CN113772642A - Electrochemical preparation method of few-layer black phosphorus nanosheet - Google Patents
Electrochemical preparation method of few-layer black phosphorus nanosheet Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- -1 tetraethylammonium hexafluorophosphate Chemical group 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 239000002055 nanoplate Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims 1
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 26
- 150000001768 cations Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
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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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Abstract
一种少层黑磷纳米片的电化学制备方法，它属于无机纳米材料制备技术领域。它要解决现有制备少层黑磷的方法存在效率较低、可控性差、难以产业化生产的问题。方法：一、制备电解液；二、在电解池中以块状黑磷为阴极，施加循环电压，得电解后的材料；三、超声分散后离心洗涤，收集上清液并真空干燥，获得少层黑磷纳米片。本发明采用极性非质子溶剂体系的电化学阴极插层法可以实现少层黑磷纳米片材料的高效制备、电流电压可控，制备工艺与设备简单，易于工业化生产，适合大规模推广；本发明所得少层黑磷纳米片材料，材料的结构完整、横向尺寸大，具有较高的质量和应用价值。本发明制备的少层黑磷纳米片材料，它作为非金属纳米材料使用。
An electrochemical preparation method of few-layer black phosphorus nanosheets belongs to the technical field of preparation of inorganic nanometer materials. It needs to solve the problems of low efficiency, poor controllability and difficulty in industrialized production in the existing method for preparing few-layer black phosphorus. Methods: 1. Preparation of electrolyte; 2. Using block black phosphorus as cathode in the electrolytic cell, applying cyclic voltage to obtain electrolyzed materials; 3. Centrifuging washing after ultrasonic dispersion, collecting supernatant and vacuum drying to obtain less layer of black phosphorus nanosheets. The invention adopts the electrochemical cathode intercalation method of the polar aprotic solvent system, which can realize the efficient preparation of the few-layer black phosphorus nanosheet material, the current and voltage are controllable, the preparation process and equipment are simple, the industrial production is easy, and the invention is suitable for large-scale promotion; The obtained few-layer black phosphorus nanosheet material has complete structure and large lateral size, and has high quality and application value. The few-layer black phosphorus nanosheet material prepared by the invention is used as a non-metallic nanomaterial.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation; in particular to an electrochemical preparation method of a few-layer black phosphorus nanosheet.
Background
The black phosphorus is a new two-dimensional material and has considerable application prospect in the research fields of devices such as electronics, photoelectricity, thermoelectricity, gas sensitivity and the like. Unlike zero-bandgap semiconductors such as graphene, black phosphorus has a direct bandgap, and the smaller the number of layers, the more its bandgap. Therefore, how to prepare high-quality ultrathin black phosphorus materials becomes a hot point for research.
Researchers have adopted mechanical stripping and ultrasonic liquid phase stripping to obtain thinner black phosphorus nanosheets. However, the sample obtained by the mechanical stripping method has limited size, low preparation efficiency, difficult thickness control and difficult industrial popularization, and is only suitable for basic research in laboratories, while the ultrasonic stripping method can realize large-scale preparation of the black phosphorus nanosheet, but has the defects of long experimental process, low yield, poor controllability and the like, and structural damage caused by long-time ultrasonic action may hinder the application of the prepared sample in electronic equipment. Furthermore, the chemical vapor deposition process for preparing two-dimensional materials such as graphene is limited by the lack of suitable substrates with appropriate interactions and lattice constants for growing black phosphorus. The application of the few-layer black phosphorus in the preparation of photoelectric devices and the like is severely restricted.
Disclosure of Invention
The invention aims to solve the problems of low efficiency, poor controllability and difficulty in industrial production of the existing method for preparing the few-layer black phosphorus, and provides an electrochemical preparation method of the few-layer black phosphorus nanosheet.
