CN108128761B - Continuous preparation method of black phosphorus - Google Patents
Continuous preparation method of black phosphorus Download PDFInfo
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- CN108128761B CN108128761B CN201810086648.3A CN201810086648A CN108128761B CN 108128761 B CN108128761 B CN 108128761B CN 201810086648 A CN201810086648 A CN 201810086648A CN 108128761 B CN108128761 B CN 108128761B
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
Abstract
The invention discloses a continuous preparation method of black phosphorus, belonging to the technical field of phosphorus chemical industry. The method comprises the following steps: and introducing gaseous phosphorus and a mineralizer into a microreactor, wherein the temperature in the microreactor is 550-750 ℃, reactants are fully mixed and react in the microreactor, and then further introducing the obtained gaseous product into a black phosphorus grower, wherein the temperature in the black phosphorus grower is 200-500 ℃, the black phosphorus grows in the black phosphorus grower, and meanwhile, the mineralizer is separated from the black phosphorus in a gaseous form and is mixed with the initial mineralizer for continuous utilization. The device not only can prepare high-purity black phosphorus, but also can realize continuous preparation of the black phosphorus, has low cost, is simple and easy to operate, can be linked with the existing industrial production equipment of yellow phosphorus and red phosphorus, and is beneficial to reducing the production cost.
Description
Technical Field
The invention relates to a continuous preparation method of black phosphorus, belonging to the technical field of phosphorus chemical industry.
Background
The black phosphorus is one of the most stable properties of phosphorus allotropes, and a great deal of theoretical and experimental researches show that the black phosphorus has excellent performances, such as higher carrier mobility and on-off ratio, adjustable layer number of direct band gaps, high anisotropy, excellent biocompatibility and the like, and shows great potential application values in the fields of solar cells, energy storage cells, biomedicine, field effect transistors, sensors, catalysis and the like.
However, the research on black phosphorus is just started at present, and many aspects are yet to be further researched, and especially, the development of a method for efficiently preparing black phosphorus is extremely important for promoting the development of the application field of black phosphorus. The high pressure method is the earliest method for preparing black phosphorus, and CN102491294A discloses a method for preparing black phosphorus of a lithium ion battery cathode material by a high pressure method. The methods proposed by CN104630879A, CN106087050 and CN105460910A have the advantages of good crystallinity of the prepared black phosphorus, low cost and the like, but the black phosphorus obtained by the methods needs to be further removed of impurities, and the methods are complex in process and high in cost, and are not beneficial to large-scale production. CN106185849A discloses a method for preparing nano-scale black phosphorus, which comprises adding red phosphorus into a high-energy ball mill, and ball milling for several hours to obtain black phosphorus. Moreover, the methods can only intermittently prepare the black phosphorus, and the industrial continuous production is difficult to carry out, so that the development of a method capable of continuously preparing the high-purity black phosphorus has great significance for promoting the application of the black phosphorus.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a continuous black phosphorus preparation method, which can not only prepare high-purity black phosphorus, but also realize continuous black phosphorus preparation, has low cost and simple and easy operation, can be linked with the existing industrial yellow phosphorus and red phosphorus production equipment, and realizes the full utilization of the equipment.
The purpose of the invention is realized by the following technical scheme: a continuous preparation method of black phosphorus specifically comprises the following steps: gaseous phosphorus and a mineralizer are fed into the microreactor, reactants are fully mixed and react in the microreactor, the obtained gaseous product is fed into the black phosphorus grower, the temperature in the black phosphorus grower is controlled by a heater, the black phosphorus can grow in the black phosphorus grower, the mineralizer is separated from the black phosphorus in a gaseous form, and the gaseous mineralizer and the initial mineralizer are mixed through a gas guide pipe and are continuously utilized.
The gaseous phosphorus is gaseous yellow phosphorus (white phosphorus) or gaseous red phosphorus (red phosphorus).
The mineralizer is a mixture of metal and iodide (mixed according to any proportion) or a mixture of metal and iodine simple substance (mixed according to any proportion); the metal is one of Sn, Bi, In, Pb and Cd or an alloy containing one or more of Sn, Bi, In, Pb and Cd, and the iodide is SnI4、SnI2、PbI2、NH4I、BiI3、PI3One or more of them.
