superior physicochemical properties make it
It is considered as the most possible material for replacing silicon, however the characteristic that band gap is zero limits the development of graphene.With graphite alkenes
Seemingly, black phosphorus is a kind of two-dimensional material of single element, there is Van der Waals force between layers, and difference can be obtained by way of removing
The flat crystal of the number of plies.Black phosphorus not only possesses superhigh current carrying transport factor (200~50000cm of class graphene2/ V*s), and
Its band gap can adjust (0.3eV~2.0eV) by the number of plies, compensate for the deficiency of graphene.In addition to this, black phosphorus material internal
Electronics and photon show the anisotropy of height in lamella, therefore are suitble to the development of future electronic industry.
The research of black phosphorus at present is in the starting stage, and development is slower, is primarily due to currently without a kind of simple height
The synthetic method of effect.1914, Bridgman heated white phosphorus to 200 DEG C, finds black phosphorus for the first time under the pressure of 1.2GPa
In the presence of；Nineteen fifty-five, German chemist Krebs, H. under normal pressure, use mercury as catalyst, and using a small amount of black phosphorus as crystal seed,
At a temperature of 370 DEG C, white phosphorus is converted to black phosphorus；1981, Tokyo University scientist Maruyama, Y. used the simple substance melted
Bismuth dissolves white phosphorus, and then Slow cooling recrystallization synthesizes acicular black phosphorus.However, the severe toxicity and ignition quality of white phosphorus limit
The application of these methods.2007, Nilges, Tom utilized Au, Sn and SnI4As combination catalyst, under vacuum conditions, add
Hot red phosphorus obtains black phosphorus to 600 DEG C, but the introducing of noble metal improves production cost and the purity of black phosphorus decreases；
CA105133009A, CA105460910 and CA105565289 also disclose the improvement to this method, but former to temperature control and red phosphorus
That expects is more demanding, and there is catalyst choice certain limitation (to be only limitted to Au, Sn, I2Or its product that reacts to each other) and simultaneously
It does not reuse；2010, Cheol-Min Park utilized high energy ball mill, synthesized the composite material of red phosphorus and black phosphorus, but
High-energy ball milling method is difficult accurately to control the pressure and temperature of inside reactor, influences the controllability of preparation process.Therefore at present
More commonly used synthetic method is high pressure (10kbar) method, but these methods have high requirement to laboratory apparatus.
Summary of the invention
The purpose of the present invention is to provide a kind of low in cost, convenient and safe rhombic system black phosphorus method for preparing single crystal.
To achieve the goals above, the present invention provides a kind of preparation method of rhombic system black phosphorus monocrystalline, wherein this method
Include: to mix phosphorus raw material with phosphor tin iodine three-way catalyst, be placed in reactor, be tamping after excluding oxygen and pass through temperature programming
Black phosphorus is prepared with cooling.
Compared with prior art, the present invention using reusable new catalyst, reaction temperature is optimized, is simplified
Heating process shortens the reaction time.Other features and advantages of the present invention will give in detail in the following detailed description section
It describes in detail bright.
Detailed description of the invention
Attached drawing is to further understand for providing to invention, and constitute part of specification, and following specific
Embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the temperature lowering curve that heats up in black phosphorus preparation process；
Fig. 2 is the X-ray powder diffraction spectrum of catalyst in embodiment 2；
Fig. 3 is the digital photograph of catalyst in embodiment 2；
Fig. 4 is the digital photograph of black phosphorus crystal in embodiment 2；
Fig. 5 is the X-ray diffractogram tested after black phosphorus crystal grinding in embodiment 2
Fig. 6 is the X-ray diffractogram in embodiment 2 after black phosphorus crystal removing；
Fig. 7 is the Raman spectrogram of black phosphorus crystal in embodiment 2；
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of preparation method of black phosphorus monocrystalline, wherein this method comprises: by phosphorus raw material, catalyst mixing,
It is placed in reactor, oxygen rear enclosed will be excluded in reactor, and black phosphorus is prepared by temperature programming and temperature-fall period.Wherein it is catalyzed
Agent is phosphor tin iodine three-way catalyst, includes Sn24P19.3I8；Discharge oxygen can be by vacuumizing or being discharged with inert gas empty
The mode of gas is realized；In Temperature Programmed Processes, pass through time t from room temperature first1It is warming up to sublimation temperature T1, then through time t2Drop
To crystallization initiation temperature T2, by time t3Reach crystallization final temperature T3.Wherein time t1、t2It does not limit, T1It is more than or equal to
450 DEG C, preferably T1More than or equal to 535 DEG C；Time t3It is relatively long, it is greater than 4 hours, T3More than or equal to 416 DEG C, it is preferable that T3
More than or equal to 450 DEG C；T3It is down to the process of room temperature not limited way, Temperature fall, air cooling-down, condensed water drop can be used
The modes such as temperature are realized.