An electrochemical preparation method of a few-layer black phosphorus nanosheet is realized according to the following steps:
firstly, dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
secondly, placing the blocky black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the blocky black phosphorus in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the blocky black phosphorus by taking the blocky black phosphorus as a cathode to obtain an electrolyzed material;
and thirdly, carrying out ultrasonic dispersion on the electrolyzed material, then carrying out centrifugal washing, collecting supernatant and carrying out vacuum drying to obtain the few-layer black phosphorus nanosheet, thus completing the preparation method.
The invention adopts an electrochemical method with high preparation efficiency, controllable current and voltage and simple preparation process and equipment to prepare the small-layer black phosphorus nanosheet material with large transverse size and complete structure, and solves the problems of low preparation efficiency, poor controllability and difficult industrial popularization in the prior preparation technology.
The ammonium cations have large diameters and are easy to insert into the black phosphorus material layers with large interlayer spacing, and the polar aprotic solvent is easy to electrolyze to generate gas to drive the ultra-fast expansion and stripping of the black phosphorus and is beneficial to further embedding of the ammonium cations; the electrochemical cathode intercalation method adopting the polar aprotic solvent system can realize the efficient and controllable preparation of the few-layer black phosphorus nanosheet material, and the obtained few-layer black phosphorus nanosheet material has the advantages of complete structure, large transverse size, high quality and high application value.
The few-layer black phosphorus nano sheet material prepared by the invention is used as a non-metal nano material.
Drawings
Fig. 1 is a process diagram of the preparation of few-layer black phosphorus nanoplates in the example;
FIG. 2 is a CV diagram of few-layer black phosphorus nanoplates in the examples;
fig. 3 is an SEM image of few-layer black phosphorus nanoplates in an example;
fig. 4 is a TEM image of few-layer black phosphorus nanoplates in the example.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the electrochemical preparation method of the few-layer black phosphorus nanosheet is realized according to the following steps:
firstly, dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
secondly, placing the blocky black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the blocky black phosphorus in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the blocky black phosphorus by taking the blocky black phosphorus as a cathode to obtain an electrolyzed material;
and thirdly, carrying out ultrasonic dispersion on the electrolyzed material, then carrying out centrifugal washing, collecting supernatant and carrying out vacuum drying to obtain the few-layer black phosphorus nanosheet, thus completing the preparation method.
The second embodiment is as follows: this embodiment is different from the first embodiment in that the ammonium salt in the first step is tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, or tetrabutylammonium tetrafluoroborate. Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: in this embodiment, different from the first or second embodiment, the polar aprotic solvent in the first step is DMSO, DMF, or NMP. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the present embodiment is different from the first to the third embodiments in that the concentration of the electrolyte in the first step is 0.01 to 0.1M. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is that the working distance in the second step is 1-2 cm. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that the cycle voltage in the second step is (1V-4V) (-5V-7V) and the application time is 60-120 min. Other steps and parameters are the same as those in one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and the first to sixth embodiments is that the ultrasonic dispersion time in the third step is 5-10 min. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and the first to seventh embodiments is that the centrifugal washing in the third step is performed 3 to 5 times by using a polar aprotic solvent and absolute ethanol, respectively. Other steps and parameters are the same as those in one of the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that the rotation speed of the centrifugal washing in the third step is 8000-12000 r/min, and the time is 10-30 min. Other steps and parameters are the same as those in one to eight of the embodiments.
The detailed implementation mode is ten: the difference between this embodiment and the first to ninth embodiments is that the temperature of the vacuum drying in the third step is 50-70 ℃ and the time is 8-12 h. Other steps and parameters are the same as those in one of the first to ninth embodiments.
The beneficial effects of the present invention are demonstrated by the following examples:
example (b):
an electrochemical preparation method of a few-layer black phosphorus nanosheet is realized according to the following steps:
firstly, dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
secondly, placing the blocky black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the blocky black phosphorus in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the blocky black phosphorus by taking the blocky black phosphorus as a cathode to obtain an electrolyzed material;
and thirdly, carrying out ultrasonic dispersion on the electrolyzed material, then carrying out centrifugal washing, collecting supernatant and carrying out vacuum drying to obtain the few-layer black phosphorus nanosheet, thus completing the preparation method.
