CN112645295A - Black phosphorus nanobelt material and preparation method thereof - Google Patents
Black phosphorus nanobelt material and preparation method thereof Download PDFInfo
- Publication number
- CN112645295A CN112645295A CN202110009539.3A CN202110009539A CN112645295A CN 112645295 A CN112645295 A CN 112645295A CN 202110009539 A CN202110009539 A CN 202110009539A CN 112645295 A CN112645295 A CN 112645295A
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- phosphorus
- needle
- cooling
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B25/003—Phosphorus
Abstract
The invention discloses a black phosphorus nanobelt material and a preparation method thereof, belonging to the technical field of black phosphorus preparation and comprising the following steps of: s1, taking red phosphorus, iodine and tin as raw materials, carrying out heat treatment by temperature programming to 612-628 ℃ under a sealed condition, and then cooling to room temperature in sections to prepare needle-shaped black phosphorus; s2, preparing the needle-shaped black phosphorus prepared by the S1 into a black phosphorus nanobelt material by a mechanical or liquid phase stripping method; the method takes red phosphorus, iodine and tin as raw materials, prepares needle-shaped black phosphorus after high-temperature treatment, and then prepares the black phosphorus nanobelt material by stripping.
Description
Technical Field
The invention belongs to the technical field of black phosphorus preparation, and particularly relates to a black phosphorus nanobelt material and a preparation method thereof.
Background
Black phosphorus is the most stable form of the three common phosphorus allotropes. The black phosphorus layers are acted by Van der Waals force, and the bonding between the layers is weaker than that in the layers, so that the phospholene nano structure can be synthesized by a mechanical or liquid phase stripping method. The anisotropic nature and semiconducting properties of phospholene nanoplatelets are an attractive topic, including nanoribbons fashioned from their two-dimensional structure. Theoretical studies have confirmed that the bandgap size and the effective mass of the carriers are very sensitive to the bandwidth and crystal orientation due to the strong anisotropy of the phospholene nanoribbons. The nanobelt material is also the basis for the development of one-dimensional nanoelectronics. However, the current technology, even the preparation of two-dimensional nanostructured phospholene, is a huge challenge, let alone the modeling of its two-dimensional structure into nanoribbons, and therefore it is necessary to study the preparation of black phosphorus nanoribbons.
Disclosure of Invention
Based on the reasons, the invention provides the black phosphorus nanobelt material and the preparation method thereof, red phosphorus, iodine and tin are used as raw materials, needle-shaped black phosphorus is prepared after high-temperature heat treatment, and then the black phosphorus nanobelt material is prepared by stripping.
The method can be realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of a black phosphorus nanobelt material, which comprises the following steps:
s1, taking red phosphorus, iodine and tin as raw materials, carrying out heat treatment by temperature programming to 612-628 ℃ under a sealed condition, and then cooling to room temperature in sections to prepare needle-shaped black phosphorus;
s2, preparing the needle-shaped black phosphorus prepared by the S1 into the black phosphorus nanobelt material by a mechanical or liquid phase stripping method.
Preferably, in S1, the mass ratio of red phosphorus, iodine and tin is 10:0.8-2: 0.8-2.
Preferably, in S1, the temperature programming refers to raising the temperature to 612-.
Preferably, in S1, the step cooling is to cool the temperature to 480-488 ℃ at a cooling rate of 0.25-0.32 ℃/min, preserve the temperature for 112-128min, cool the temperature to 108-126 ℃ at a cooling rate of 0.8-1.3 ℃/min, and finally cool the temperature to room temperature naturally.
Preferably, in S1, after cooling to room temperature, the product is washed with acetone and absolute ethanol for several times, and dried to obtain needle-shaped black phosphorus.
Preferably, in S1, red phosphorus, iodine and tin are weighed in a nitrogen atmosphere, mixed and sealed in a quartz tube.
The second purpose of the invention is to provide the black phosphorus nanobelt material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method takes red phosphorus, iodine and tin as raw materials, the raw materials are sealed in a quartz tube in proportion, heat treatment is carried out, when the temperature is raised to 612-; in the proportion range of P, Sn and I and in the heat treatment, growth sites formed by P-Sn-I are small, so that the growth of black phosphorus is mainly concentrated on the small nucleation sites in one area; the needle-shaped structure is formed from inside to outside, and the width of the needle-shaped structure is increased from the size of a central nanometer to a plurality of millimeters at the periphery; therefore, the formation of the acicular black phosphorus with different sizes is promoted by increasing the nucleation sites from inside to outside, and then the black phosphorus nanobelt can be prepared by mechanical or liquid phase stripping;
(2) the preparation method of the black phosphorus nanobelt material provided by the invention is simple and safe to operate, has high product quality, fills the blank of the existing nanobelt material preparation method, and lays a foundation for researching one-dimensional nanomaterials.
Drawings
FIG. 1 is an optical picture of acicular black phosphorus prepared in example 1;
FIG. 2 is a scanning electron microscope picture of the black phosphorus nanobelt material prepared in example 2;
FIG. 3 is a transmission electron microscope photograph of the black phosphorus nanobelt material prepared in example 1;
FIG. 4 is an XRD pattern of the material prepared in example 1;
FIG. 5 is a schematic diagram of a quartz tube structure;
FIG. 6 is an optical picture of the product of comparative example 1;
fig. 7 is an optical picture of the product of comparative example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and practical for those skilled in the art, the present invention will be described in detail below with reference to the accompanying drawings and the detailed description, but the present invention is not limited to the following examples.
The following raw materials and reagents are commercially available unless otherwise specified; the detection methods are conventional methods unless otherwise specified.
The mechanical or liquid phase stripping methods described below can be applied by conventional methods known in the art.
