CN104787736B - A kind of method preparing double-decker black phosphorus on a large scale - Google Patents
A kind of method preparing double-decker black phosphorus on a large scale Download PDFInfo
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- CN104787736B CN104787736B CN201510157436.6A CN201510157436A CN104787736B CN 104787736 B CN104787736 B CN 104787736B CN 201510157436 A CN201510157436 A CN 201510157436A CN 104787736 B CN104787736 B CN 104787736B
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Abstract
The invention provides a kind of method preparing double-decker black phosphorus on a large scale, it is characterised in that the method comprises the steps: 1) by white phosphorus or red phosphorus under 68 Kbar pressure, in temperature 600 800 DEG C, react at least 1 min；2) step 1) gains are placed in ethanol water immersion 46 h；3) utilizing ultrasonic Treatment at least 10 min, ultrasonic power is 70 80 W.The preparation technology of the present invention is simple, it is possible to obtain the double-decker black phosphorus of higher production rate, its production rate is up to 91.0%；Preparation technology of the present invention is with low cost, it is easy to large-scale application.
Description
Technical field
The present invention relates to double-decker black phosphorus preparation technology field, be specifically related to one and prepare double-decker black phosphorus on a large scale
Method.
Technical background
Two dimensional crystal material, because possessing superior electric property, is paid much attention to by semi-conducting material research field.Two
The appearance of two-dimensional material truly has been declared in the discovery of dimension Graphene, the most always as study hotspot.
But, owing to the processing cost of Graphene is high, and not there is quasiconductor band gap, it is impossible to realize patrolling of digital circuit
Collect Push And Release, hinder the application of Graphene.
Therefore, the demand seeking a kind of material substituting Graphene seems the most urgent.
Black phosphorus, as the newfound material being prepared as two dimensional crystal material, became new scientific research focus over the past two years.
" natural nanotechnology " magazine in 2014 has published the research utilizing black phosphorus to prepare FET device so that black phosphorus
Research again reach a climax.
But, in the prior art, the method preparing double-decker black phosphorus the most also rests in mechanical stripping method, effect
Rate is the lowest.Therefore, have under the basis of broad prospect of application at known black phosphorus, it would be highly desirable to exploitation one prepares bilayer on a large scale
The method of structure black phosphorus.
Summary of the invention
For the shortcoming of prior art, it is an object of the invention to provide a kind of side preparing double-decker black phosphorus on a large scale
Method, the method comprises the steps:
1) by white phosphorus or red phosphorus under 6-8 Kbar pressure, in temperature 600-800 DEG C, at least 1 min is reacted；
2) step 1) gains are placed in ethanol water immersion 4-6 h；
3) utilizing ultrasonic Treatment at least 10 min, ultrasonic power is 70-80 W.
Preferably, the temperature in described step 1) is 750 DEG C.
When carrying out high temperature high pressure process, sheet interlayer can produce bubble and each lamella of black phosphorus is mutually peeled off.Inventor finds,
Under pressure is 6-8 Kbar, when temperature is 750 DEG C, the beneficially stripping of each interlayer of black phosphorus.But need to point out time, in this situation
Under, the stripping of each interlayer, do not reach to maximize, simply after 750 DEG C process, in conjunction with subsequent step of the present invention,
The highest available double-decker black phosphorus production rate.For preparation extensive for black phosphorus, temperature is the highest, and cost accordingly will
It is the highest, it is often more important that, temperature is the highest, it is not necessary to just can obtain more preferable double-decker black phosphorus survival rate.Such as one of them
Shown in embodiment, when temperature reaches 1050 DEG C, the production rate scope of double-decker black phosphorus reduces by a small margin.
Preferably, the response time of described step 1) is 10 min.
Response time is the most important for the stripping of black phosphorus lamella, although high-temperature process is not required to the long time, but longer
The process time can obtain more preferable double-decker black phosphorus production rate.The process time of 10 min, simply obtaining good bilayer
On the premise of structure black phosphorus survival rate, provide cost savings.