In step one of this example, the ammonium salt is tetrabutylammonium hexafluorophosphate.
In the first step of this embodiment, the polar aprotic solvent is DMSO.
In the first step of this embodiment, the concentration of the electrolyte is 0.05M.
In the second step of this embodiment, the working distance is 2 cm.
In the second step of this embodiment, the cyclic voltage is 1V to-5V, and the application time is 90 min.
The time for ultrasonic dispersion in step three of this example was 5 min.
The centrifugation in step three of this example was performed 3 times with DMSO and absolute ethanol, respectively.
In the third step of this example, the rotation speed of the centrifugal washing is 10000r/min, and the time is 30 min.
The temperature of vacuum drying in step three of this example was 60 ℃ for 12 hours.
In the preparation process of the few-layer black phosphorus nanosheet prepared in the embodiment, as shown in fig. 1, as the energization time increases (in fig. 1, the part a is 0min, the part b is 5min, the part c is 10min, and the part d is 15min), the volume of the blocky black phosphorus expands obviously, black powder falls off, and the color of the solution gradually becomes dark.
The CV diagram of the few-layer black phosphorus nanosheet prepared in this example is shown in FIG. 2, and it can be seen that the peak of the peak at about-0.5V is related to TBA+Clear cathodic peak current associated with cation intercalation, indicating TBA+The cation was successfully inserted into the bulk BP, which appeared from TBA during the reverse scan at around-0.5V+New peaks due to cation deintercalation.
As shown in fig. 3, it can be seen that with the application of voltage, the layered structure of black phosphorus is gradually opened, the gap between layers is gradually expanded into an accordion shape, the expanded gap is favorable for further permeation of cations, and finally the BP nanosheet is stripped off.
In a TEM image of the few-layer black phosphorus nanosheet prepared in this example, as shown in fig. 4, it can be seen that the block black phosphorus is exfoliated into an ultrathin black phosphorus nanosheet with a large transverse dimension and a complete structure.
The black phosphorus nanosheet material is prepared by the method which is high in preparation efficiency (high in macroscopic speed), controllable in current and voltage and simple in preparation process and equipment; the obtained few-layer black phosphorus nanosheet is high in yield, large in transverse size, complete in structure and suitable for industrial popularization.
Claims (10)
1. An electrochemical preparation method of a few-layer black phosphorus nanosheet is characterized by comprising the following steps:
firstly, dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
secondly, placing the blocky black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the blocky black phosphorus in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the blocky black phosphorus by taking the blocky black phosphorus as a cathode to obtain an electrolyzed material;
and thirdly, carrying out ultrasonic dispersion on the electrolyzed material, then carrying out centrifugal washing, collecting supernatant and carrying out vacuum drying to obtain the few-layer black phosphorus nanosheet, thus completing the preparation method.
2. The method of claim 1, wherein in step one, said ammonium salt is tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, or tetrabutylammonium tetrafluoroborate.
3. The electrochemical preparation method of few-layer black phosphorus nanoplate as claimed in claim 1, wherein the polar aprotic solvent in step one is DMSO, DMF or NMP.
4. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the concentration of the electrolyte in step one is 0.01-0.1M.
5. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the working distance in step two is 1-2 cm.
6. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the cycling voltage in step two is (1V-4V) (-5V-7V) and the application time is 60-120 min.
7. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the time for ultrasonic dispersion in step three is 5-10 min.
8. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the centrifugal washing in step three is performed 3-5 times by respectively using a polar aprotic solvent and absolute ethyl alcohol.
9. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the rotation speed of the centrifugal washing in the third step is 8000-12000 r/min, and the time is 10-30 min.
