CN105460910B - A kind of constant temperature and the extensive method for preparing banding black phosphorus - Google Patents
A kind of constant temperature and the extensive method for preparing banding black phosphorus Download PDFInfo
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- CN105460910B CN105460910B CN201510801468.5A CN201510801468A CN105460910B CN 105460910 B CN105460910 B CN 105460910B CN 201510801468 A CN201510801468 A CN 201510801468A CN 105460910 B CN105460910 B CN 105460910B
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a kind of constant temperature and the extensive method for preparing banding black phosphorus to prepare black phosphorus in a manner of a kind of constant temperature.Specifically with cheap red phosphorus, tin and iodine are raw material, by solid phase reaction, under stationary temperature and relatively low pressure, prepare the banding black phosphorus of pure phase.It is simple that the present invention prepares the step of black phosphorus, strong operability, has following significant technical advantage：First, using nontoxic raw material, clean environment firendly；2nd, tin tetraiodide is replaced using iodo, cost is greatly reduced；3rd, black phosphorus high conversion rate；4th, substitute tube furnace using muffle furnace and carry out black phosphorus growth, black phosphorus yield is greatly improved, single black phosphorus yield is dependent only on the volume of muffle furnace, and the single yield than growing black phosphorus with tube furnace improves at least more than 10 times.Prepared banding black phosphorus has good crystallinity, is more easy to the characteristics of mechanical stripping goes out the thin layer black phosphorus of large area, and the preparation and application to the subsequently photoelectric device based on black phosphorus provide a great convenience.
Description
Technical field
The present invention relates to the synthesis field of chemical material, and in particular to a kind of constant temperature and the extensive side for preparing banding black phosphorus
Method.
Technical background
Class graphene two-dimensional semiconductor material is due to high conductivity, high tenacity and great specific surface area, being considered as
It is expected to substitute traditional semiconductor silicon, triggers new round revolution in electronics technology field.However, because graphene is without energy band knot
Structure, it is impossible to the Push And Release of logic circuit is realized, this strongly limits it in the application of electronic device and field of photoelectric devices, such as light
Electric explorer, solar cell, field-effect transistor etc..In recent years, find New Two Dimensional semi-conducting material and have become material
One of important research field of science.
Black phosphorus is common four kind allotrope (red phosphorus, white phosphorus, violet phosphorus, black phosphorus) Midst density maximum (2.69g/ of phosphorus
cm3), most stable of one, there is the layer structure of similar graphite, combined between layers by Van der Waals force.However, its structure
In be different from the maximum feature of graphite and be, the phosphorus atoms in its same layer are not in the layer of fold along b axles in the same plane
Shape arranges, and interlamellar spacing is bigger than graphite (about 5 angstroms).In addition, it is direct band-gap semicondictor, have good hole mobility and
Optical characteristics, and the theoretical cell capacity 2596mAh/g higher than graphite, these advantages all cause it in electronics and phototube
Part field has great application prospect.
Traditional method for preparing black phosphorus is to be made by being heated under high pressure (12000atm) under white phosphorus, or normal pressure of mercury
It is prepared by catalyst.These methods have the characteristics of high toxicity, unclean environmentally friendly.Recently, also there are article report red phosphorus, tin
Change gold, tin tetraiodide is that raw material prepares black phosphorus, but the cost of gold and tin tetraiodide is high in raw material used, and tin tetraiodide also needs
To prepare in advance, substantially increase preparation cost, technique is cumbersome, up to 600 Euros of the black phosphorus unit price of present commercial sale/
Gram.On the other hand, preparation method reported above is due to needing thermograde, and Preparation equipment is tube furnace, the yield of black phosphorus by
To very big limitation, scale of mass production can not be realized.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of constant temperature is provided and prepares banding black phosphorus on a large scale
Method, this method optimize the preparation process of black phosphorus, and tin tetraiodide, specific Cost comparisons are substituted using the cheap raw material crystalline flake of iodine：
Tin tetraiodide 304RMB/g, the crystalline flake of iodine：12RMB/g, cost (cost than originally reduces 96%) is substantially reduced, meanwhile, eliminate
Original the step of preparing tin tetraiodide, manpower and materials are saved.On the other hand, for the practical application of large-scale production, attempt
Black phosphorus is grown with the method for constant temperature, raw material is put into tube sealing in quartz ampoule first, placed into muffle furnace, is put into muffle furnace
Quartz ampoule quantity is dependent only on the volume of muffle furnace, therefore the yield of black phosphorus prepared by single obtains relative to quartz ampoule
At least more than 10 times of raising.Specifically with red phosphorus, tin and iodine are raw material, by solid phase reaction, are prepared in constant temperature muffle furnace
The banding black phosphorus of pure phase.Experiment finds that the black phosphorus of this banding has relative to the bulk black phosphorus prepared before and is more easy to mechanical stripping
Separate out the advantage of the black squama of large area thin layer.
