CN112830462A - Method for safely and efficiently synthesizing high-purity black phosphorus - Google Patents
Method for safely and efficiently synthesizing high-purity black phosphorus Download PDFInfo
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- CN112830462A CN112830462A CN202110150552.0A CN202110150552A CN112830462A CN 112830462 A CN112830462 A CN 112830462A CN 202110150552 A CN202110150552 A CN 202110150552A CN 112830462 A CN112830462 A CN 112830462A
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Abstract
The invention discloses a method for safely and efficiently synthesizing high-purity black phosphorus, which belongs to the technical field of black phosphorus preparation and comprises the following steps: s1, weighing red phosphorus, tin and iodine in a protective gas atmosphere, and sealing in a reactor; s2, heating the reactor in the S1 to 480-490 ℃, carrying out heat treatment, and then cooling to room temperature to obtain black phosphorus crystals; the pressure in the reactor during the heat treatment is: 70% multiplied by the maximum pressure intensity which can be borne in the reactor to the maximum pressure intensity which can be borne in the reactor; the method for safely and efficiently synthesizing high-purity black phosphorus provided by the invention effectively controls the pressure in the reaction process, effectively reduces the danger of preparing the high-purity black phosphorus, has high production efficiency, and is suitable for large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of black phosphorus preparation, and particularly relates to a safe and efficient method for synthesizing high-purity black phosphorus.
Background
Black phosphorus is the most stable of the three common phosphorus allotropes, and has a graphite-like sheet structure, but the phosphorus atoms in the same layer are not on the same plane, and have a honeycomb-like folded structure. The layer has stronger covalent bond and single electron pair, so each atom is saturated, the atoms between layers are acted by Van der Waals force, the interlayer bonding is weaker than that in the layer, and the conductivity is good.
In recent years, the demand of research institutes and colleges for black phosphorus materials is rapidly increased, so that the large-scale preparation of the two-dimensional black phosphorus material has great market potential. Meanwhile, the two-dimensional black phosphorus is used as an excellent substrate, can load precious metal materials such as platinum, rhodium, gold, silver and the like, develops black phosphorus downstream products such as catalysts with high activity and selectivity and has a great application prospect. However, the price of the black phosphorus material in China is high at present, and the problems of high explosion tendency, high danger degree and low synthesis efficiency exist in high-temperature sintering of high-purity black phosphorus, so the application provides a method for safely and efficiently synthesizing the high-purity black phosphorus.
Disclosure of Invention
In order to solve the problems, the invention provides a method for safely and efficiently synthesizing high-purity black phosphorus, which realizes the breakthrough of 0 explosion by effectively controlling the pressure in the reaction process, has safe reaction process and high efficiency of the synthesized product, and is suitable for large-scale production and application.
The technical scheme of the invention is as follows:
the first purpose of the invention is to provide a safe and efficient method for synthesizing high-purity black phosphorus, which comprises the following steps:
s1, weighing red phosphorus, tin and iodine in a protective gas atmosphere, and sealing in a reactor;
s2, heating the reactor in the S1 to 480-490 ℃, carrying out heat treatment, and then cooling to room temperature to obtain black phosphorus crystals;
the pressure in the reactor during the heat treatment is: 70% x the maximum pressure that can be borne in the reactor to the maximum pressure that can be borne in the reactor.
Preferably, in S1, the molar ratio of red phosphorus, tin and iodine is 10:2: 1.
Preferably, in S1, the reactor is a quartz tube, and the maximum pressure that can be withstood in the quartz tube is 21 MPa.
Preferably, in S2, the temperature of the quartz tube is increased to 480-490 ℃, the temperature is maintained for 5 hours, and the pressure in the quartz tube is 16-20 MPa in the heat preservation process.
Preferably, in S2, the quartz tubes are placed in a muffle furnace for heat treatment, and 20 to 30 quartz tubes are placed simultaneously for each reaction and separated from each other.
Preferably, in S2, the cooled product is ultrasonically washed with acetone and ethanol sequentially for multiple times, and then vacuum-dried.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, red phosphorus, tin and iodine are sealed in a reactor under a protective gas atmosphere, then the temperature is raised to 480-490 ℃ for heat preservation and heat treatment, and the risk of preparing high-purity black phosphorus is effectively reduced by effectively controlling the pressure in the reaction process (controlling the pressure range in the reactor in the heat treatment process to be 70% multiplied by the maximum pressure born in the reactor to be the maximum pressure born in the reactor), so that the production efficiency is high, and the method is suitable for large-scale preparation;
(2) the above-mentioned nearly 0 explosion can be achieved by controlling the pressure, which has not been reported before; the preparation method is efficient (the yield is more than 97 percent); the synthesized black phosphorus crystal has high purity and good crystallinity.