Preferably, described step 2) in, the volume ratio of second alcohol and water is 2-3:1, and soak time is 5 h.It is furthermore preferred that institute
The volume ratio stating second alcohol and water is 12:5.
Inventor finds, is placed in ethanol water after a period of time by the black phosphorus after high temperature high pressure process, rather than vertical
I.e. carrying out supersound process, the productivity ratio of the double-decker black phosphorus of gained is more preferable.When the volume ratio of second alcohol and water is 12:5, double-deck
The lifting of structure black phosphorus production rate is the most notable.
Preferably, described ultrasonic power is 75 W, and the process time is 15 min.It is furthermore preferred that described ultrasonic power
Being 75 W, the process time is 30 min
Inventor finds, in the present invention, the preparation of double-decker black phosphorus to be realized, ultrasonic power at least to reach
More than 60W, time more than 70W power, can obtain preferable production rate.When power is 75 W, and the process time is 15 min, generate
Rate reaches good level.When being 30 min between when treated, production rate also has small elevation.
Beneficial effects of the present invention:
The preparation technology of the present invention is simple, it is possible to obtain the double-decker black phosphorus of higher production rate, its production rate up to
91.0%；Preparation technology of the present invention is with low cost, it is easy to large-scale application.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be that following example are simply used
In the present invention is further detailed, it is impossible to be interpreted as limiting the scope of the invention, being skilled in technique of this field
Some nonessential improvement and adjustment that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
In all of the embodiments illustrated, environment under high pressure is provided by Riken CAP-07 instrument.The thickness of black phosphorus utilizes atomic force
Microscope is tested, and thickness is about 10, it is determined that for double-decker black phosphorus.
Embodiment 1
1) by white phosphorus under 6Kbar pressure, in temperature 600 DEG C, 1 min is reacted；
2) being placed in ethanol water by step 1) gains and soak 4 h, ethanol is 2:1 with the volume ratio of water；
3) utilizing ultrasonic Treatment 10 min, ultrasonic power is 70W.
Embodiment 2
1) by white phosphorus under 8Kbar pressure, in temperature 800 DEG C, 10min is reacted；
2) being placed in ethanol water by step 1) gains and soak 6 h, ethanol is 3:1 with the volume ratio of water；
3) utilizing ultrasonic Treatment 15 min, ultrasonic power is 80W.
Embodiment 3
1) by red phosphorus under 7Kbar pressure, in temperature 750 DEG C, 10min is reacted；
2) step 1) gains are placed in ethanol water immersion 5h, and ethanol is 12:5 with the volume ratio of water；
3) utilizing ultrasonic Treatment 15 min, ultrasonic power is 75W.
Embodiment 4
1) by white phosphorus under 7Kbar pressure, in temperature 750 DEG C, 10min is reacted；
2) step 1) gains are placed in ethanol water immersion 5h, and ethanol is 12:5 with the volume ratio of water；
3) utilizing ultrasonic Treatment 30 min, ultrasonic power is 75W.
Comparative example
1) by red phosphorus under 7Kbar pressure, in temperature 1050 DEG C, 10min is reacted；
2) step 1) gains are placed in ethanol water immersion 5h, and ethanol is 12:5 with the volume ratio of water；
3) utilizing ultrasonic Treatment 30 min, ultrasonic power is 75W.
Experimental example
Embodiment 1-embodiment 4 and comparative example are carried out the production rate detection of double-decker black phosphorus.The results are shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example | |
| Double-decker black phosphorus production rate (%) | 81.4% | 83.7% | 89.5% | 91.0% | 72.5% |
Claims (7)
1. the method preparing double-decker black phosphorus on a large scale, it is characterised in that described method comprises the steps:
1) by white phosphorus or red phosphorus under 6-8 Kbar pressure, in temperature 600-800 DEG C, at least 1 min is reacted；
2) step 1) gains are placed in ethanol water immersion 4-6 h；
3) utilizing ultrasonic Treatment at least 10 min, ultrasonic power is 70-80 W.