Above-mentioned constant temperature and the extensive method for preparing banding black phosphorus are through the following steps that realize；By high-purity red phosphorus, tin
With iodine 10-40 in mass ratio:0.2-3:0.05-0.4 is mixed, and is fitted into quartz ampoule, the muffle furnace of constant temperature is put into after direct tube sealing
In, 500~650 DEG C of in-furnace temperature is set, is incubated 2-5h, 5 to 10h 300 to 480 DEG C is cooled to again afterwards, is incubated 2-5h, then
Room temperature is cooled to after 3 to 10h.The banding black phosphorus of gained is evenly distributed in quartz ampoule.
The form of described high-purity red phosphorus is powder or particle, and purity is not less than 99.99%, and the form of described tin is
Fragment or powder, the form of described iodine is sheet.The form for obtaining black phosphorus is banding (strip).
With the method high toxicity of existing synthesis black phosphorus at present, yielding poorly, high pressure prepares the characteristics of cost is higher and compared, this
It is simple that invention prepares the step of black phosphorus, strong operability, has following significant technical advantage：First, using nontoxic raw material, cleaning
Environmental protection；2nd, tin tetraiodide is replaced using iodo, cost is greatly reduced；3rd, black phosphorus conversion ratio reaches 97%；4th, taken using muffle furnace
Black phosphorus is prepared for tube furnace, black phosphorus yield can be increased substantially so that single black phosphorus yield is dependent only on the volume of muffle furnace,
At least more than 10 times are improved relative to the single yield of tube furnace growth black phosphorus.Importantly, prepared black phosphorus has
The pattern of strip, surface is smooth, goes out the relatively thin black phosphorus of large area beneficial to mechanical stripping, this answering on photoelectric device to black phosphorus
With significant.
Brief description of the drawings
Fig. 1 is the outside drawing that embodiment 1 obtains black phosphorus product in quartz ampoule, and (a) is overall appearance, and (b) is quartz ampoule
Outward appearance is amplified in end, and (c) is the outside drawing of black phosphorus.
Fig. 2 is the XRD of black phosphorus prepared by embodiment 1.
Fig. 3 is the SEM figures of black phosphorus prepared by embodiment 1；(a), (b) is respectively the black phosphorus SEM figures under different angle..
Fig. 4 is the light microscopic figure after banding black phosphorus mechanical stripping prepared by embodiment 1；(a), (b), (c) are respectively different angles
Light microscopic figure under degree.
Embodiment
Below in conjunction with drawings and the specific embodiments, the invention will be further described.
Embodiment 1
By tin, high-purity red phosphorus, iodine is according to tin:Red phosphorus:Iodine=0.6:20:0.1 ratio (mass ratio) mixing, is then charged into
Direct tube sealing in quartz ampoule；Then the quartz ampoule after tube sealing is put into muffle furnace, the quartz ampoule quantity being put into is boiled depending on horse
Furnace volume；The reaction time is set, then heats to 650 DEG C, 2h is incubated, cools to 300 DEG C afterwards, continues to be incubated 2h, finally
It is slowly cooled to room temperature (10h).The strip black phosphorus of gained is evenly distributed in quartz ampoule, as shown in Figure 1.
Products therefrom is black ribbon block, and Fig. 2 is its XRD, and its SEM is as shown in Figure 3, it can be seen that products therefrom is
Black phosphorus.And through measurement, gained black phosphorus quality is about 97% of red phosphorus quality in raw material.
The black phosphorus of gained strip is chosen, mechanical stripping is constantly carried out with adhesive tape, is finally bonded at silicon/silicon dioxide substrate
On, observed with light microscopic microscope, it can be found that as shown in Figure 4 compared with the relatively thin black phosphorus of the strip of how much area.Embodiment 2
By tin, high-purity red phosphorus, iodine is according to tin:Red phosphorus:Iodine=1:18:0.4 ratio mixing, is then charged into quartz ampoule straight
Connect tube sealing；Then the quartz ampoule after tube sealing is put into muffle furnace, quartz ampoule quantity depends on muffle furnace volume；Set reaction
Time, 750 DEG C are then heated to, be incubated 5h, cool to 400 DEG C afterwards, continued to be incubated 5h, be finally slowly cooled to room temperature
(15h).The strip black phosphorus of gained is evenly distributed in quartz ampoule.