Drawings
FIG. 1 is an X-ray diffraction pattern of the black phosphorus crystal prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention. The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the starting materials and reagents are commercially available unless otherwise specified.
The invention provides a method for safely and efficiently synthesizing high-purity black phosphorus, which comprises the following steps:
s1, weighing red phosphorus, tin and iodine in a protective gas atmosphere, and sealing in a reactor;
s2, heating the reactor in the S1 to 480-490 ℃, carrying out heat treatment, and then cooling to room temperature to obtain black phosphorus crystals;
in the preparation process, the explosion of nearly 0 can be realized by controlling the pressure, and the specific control conditions are as follows:
the pressure in the reactor during the heat treatment is: not higher than the maximum pressure intensity which can be borne in the reactor and not lower than 70 percent of the maximum pressure intensity which can be borne in the reactor, the explosion phenomenon can not occur in the preparation process, and the preparation method is safe and efficient.
Example 1
A method for safely and efficiently synthesizing high-purity black phosphorus comprises the following steps:
(1) weighing 10mmol of red phosphorus in a glove box filled with nitrogen according to a molar ratio of 10:2:1, respectively weighing tin and iodine;
(2) adding the substances weighed in the step (1) into a quartz tube with the diameter of 10 x 1.5 x 100mm (the maximum pressure which can be borne by the quartz tube is 21 MPa);
(3) placing the sealed quartz tubes obtained in the step (2) in a room-temperature muffle furnace for reaction, (20 tubes can be placed at one time, and in order to ensure that the tubes are not influenced mutually, a block is adopted to separate each tube), raising the temperature to 485 ℃, preserving the heat for 5 hours (in the heat preservation process, the pressure in the quartz tube is 16MPa), and cooling to room temperature to obtain a black phosphorus crystal product;
(4) taking out the product reacted in the step (3), washing, adding 20mL of acetone, performing ultrasound for 2min, pouring out the ultrasound solution, and repeating the steps for three times; adding 20mL of absolute ethyl alcohol, performing ultrasonic treatment for 2min, pouring out the ultrasonic solution, and repeating the steps for three times to obtain blocky black phosphorus containing residual absolute ethyl alcohol;
(5) putting the block black phosphorus obtained in the step (4) into a vacuum drying oven for drying for 24 hours to obtain block black phosphorus crystals;
(6) and (4) putting the blocky black phosphorus crystal obtained in the step (5) into a glove box filled with nitrogen, weighing the mass, preparing 100 tubes of black phosphorus crystal by the method, exploding 0, and obtaining the average yield of 75% when the yield is 97%.
Example 2
A method for safely and efficiently synthesizing high-purity black phosphorus comprises the following steps:
(1) weighing 12mmol of red phosphorus in a glove box filled with nitrogen according to a molar ratio of 10:2:1, respectively weighing tin and iodine;
(2) adding the substances weighed in the step (1) into a quartz tube with the diameter of 10 x 1.5 x 100mm (the maximum pressure which can be borne by the quartz tube is 21 MPa);
(3) placing the sealed quartz tubes obtained in the step (2) in a room-temperature muffle furnace for reaction, (30 tubes can be placed at one time, and in order to ensure that the tubes are not influenced mutually, a block is adopted to separate each tube), raising the temperature to 485 ℃, preserving the heat for 5 hours (in the heat preservation process, the pressure in the quartz tube is 20MPa), and cooling to room temperature to obtain a black phosphorus crystal product;
(4) taking out the product reacted in the step (3), washing, adding 20mL of acetone, performing ultrasound for 2min, pouring out the ultrasound solution, and repeating the steps for three times; adding 20mL of absolute ethyl alcohol, performing ultrasonic treatment for 2min, pouring out the ultrasonic solution, and repeating the steps for three times to obtain blocky black phosphorus containing residual absolute ethyl alcohol;
(5) putting the block black phosphorus obtained in the step (4) into a vacuum drying oven for drying for 24 hours to obtain block black phosphorus crystals;
(6) and (3) putting the blocky black phosphorus crystal obtained in the step (5) into a glove box filled with nitrogen, weighing the mass, preparing 100 tubes of black phosphorus crystal by the method, exploding 0, and obtaining the average yield of 77% with the yield of 98%.