10. The electrochemical preparation method of few-layer black phosphorus nanosheet according to claim 1, wherein the vacuum drying in step three is carried out at a temperature of 50-70 ℃ for 8-12 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650218A (en) * | 2022-11-16 | 2023-01-31 | 西安交通大学 | Normal-temperature molten salt with wide potential window, and preparation method and application thereof |
| CN118878279A (en) * | 2024-07-10 | 2024-11-01 | 中煤科工开采研究院有限公司 | Phosphorene toughened grouting material suitable for large deformation tunnels in coal mines and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876199A (en) * | 2015-04-21 | 2015-09-02 | 合肥国轩高科动力能源股份公司 | Method for preparing few-layer black scales by ultrasonically stripping black scale |
| US20160126323A1 (en) * | 2014-10-10 | 2016-05-05 | Korea Basic Science Institute | Method of preparing monoatomic layer black phosphorous by irradiating ultrasound |
| CN109019540A (en) * | 2018-08-17 | 2018-12-18 | 深圳市中科墨磷科技有限公司 | A method of preparing black phosphorus nanometer sheet |
| CN109549954A (en) * | 2018-12-13 | 2019-04-02 | 中国科学院深圳先进技术研究院 | A kind of phosphorous-based materials preparation and its preparation method and application |
| KR20190042291A (en) * | 2017-10-16 | 2019-04-24 | 성균관대학교산학협력단 | Black phosphorus and graphene composite and method of manufacturing the composite |
| CN110817816A (en) * | 2019-11-25 | 2020-02-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area thin-layer high-quality black phosphorus nanosheets and preparation method thereof by electrochemical exfoliation |
| CN112279228A (en) * | 2019-07-23 | 2021-01-29 | 西北工业大学 | Black phosphorus nanosheet and preparation method and application thereof |
| CN113235107A (en) * | 2021-04-29 | 2021-08-10 | 西安交通大学苏州研究院 | Oxygen evolution reaction electrocatalyst and preparation method thereof |
-
2021
- 2021-09-24 CN CN202111121334.0A patent/CN113772642B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160126323A1 (en) * | 2014-10-10 | 2016-05-05 | Korea Basic Science Institute | Method of preparing monoatomic layer black phosphorous by irradiating ultrasound |
| CN104876199A (en) * | 2015-04-21 | 2015-09-02 | 合肥国轩高科动力能源股份公司 | Method for preparing few-layer black scales by ultrasonically stripping black scale |
| KR20190042291A (en) * | 2017-10-16 | 2019-04-24 | 성균관대학교산학협력단 | Black phosphorus and graphene composite and method of manufacturing the composite |
| CN109019540A (en) * | 2018-08-17 | 2018-12-18 | 深圳市中科墨磷科技有限公司 | A method of preparing black phosphorus nanometer sheet |
| CN109549954A (en) * | 2018-12-13 | 2019-04-02 | 中国科学院深圳先进技术研究院 | A kind of phosphorous-based materials preparation and its preparation method and application |
| CN112279228A (en) * | 2019-07-23 | 2021-01-29 | 西北工业大学 | Black phosphorus nanosheet and preparation method and application thereof |
| CN110817816A (en) * | 2019-11-25 | 2020-02-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area thin-layer high-quality black phosphorus nanosheets and preparation method thereof by electrochemical exfoliation |
| CN113235107A (en) * | 2021-04-29 | 2021-08-10 | 西安交通大学苏州研究院 | Oxygen evolution reaction electrocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李子炯等著, 中国原子能出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650218A (en) * | 2022-11-16 | 2023-01-31 | 西安交通大学 | Normal-temperature molten salt with wide potential window, and preparation method and application thereof |
| CN115650218B (en) * | 2022-11-16 | 2024-05-24 | 西安交通大学 | A room-temperature molten salt with a wide potential window and its preparation method and application |
| CN118878279A (en) * | 2024-07-10 | 2024-11-01 | 中煤科工开采研究院有限公司 | Phosphorene toughened grouting material suitable for large deformation tunnels in coal mines and preparation method thereof |
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