Preferably, the temperature in the microreactor is 550-700 ℃.
Preferably, the temperature in the black phosphorus grower is 200-500 ℃.
The heater of the invention comprises a tube furnace, a muffle furnace and the like, and all heaters which can meet the requirements of the device can be used for the invention.
The invention has the beneficial effects that:
(1) the invention can prepare high-purity black phosphorus with high purity and good crystallinity.
(2) The preparation method is simple, mild in condition, easy to control and low in cost.
(3) The device not only can realize the continuous preparation of the black phosphorus, but also can be linked with the production equipment of yellow phosphorus and red phosphorus in the current industry, thereby realizing the full utilization of the equipment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a schematic representation of a black phosphorus prepared in example 1.
Fig. 3 is an XRD pattern of black phosphorus prepared in example 1.
Figure 4 is an XRD pattern of black phosphorus prepared in example 2.
Figure 5 is an XRD pattern of black phosphorus prepared in example 3.
Fig. 6 is an XRD pattern of black phosphorus prepared in example 4.
Figure 7 is an XRD pattern of black phosphorus prepared in example 5.
Figure 8 is an XRD pattern of black phosphorus prepared in example 6.
Figure 9 is the XRD pattern of black phosphorus prepared in example 7.
Detailed Description
Example 1
Mixing gaseous yellow phosphorus with mineralizer (Sn and SnI)4Mixing according to the mass ratio of 1: 1), slowly feeding into a microreactor, wherein the temperature in the microreactor is 550 ℃, fully mixing and reacting in the microreactor, further feeding the obtained gaseous product into a black phosphorus grower, wherein the temperature in the black phosphorus grower is 200 ℃, black phosphorus grows in the black phosphorus grower, meanwhile, a mineralizer is separated from black phosphorus in a gaseous form and is mixed with an initial mineralizer for continuous use, and after reacting for a period of time, opening the black phosphorus grower to obtain high-purity black phosphorus with the purity of more than 99.9%, wherein the obtained black phosphorus material object diagram and XRD diagram are shown in fig. 2 and fig. 3, and as can be seen from fig. 3, four obvious characteristic peaks of the black phosphorus are respectively at 17.03 °, 26.61 °, 34.32 ° and 52.42 ° and respectively correspond to four crystal faces of the black phosphorus: (020) (021), (040), (060),the result shows that the obtained black phosphorus is orthorhombic and has good crystallinity.
Example 2
Mixing gaseous yellow phosphorus with mineralizer (Bi, PbI)2 、BiI3Mixing according to the mass ratio of 1:1: 2) and slowly feeding into a microreactor, wherein the temperature in the microreactor is 570 ℃, the microreactor is fully mixed and reacted in the microreactor, the obtained gaseous product is further fed into a black phosphorus grower, the temperature in the black phosphorus grower is 250 ℃, black phosphorus grows in the black phosphorus grower, meanwhile, a mineralizer is separated from the black phosphorus in a gaseous form and is mixed with an initial mineralizer for continuous utilization, and after reacting for a period of time, the black phosphorus grower is opened, so that high-purity black phosphorus can be obtained, and the purity is more than 99.9%. The XRD pattern of the black phosphorus prepared in this example is shown in fig. 4, and it can be seen from the pattern that four distinct characteristic peaks of the black phosphorus are respectively at 17.05 °, 26.40 °, 34.23 °, and 52.37 °, which respectively correspond to four crystal planes of the black phosphorus: (020) and (021), (040) and (060) show that the orthorhombic black phosphorus is obtained and the crystallinity is good.