According to the present invention, the preparation of black phosphorus is divided into two processes, respectively catalyst preparation and black phosphorus preparation, this process
It is to industrialize large scale preparation catalyst for convenience, reduces the process that material is launched, but is not excluded for merging two steps, it will
The reactor of black phosphorus synthesis is added in catalyst raw material and red phosphorus, during temperature programming and cooling in-situ preparation catalyst from
And synthesize black phosphorus.
According to the present invention, the phosphor tin iodine three-way catalyst be comprising phosphorus, tin, iodine atom mixture, tin atom and iodine
Molar ratio >=2.5 of atom, preferably >=3, molar ratio >=2 of phosphorus atoms and iodine atom preferably >=2.4 are warming up to 450 DEG C
More than, 500 DEG C or more are preferably risen to, kept for 10 hours or more, preferably kept for 72 hours or more, it is down to room temperature, is produced
Object is used as catalyst after grinding uniformly.
Embodiment 1
Catalyst preparation:
By 12mmol Sn, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 40mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 91%, for bulk.
Embodiment 2
Catalyst preparation:
By 12mmol Sn, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 99%, for bulk.
Embodiment 3
Catalyst preparation:
By 1.5mmol Sn, 0.25mmol I2, 1.2mmol red phosphorus is added in hyaline-quartz pipe, then (interior to quartz ampoule
Diameter 1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.450 DEG C are warming up to, is kept for 10 hours, is down to
Room temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 30mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 99%, for bulk.
Embodiment 4
Catalyst preparation:
By 12mmol Sn, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.550 DEG C are warming up to, is kept for 96 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 99%, for bulk.
Embodiment 5
Catalyst preparation:
By 10mmol Sn, 2mmol I2, 8mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter 1cm,
Long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room temperature,
It is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 88%, for bulk.
Embodiment 6
Catalyst preparation:
By 20mmolSn, 2mmol I2, 20mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter 1cm,
Long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room temperature,
It is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 96%, for bulk.
Embodiment 7
Catalyst preparation:
By 12mmol Sn, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-450 DEG C of room temperature -
30min-450 DEG C -480min-416 DEG C-room temperature, obtained black phosphorus conversion ratio is 46%, for bulk.
Embodiment 8
Catalyst preparation:
By 12mmol Sn, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-535 DEG C of room temperature -
30min-535 DEG C -480min-450 DEG C-room temperature, obtained black phosphorus conversion ratio is 80%, for bulk.
Embodiment 9
Catalyst preparation:
By 8mmol Sn, 1mmol SnI4, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C -120min-200 DEG C-room temperature, obtained black phosphorus conversion ratio is 98%, for bulk.
Embodiment 10
Catalyst preparation:
By 10mmolSn, 2mmol SnI2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C -120min-200 DEG C-room temperature, obtained black phosphorus conversion ratio is 98%, for bulk.
Embodiment 11
Catalyst preparation:
By 3.2mmol Sn4P3, 2mmol I2, it is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room temperature, is ground with agate
Alms bowl is uniformly stand-by by product grinding.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C -120min-200 DEG C-room temperature, obtained black phosphorus conversion ratio is 98%, for bulk.
Embodiment 12
Catalyst preparation:
By 9.6mmol Sn3P, 2mmol I2, it is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room temperature, is ground with agate
Alms bowl is uniformly stand-by by product grinding.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C -120min-200 DEG C-room temperature, obtained black phosphorus conversion ratio is 90%, for bulk.
Embodiment 13
Catalyst preparation:
By 1.3mmol PI3, 12mmol Sn, 8.3mmol red phosphorus is added in hyaline-quartz pipe, then (interior to quartz ampoule
Diameter 1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to
Room temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C -120min-200 DEG C-room temperature, obtained black phosphorus conversion ratio is 95%, for bulk.