Method the most according to claim 1, it is characterised in that the temperature in described step 1) is 750 DEG C.
Method the most according to claim 1, it is characterised in that the response time of described step 1) is 10 min.
Method the most according to claim 1, it is characterised in that described step 2) in, the volume ratio of second alcohol and water is 2-3:
1, soak time is 5 h.
Method the most according to claim 4, it is characterised in that the volume ratio of described second alcohol and water is 12:5.
Method the most according to claim 1, it is characterised in that described ultrasonic power is 75 W, the process time is 15
min。
Method the most according to claim 1, it is characterised in that described ultrasonic power is 75 W, the process time is 30
min。
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| CN104787736B true CN104787736B (en) | 2016-12-28 |
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| CN106384719B (en) * | 2015-08-06 | 2020-06-23 | 王贝贝 | Processing method for etching black phosphorus two-dimensional material body by using oxygen plasma |
| CN105116034B (en) * | 2015-09-08 | 2018-02-27 | 浙江美罗机电有限公司 | A kind of sensor based on black phosphorus electrode and preparation method thereof |
| CN105297133B (en) * | 2015-10-28 | 2017-12-12 | 南京理工大学 | A kind of preparation method of the few layer antimony alkene of monocrystalline |
| CN105460910B (en) * | 2015-11-19 | 2018-02-27 | 浙江大学 | A kind of constant temperature and the extensive method for preparing banding black phosphorus |
| CN105600761B (en) * | 2015-12-25 | 2018-03-09 | 湖北中科墨磷科技有限公司 | A kind of large scale black phosphorus piece and preparation method thereof |
| CN106744754A (en) * | 2016-11-14 | 2017-05-31 | 深圳大学 | A kind of red phosphorus preprocess method prepared for black phosphorus |
| CN107275646B (en) * | 2017-06-16 | 2020-03-10 | 福州大学 | Proton exchange membrane fuel cell catalyst with core-shell structure and preparation method thereof |
| CN108128761B (en) * | 2018-01-30 | 2021-06-18 | 昆明理工大学 | Continuous preparation method of black phosphorus |
| JP7248242B2 (en) * | 2019-06-27 | 2023-03-29 | 堺化学工業株式会社 | Method for producing black phosphorus-containing composition and black phosphorus-containing composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638292A (en) * | 1986-06-27 | 1988-01-14 | Nippon Chem Ind Co Ltd:The | Production of black phosphorus single crystal |
| CN102491294A (en) * | 2011-12-01 | 2012-06-13 | 东北师范大学 | Method for preparing black phosphorus of negative electrode materials of high-capacity lithium-ion battery |
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638292A (en) * | 1986-06-27 | 1988-01-14 | Nippon Chem Ind Co Ltd:The | Production of black phosphorus single crystal |
| CN102491294A (en) * | 2011-12-01 | 2012-06-13 | 东北师范大学 | Method for preparing black phosphorus of negative electrode materials of high-capacity lithium-ion battery |
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
Non-Patent Citations (1)
| Title |
|---|
| High-Quality Black Phosphorus Atomic Layers by Liquid-Phase Exfoliation;Poya Yasaei et al.;《Advanced Materials》;20150202;第27卷;第1887页左栏第2段-右栏第1段、第1890页右栏实验部分 * |
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Effective date of registration: 20161108 Address after: 401321 Chongqing city Banan District Yang Yudong Stone Street No. 89 No. -4 Applicant after: Chongqing Jinsheng Machinery Parts Manufacturing Co.,Ltd. Address before: Tianhe District Tong East Road Guangzhou city Guangdong province 510665 B-101 No. 5, room B-118 Applicant before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20161108 Address after: Tianhe District Tong East Road Guangzhou city Guangdong province 510665 B-101 No. 5, room B-118 Applicant after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: The middle Tianfu Avenue in Chengdu city Sichuan province 610041 No. 1388 1 8 storey building No. 866 Applicant before: CHENGDU YUYA SCIENCE & TECHNOLOGY Co.,Ltd. |
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