Example 3
Mixing gaseous yellow phosphorus with mineralizer (In and NH)4I is mixed according to the mass ratio of 3: 1) and slowly fed into a microreactor, the temperature in the microreactor is 600 ℃, the microreactor is fully mixed and reacted in the microreactor, the obtained gaseous product is further fed into a black phosphorus grower, the temperature in the black phosphorus grower is 300 ℃, black phosphorus grows in the black phosphorus grower, meanwhile, a mineralizer is separated from the black phosphorus in a gaseous form and is mixed with an initial mineralizer for continuous utilization, and after reaction for a period of time, the black phosphorus grower is opened, so that high-purity black phosphorus can be obtained, wherein the purity is more than 99.9%. The XRD spectrum of the black phosphorus prepared in this example is shown in fig. 5, and it can be seen from the graph that four distinct characteristic peaks of the black phosphorus are respectively at 17.22 °, 26.53 °, 34.62 °, and 52.41 °, which respectively correspond to four crystal planes of the black phosphorus: (020) and (021), (040) and (060) show that the orthorhombic black phosphorus is obtained and the crystallinity is good.
Example 4
Mixing gaseous yellow phosphorus with mineralizer (Pb and BiI)3Mixing according to the mass ratio of 2: 1) slowlyAnd (2) feeding the mixture into a microreactor, wherein the temperature in the microreactor is 650 ℃, the mixture is fully mixed and reacted in the microreactor, the obtained gaseous product is further fed into a black phosphorus grower, the temperature in the black phosphorus grower is 400 ℃, the black phosphorus grows in the black phosphorus grower, meanwhile, a mineralizer is separated from the black phosphorus in a gaseous form and is mixed with an initial mineralizer for continuous utilization, and after the mixture is reacted for a period of time, the black phosphorus grower is opened, so that the high-purity black phosphorus with the purity of more than 99.9 percent can be obtained. The XRD spectrum of the black phosphorus prepared in this example is shown in fig. 6, and it can be seen from the graph that four distinct characteristic peaks of the black phosphorus are respectively at 17.29 °, 26.27 °, 34.46 °, and 52.45 °, and respectively correspond to four crystal planes of the black phosphorus: (020) and (021), (040) and (060) show that the orthorhombic black phosphorus is obtained and the crystallinity is good.
Example 5
Mixing gaseous yellow phosphorus with mineralizer (Cd and PI)3Mixing according to the mass ratio of 4: 1), slowly feeding into a microreactor, wherein the temperature in the microreactor is 700 ℃, fully mixing and reacting in the microreactor, further feeding the obtained gaseous product into a black phosphorus grower, wherein the temperature in the black phosphorus grower is 500 ℃, the black phosphorus grows in the black phosphorus grower, meanwhile, a mineralizer is separated from the black phosphorus in a gaseous form and is mixed with an initial mineralizer for continuous utilization, and after reacting for a period of time, opening the black phosphorus grower to obtain the high-purity black phosphorus, wherein the purity is more than 99.9%. The XRD pattern of the black phosphorus prepared in this example is shown in fig. 7, and it can be seen from the pattern that four distinct characteristic peaks of the black phosphorus are respectively at 17.45 °, 26.63 °, 34.47 °, and 52.70 °, which respectively correspond to four crystal planes of the black phosphorus: (020) and (021), (040) and (060) show that the orthorhombic black phosphorus is obtained and the crystallinity is good.
Example 6
Mixing gaseous yellow phosphorus with mineralizer (Sn and I)2Mixed according to the mass ratio of 1: 1) is slowly fed into a microreactor, the temperature in the microreactor is 650 ℃, the microreactor is fully mixed and reacted in the microreactor, the obtained gaseous product is further fed into a black phosphorus grower, the temperature in the black phosphorus grower is 500 ℃, black phosphorus grows in the black phosphorus grower, and meanwhile, the black phosphorus grows in the black phosphorus growerThe mineralizer is separated from the black phosphorus in a gaseous form and is mixed with the initial mineralizer for continuous utilization, and after the reaction is carried out for a period of time, the black phosphorus grower is opened, so that the high-purity black phosphorus can be obtained, wherein the purity is more than 99.9%. The XRD pattern of the black phosphorus prepared in this example is shown in fig. 8, and it can be seen from the pattern that four distinct characteristic peaks of the black phosphorus are respectively at 17.25 °, 26.73 °, 34.97 °, and 52.40 °, which respectively correspond to four crystal planes of the black phosphorus: (020) and (021), (040) and (060) show that the orthorhombic black phosphorus is obtained and the crystallinity is good.