Embodiment 14
Catalyst preparation:
By 4mmol SnIP, 8mmol Sn, 4mmol red phosphorus is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C -120min-200 DEG C-room temperature, obtained black phosphorus conversion ratio is 80%, for bulk.
Embodiment 15
Catalyst preparation:
By 12mmol Pb, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 95%, for bulk.
Embodiment 16
Catalyst preparation:
By 12mmol Pb, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 25mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 95%, for bulk.
Embodiment 17
Catalyst preparation:
By 8mmol Pb, 4mmol Sn, 2mmol I2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz
Pipe (internal diameter 1cm, long 10cm) is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, holding 72 is small
When, it is down to room temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 25mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 96%, for bulk.
Embodiment 18
Catalyst preparation:
It will be by 10mmol Pb, 2mmol PbI2, 9.65mmol red phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule
(internal diameter 1cm, long 10cm) is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours,
It is down to room temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 25mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 95%, for bulk.
Embodiment 19
Catalyst preparation:
By 12mmol Sn, 2mmol I2, 9.65mmol black phosphorus, be added hyaline-quartz pipe in, then to quartz ampoule (internal diameter
1cm, long 10cm) it is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.500 DEG C are warming up to, is kept for 72 hours, is down to room
Temperature, it is with agate mortar that product grinding is uniformly stand-by.
Black phosphorus preparation:
Catalyst 20mg, red phosphorus 300mg are taken, is added in hyaline-quartz pipe, then to quartz ampoule (internal diameter 1cm, long 10cm)
It is vacuumized, when vacuum degree reaches 1Pa encapsulation quartz ampoule.It is reacted according to following heating schedule: -60min-650 DEG C of room temperature -
60min-650 DEG C -480min-500 DEG C-room temperature, obtained black phosphorus conversion ratio is 99%, for bulk.
Embodiment 20
Product black phosphorus in embodiment 1 is taken out, remaining catalyst (20mg) is transferred to another quartz ampoule (internal diameter
1cm, long 10cm), 300mg red phosphorus is added, then quartz ampoule is vacuumized, encapsulates quartz ampoule when vacuum degree reaches 1Pa,
It is reacted according to following heating schedule: -60min-650 DEG C -120min-650 DEG C -480min-500 DEG C-room temperature of room temperature, temperature-fall period
In such a way that condensed water cools.
Obtaining black phosphorus conversion ratio is about 82%, for bulk.
Claims (10)
1. a kind of preparation method of rhombic system black phosphorus monocrystalline is placed in reactor this method comprises: catalyst and red phosphorus are mixed
Middle exclusion oxygen is simultaneously tamping, and prepares black phosphorus by temperature programming and temperature-fall period；In Temperature Programmed Processes, first from room temperature
To sublimation temperature (T1) guarantee that red phosphorus distils completely, then it is down to crystallization initiation temperature (T2), by crystallization time (t3), it is down to knot
Brilliant final temperature (T3), it is cooled to room temperature harvest black phosphorus crystal, wherein T1>=450 DEG C, t3>=4 hours, T3≥416℃；This method
It is characterized in that catalyst is phosphor tin iodine three-way catalyst, includes Sn24P19.3I8。
2. the preparation method of rhombic system black phosphorus monocrystalline according to claim 1, wherein sublimation temperature (T1) it is preferably T1≥
535 DEG C, crystallize final temperature (T3) it is preferably T3≥450℃。
3. the preparation method of rhombic system black phosphorus monocrystalline according to claim 1 or 2, wherein phosphor tin iodine three-way catalyst
The preparation method comprises the following steps: containing only the mixture of three kinds of elements of phosphor tin iodine, wherein molar ratio >=2.5 of tin atom and iodine atom, phosphorus are former
Molar ratio >=2 of son and iodine atom exclude air sealing, are warming up to maximum temperature >=450 DEG C, retention time >=10 hour, drop
It include Sn in product to room temperature24P19.3I8。
4. the preparation method of rhombic system black phosphorus monocrystalline according to claim 1 or 2, wherein phosphor tin iodine three-way catalyst
Preparation method is preferred are as follows: the mixture of three kinds of elements of phosphor tin iodine is contained only, the molar ratio of tin atom and iodine atom in mixture >=
3, molar ratio >=2.4 of phosphorus atoms and iodine atom exclude air sealing, are warming up to maximum temperature >=500 DEG C, retention time
>=10 hours, it is down to room temperature, temperature-fall period >=72 hour include Sn in product24P19.3I8。
5. the preparation method of rhombic system black phosphorus monocrystalline according to claim 3 or 4, wherein containing only three kinds of members of phosphor tin iodine
The mixture of element is preferably phosphorus simple substance, tin simple substance, elemental iodine.