The black phosphorus prepared in the above examples 1 and 2 is similar to the black phosphorus prepared in the following examples, and only the structure of the black phosphorus prepared in the example 1 is characterized, as shown in fig. 1, by X-ray diffraction (XRD) of the black phosphorus crystal prepared in the example 1, all diffraction peaks can be marked to (0k0) black phosphorus crystal, and no other impurity peak appears. The strongest peak value in the XRD pattern is (040) peak, the intensity reaches 24640, and the narrow half-height width is 0.1419 degrees, which shows that the prepared black phosphorus crystal has high purity and good crystallinity, the test condition is 40KV voltage, 30mAPD3200, and the angle increment is 0.05 degrees/s. It is noted that the samples were not subjected to any decontamination prior to testing. Therefore, the red phosphorus, tin and iodine are sealed in the reactor under the protective gas atmosphere, then the temperature is raised to 480-490 ℃ for heat preservation and heat treatment, the risk of preparing high-purity black phosphorus is effectively reduced by effectively controlling the pressure in the reaction process, the production efficiency is high, and the method is suitable for large-scale preparation; the above-mentioned nearly 0 explosion can be achieved by controlling the pressure, which has not been reported before; the preparation method is efficient, the preparation yield is more than 97%, and the synthesized black phosphorus crystal has high purity and good crystallinity and is suitable for large-scale production and application of black phosphorus.
While embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic principles and methods. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (6)
1. The method for safely and efficiently synthesizing high-purity black phosphorus is characterized by comprising the following steps of:
s1, weighing red phosphorus, tin and iodine in a protective gas atmosphere, and sealing in a reactor;
s2, heating the reactor in the S1 to 480-490 ℃, carrying out heat treatment, and then cooling to room temperature to obtain black phosphorus crystals;
the pressure in the reactor during the heat treatment is: 70% x the maximum pressure that can be borne in the reactor to the maximum pressure that can be borne in the reactor.
2. The method for safely and efficiently synthesizing high-purity black phosphorus according to claim 1, wherein the molar ratio of the red phosphorus to the tin to the iodine in S1 is 10:2: 1.
3. The method for safely and efficiently synthesizing high-purity black phosphorus according to claim 1, wherein in S1, the reactor is a quartz tube, and the maximum pressure which can be borne in the quartz tube is 21 MPa.
4. The method for safely and efficiently synthesizing high-purity black phosphorus according to claim 3, wherein in S2, the quartz tube is heated to 480-490 ℃ and then is kept warm for 5 hours, and in the process of keeping warm, the pressure in the quartz tube is 16-20 MPa.
5. The method for safely and efficiently synthesizing high-purity black phosphorus according to claim 3, wherein in S2, the quartz tubes are placed in a muffle furnace for heat treatment, 20-30 quartz tubes are placed at the same time for each reaction, and each quartz tube is separated.
6. The method for safely and efficiently synthesizing high-purity black phosphorus according to claim 1, wherein in S2, the cooled product is subjected to ultrasonic cleaning with acetone and ethanol for multiple times in sequence, and then is subjected to vacuum drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113668053A (en) * | 2021-10-25 | 2021-11-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus film reaction device and black phosphorus film preparation method |
| CN115522260A (en) * | 2022-10-31 | 2022-12-27 | 陕西科技大学 | Preparation method of high-stability black phosphorus single crystal |
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| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| CN105460910A (en) * | 2015-11-19 | 2016-04-06 | 浙江大学 | A constant-temperature large-scale preparing method of belt-shaped black phosphorus |
| CN107777675A (en) * | 2017-11-03 | 2018-03-09 | 陕西品达石化有限公司 | A kind of preparation method of two dimensional crystal black phosphorus alkene |
| US20190382268A1 (en) * | 2018-06-15 | 2019-12-19 | Black P2 (USA) INC. | Method for Producing Black Phosphorus |
| CN111285339A (en) * | 2020-03-15 | 2020-06-16 | 湖北中科墨磷科技有限公司 | Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal |
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- 2021-02-03 CN CN202110150552.0A patent/CN112830462A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| CN105460910A (en) * | 2015-11-19 | 2016-04-06 | 浙江大学 | A constant-temperature large-scale preparing method of belt-shaped black phosphorus |
| CN107777675A (en) * | 2017-11-03 | 2018-03-09 | 陕西品达石化有限公司 | A kind of preparation method of two dimensional crystal black phosphorus alkene |
| US20190382268A1 (en) * | 2018-06-15 | 2019-12-19 | Black P2 (USA) INC. | Method for Producing Black Phosphorus |
| CN111285339A (en) * | 2020-03-15 | 2020-06-16 | 湖北中科墨磷科技有限公司 | Sn (tin)3P4Preparation method of induced two-dimensional black phosphorus crystal |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113668053A (en) * | 2021-10-25 | 2021-11-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus film reaction device and black phosphorus film preparation method |
| CN115522260A (en) * | 2022-10-31 | 2022-12-27 | 陕西科技大学 | Preparation method of high-stability black phosphorus single crystal |
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