Example 7
Mixing gaseous yellow phosphorus with mineralizer (Fe-Sn alloy and SnI)4Mixing according to the mass ratio of 2: 1), slowly feeding into a microreactor, wherein the temperature in the microreactor is 670 ℃, fully mixing and reacting in the microreactor, further feeding the obtained gaseous product into a black phosphorus grower, wherein the temperature in the black phosphorus grower is 520 ℃, the black phosphorus grows in the black phosphorus grower, meanwhile, a mineralizer is separated from the black phosphorus in a gaseous form and is mixed with an initial mineralizer for continuous utilization, and after reacting for a period of time, opening the black phosphorus grower to obtain the high-purity black phosphorus, wherein the purity is more than 99.9%. The XRD spectrum of the black phosphorus prepared in this example is shown in fig. 9, and it can be seen from the graph that four distinct characteristic peaks of the black phosphorus are respectively at 17.37 °, 26.42 °, 34.50 °, and 52.60 °, which respectively correspond to four crystal planes of the black phosphorus: (020) and (021), (040) and (060) show that the orthorhombic black phosphorus is obtained and the crystallinity is good.
Claims (3)
1. A continuous preparation method of black phosphorus is characterized by comprising the following steps: introducing gaseous phosphorus and a mineralizer into a microreactor, introducing an obtained gaseous product into a black phosphorus grower after reactants are fully mixed and react in the microreactor, controlling the temperature in the black phosphorus grower through a heater, enabling the black phosphorus to grow in the black phosphorus grower, simultaneously separating the mineralizer from the black phosphorus in a gaseous form, and mixing the gaseous mineralizer with an initial mineralizer through a gas guide pipe for continuous utilization;
the gaseous phosphorus is gaseous yellow phosphorus or gaseous red phosphorus;
the mineralizer is a mixture of metal and iodide or a mixture of metal and iodine elementary substance; the metal is one of Sn, Bi, In, Pb and Cd or an alloy containing one or more of Sn, Bi, In, Pb and Cd, and the iodide is SnI4、SnI2、PbI2、NH4I、BiI3、PI3One or more of them.
2. The continuous production method of black phosphorus according to claim 1, wherein: the temperature in the microreactor is 550-700 ℃.
3. The continuous production method of black phosphorus according to claim 1, wherein: the temperature in the black phosphorus grower is 200-500 ℃.
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| CN108910846B (en) * | 2018-06-26 | 2020-10-27 | 贵州微化科技有限公司 | Method for preparing low-arsenic yellow phosphorus by using microchannel reactor |
| CN109650359B (en) * | 2018-12-29 | 2020-07-03 | 广西越洋科技股份有限公司 | Industrial continuous production equipment and method for black phosphorus |
| CN110331442A (en) * | 2019-08-07 | 2019-10-15 | 深圳市中科墨磷科技有限公司 | A kind of additional thermal field device of aided two-dimensional black phosphorus crystal growth and its application |
| 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 |
| 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) |
| CN111334780A (en) * | 2020-03-02 | 2020-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus film, preparation method and application thereof |
| CN112095146B (en) * | 2020-07-24 | 2022-03-22 | 深圳市中科墨磷科技有限公司 | Reactor for black phosphorus crystal amplification preparation and application thereof |
| CN113174634B (en) * | 2021-04-27 | 2022-05-31 | 陕西科技大学 | Crystal red phosphorus nanowire and preparation method thereof |
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| KR100788487B1 (en) * | 2006-08-08 | 2007-12-24 | 재단법인서울대학교산학협력재단 | Method for preparing black phosphorus and black phosphorus-carbon composites, the prepared black phosphorus and black phosphorus-carbon composites and lithium rechargeable battery comprising the same and method for using the rechargeable battery |
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| 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 |
| 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 |
| CN105565289B (en) * | 2016-01-29 | 2020-05-08 | 西北大学 | Preparation method of black phosphorus and phospholene |
| CN106087050A (en) * | 2016-05-30 | 2016-11-09 | 南京工业大学 | A kind of method preparing rhombic system black phosphorus monocrystalline under low pressure |
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