Embodiment 3
By tin, high-purity red phosphorus, iodine is according to tin:Red phosphorus:Iodine=3:40:0.5 ratio mixing, is then charged into quartz ampoule straight
Connect tube sealing；Then the quartz ampoule after tube sealing is put into muffle furnace, quartz ampoule quantity depends on muffle furnace volume；Set reaction
Time, 500 DEG C are then heated to, be incubated 10h, cool to 200 DEG C afterwards, continued to be incubated 8h, be finally slowly cooled to room temperature
(20h).The strip black phosphorus of gained is evenly distributed in quartz ampoule.
Embodiment 4
By tin, high-purity red phosphorus, iodine is according to tin:Red phosphorus:Iodine=0.2:10:0.05 ratio mixing, is then charged into quartz ampoule
In direct tube sealing；Then the quartz ampoule after tube sealing is put into muffle furnace, quartz ampoule quantity depends on muffle furnace volume；Set
In the reaction time, 600 DEG C are then heated to, be incubated 1h, cool to 350 DEG C afterwards, continued to be incubated 5h, be finally slowly cooled to room temperature
(6h).The strip black phosphorus of gained is evenly distributed in quartz ampoule.
Claims (2)
1. a kind of constant temperature and the extensive method for preparing banding black phosphorus, it is characterised in that this method comprises the following steps：
By high-purity red phosphorus, tin and iodine according to mass ratio 10-40:0.2-3:0.05-0.4 is mixed, and is fitted into quartz ampoule, direct tube sealing
It is put into afterwards in the muffle furnace of constant temperature, sets 500~650 DEG C of in-furnace temperature, is incubated 2-5h, cools to 300 with 5 to 10h again afterwards
~480 DEG C, 2-5h is incubated, then room temperature is cooled to 3 to 10h, banding black phosphorus is obtained in quartz ampoule.
2. constant temperature according to claim 1 and the extensive method for preparing banding black phosphorus, it is characterised in that described is high-purity
Red phosphorus purity is not less than 99.99%.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106711408B (en) * | 2015-11-13 | 2019-05-10 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanometer sheet-graphene composite film cathode and preparation |
| CN106498492A (en) * | 2016-11-01 | 2017-03-15 | 南京工业大学 | A kind of method for preparing rhombic system black phosphorus monocrystalline |
| CN106744754A (en) * | 2016-11-14 | 2017-05-31 | 深圳大学 | A kind of red phosphorus preprocess method prepared for black phosphorus |
| CN108059137B (en) * | 2017-12-04 | 2020-09-08 | 中国科学院电工研究所 | Preparation method of black phosphorus nano material |
| CN108128761B (en) * | 2018-01-30 | 2021-06-18 | 昆明理工大学 | Continuous preparation method of black phosphorus |
| CN108408703A (en) * | 2018-06-15 | 2018-08-17 | 广西越洋科技股份有限公司 | A kind of production method of black phosphorus |
| CN110498404B (en) * | 2019-07-22 | 2021-01-22 | 山东玥能新材料科技有限公司 | Method for in-situ preparation of black phosphorus-carbon nanotube composite material |
| KR102255946B1 (en) * | 2019-08-07 | 2021-05-25 | 한국표준과학연구원 | Methods of forming black phosphorous |
| CN111170291B (en) * | 2020-01-21 | 2023-01-31 | 上海交通大学 | Method for quickly preparing black phosphorus at low cost |
| CN112645295A (en) * | 2021-01-05 | 2021-04-13 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN112830462A (en) * | 2021-02-03 | 2021-05-25 | 陕西科技大学 | Method for safely and efficiently synthesizing high-purity black phosphorus |
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113620264B (en) * | 2021-08-27 | 2023-03-17 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| CN114772564B (en) * | 2022-04-27 | 2023-04-07 | 中南大学 | Black phosphorus arsenic quantum dot and preparation method thereof |
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| CN102219180B (en) * | 2010-04-14 | 2013-05-01 | 中国科学院理化技术研究所 | Method for synthesizing one-dimensional inorganic nano material with conical structure by pressure control in VLS (Vapor-Liquid-Solid) process |
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| CN104630879A (en) * | 2015-02-28 | 2015-05-20 | 安庆美晶新材料有限公司 | Method for preparing black phosphorus monocrystal from high-purity red phosphorus under atmospheric pressure |
| CN104787736B (en) * | 2015-04-04 | 2016-12-28 | 重庆市金升机械配件制造有限公司 | A kind of method preparing double-decker black phosphorus on a large scale |
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