6. the preparation method of rhombic system black phosphorus monocrystalline according to claim 3 or 4, wherein containing only three kinds of members of phosphor tin iodine
The mixture of element is preferably phosphorus simple substance, tin simple substance, iodine tin compound.
7. the preparation method of rhombic system black phosphorus monocrystalline according to claim 3 or 4, wherein containing only three kinds of members of phosphor tin iodine
The mixture of element is preferably phosphor tin compound, elemental iodine.
8. the preparation method of rhombic system black phosphorus monocrystalline according to claim 3 or 4, wherein containing only three kinds of members of phosphor tin iodine
The mixture of element is preferably phosphorus simple substance, tin simple substance, phosphorus iodine compound.
9. the preparation method of rhombic system black phosphorus monocrystalline according to claim 3 or 4, wherein containing only three kinds of members of phosphor tin iodine
The mixture of element is preferably SnIP and tin simple substance.
10. the preparation method of rhombic system black phosphorus monocrystalline described in any one of -9 according to claim 1, wherein tin atom can
To be substituted completely or partially by lead atom.
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| CN110467165A (en) * | 2019-08-29 | 2019-11-19 | 昆明理工大学 | A method of high-purity black phosphorus is prepared using fixed-bed catalytic |
| CN110658178A (en) * | 2019-09-29 | 2020-01-07 | 江苏拉曼医疗设备有限公司 | Fluorescence background subtraction method for Raman spectrum |
| CN110963474A (en) * | 2019-12-03 | 2020-04-07 | 昆明理工大学 | Preparation method of black phosphorus-based nano material |
| CN111020697A (en) * | 2019-12-06 | 2020-04-17 | 深圳市中科墨磷科技有限公司 | Sn-doped tin4P3Method for efficiently preparing two-dimensional black phosphorus crystal for catalyst |
| CN111111712A (en) * | 2019-12-19 | 2020-05-08 | 昆明理工大学 | Multi-section temperature rise and fall preparation of black phosphorus catalyst AxByCzMethod (2) |
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| CN113493929A (en) * | 2020-03-18 | 2021-10-12 | 深圳市中科墨磷科技有限公司 | Preparation method of black phosphorus single crystal wafer |
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| CN110467165A (en) * | 2019-08-29 | 2019-11-19 | 昆明理工大学 | A method of high-purity black phosphorus is prepared using fixed-bed catalytic |
| CN110467165B (en) * | 2019-08-29 | 2023-03-10 | 昆明理工大学 | Method for preparing high-purity black phosphorus by adopting fixed bed catalysis |
| CN110658178A (en) * | 2019-09-29 | 2020-01-07 | 江苏拉曼医疗设备有限公司 | Fluorescence background subtraction method for Raman spectrum |
| CN110963474A (en) * | 2019-12-03 | 2020-04-07 | 昆明理工大学 | Preparation method of black phosphorus-based nano material |
| CN111020697A (en) * | 2019-12-06 | 2020-04-17 | 深圳市中科墨磷科技有限公司 | Sn-doped tin4P3Method for efficiently preparing two-dimensional black phosphorus crystal for catalyst |
| CN111111712A (en) * | 2019-12-19 | 2020-05-08 | 昆明理工大学 | Multi-section temperature rise and fall preparation of black phosphorus catalyst AxByCzMethod (2) |
| CN113493929A (en) * | 2020-03-18 | 2021-10-12 | 深圳市中科墨磷科技有限公司 | Preparation method of black phosphorus single crystal wafer |
| CN112939065A (en) * | 2021-03-12 | 2021-06-11 | 昆明理工大学 | Preparation method of black phosphorus catalyst |
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