Example 1
A preparation method of a black phosphorus nanobelt material comprises the following steps:
(1) weighing red phosphorus, iodine and tin in a glove box filled with nitrogen according to the mass ratio of 5:1: 1;
(2) adding the substances weighed in the step (1) into a quartz tube with the diameter of 10 x 1.5 x 180 mm;
(3) sealing the quartz tube filled with the substances in the step (2) at a position 80mm away from the opening, wherein one end of the quartz tube is a round bottom, the other end of the quartz tube is provided with an opening, a closing-up is arranged 80mm below the opening, and a 6 x 10mm quartz column is placed at the sealing position for safe sealing; the quartz tube structure is shown in FIG. 5;
(4) placing the sealed quartz tube obtained in the step (3) in a room temperature muffle furnace for reaction, raising the temperature to 612 ℃ at a heating rate of 2.6 ℃/min, preserving the temperature for 285min, lowering the temperature to 480 ℃ at a cooling rate of 0.25 ℃/min, preserving the temperature for 112min, lowering the temperature to 108 ℃ at a cooling rate of 0.8 ℃/min, and naturally cooling to room temperature to obtain a mineralizer-containing needle-shaped black phosphorus crystal;
(5) taking out the reaction product obtained in the step (4), 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 needle-shaped black phosphorus containing residual absolute ethyl alcohol;
(6) drying the needle-shaped black phosphorus obtained in the step (5) in a vacuum drying oven for 24 hours to obtain needle-shaped black phosphorus crystals;
(7) and (4) carrying out liquid phase stripping on the needle-shaped black phosphorus crystal obtained in the step (6) to obtain the black phosphorus nanobelt.
Example 2
A preparation method of a black phosphorus nanobelt material comprises the following steps:
(1) weighing red phosphorus, iodine and tin in a glove box filled with nitrogen according to the mass ratio of 10:0.8: 0.8;
(2) adding the substances weighed in the step (1) into a quartz tube with the diameter of 10 x 1.5 x 180 mm;
(3) sealing the quartz tube filled with the substances in the step (2) at a position 80mm away from the opening, wherein one end of the quartz tube is a round bottom, the other end of the quartz tube is provided with an opening, a closing-up is arranged 80mm below the opening, and a 6 x 10mm quartz column is placed at the sealing position for safe sealing; the quartz tube structure is shown in FIG. 5;
(4) placing the sealed quartz tube obtained in the step (3) in a room temperature muffle furnace for reaction, raising the temperature to 628 ℃ at a heating rate of 3 ℃/min, preserving the heat for 308min, lowering the temperature to 488 ℃ at a cooling rate of 0.32 ℃/min, preserving the heat for 128min, lowering the temperature to 126 ℃ at a cooling rate of 1.3 ℃/min, and naturally cooling to room temperature to obtain a needle-shaped black phosphorus crystal containing a mineralizer;
(5) taking out the product reacted in the step (4), 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 needle-shaped black phosphorus containing residual absolute ethyl alcohol;
(6) drying the needle-shaped black phosphorus obtained in the step (5) in a vacuum drying oven for 24 hours to obtain needle-shaped black phosphorus crystals;
(7) and (4) placing the needle-shaped black phosphorus crystal obtained in the step (6) into a glove box filled with nitrogen for mechanical stripping to obtain the black phosphorus nanobelt.
Comparative example 1
The steps are the same as those of the embodiment 1, except that the mass ratio of red phosphorus to iodine to tin is 10:0.5:0.5, when the content of iodine and tin is low, growth sites are difficult to form, so that the red phosphorus is attached to the tube wall after the reaction is finished and black phosphorus cannot be formed; as shown in fig. 6.
Comparative example 2
The method is the same as the embodiment 1, except that the mass ratio of red phosphorus to iodine to tin is 10:3:3, and when the content of iodine and tin is higher, the formed growth sites are larger and distributed in a larger area, so that the formed black phosphorus is arranged in a stacked manner; as shown in fig. 7.
The materials prepared in example 1 and example 2 were characterized as follows.
Fig. 1 is an optical picture of the needle-shaped black phosphorus prepared in example 1, and it can be seen from fig. 1 that the obtained black phosphorus nanocrystals are in a needle-shaped divergent form, and the surface of the material has a brilliant luminescence, so that it can be judged that the obtained needle-shaped black phosphorus crystals have high quality. FIG. 2 is a scanning electron microscope photograph of the black phosphorus nanobelt material prepared in example 2, which can be obtained from FIG. 2, and the prepared black phosphorus nanobelt material has a linear layered structure; FIG. 3 is a TEM image of the black phosphorus nanobelt material prepared in example 1, which can be obtained from FIG. 3, and the prepared black phosphorus nanobelt material has a shape of nanobelt and is grown in a highly directional manner as observed under a TEM; FIG. 4 is the XRD pattern of the material from example 1, as can be obtained from FIG. 4, the XRD pattern of the resulting crystalline material is consistent with the peaks of standard black phosphorus PDF card, both at (0X0), indicating that BP is grown in a highly directional manner.
In summary, the invention uses red phosphorus, iodine and tin as raw materials, the raw materials are sealed in a quartz tube in proportion, heat treatment is carried out, when the temperature is raised to 612-628 ℃, the red phosphorus, the tin and the iodine in the tube are sublimated into gas, in the process of slow temperature reduction, the formed P-Sn-I compound is firstly attached to the tube wall to form a growth site, and the gaseous phosphorus is divergently grown along the growth site in a bundle shape in the subsequent temperature reduction process; in the proportion range of P, Sn and I and in the heat treatment, growth sites formed by P-Sn-I are small, so that the growth of black phosphorus is mainly concentrated on the small nucleation sites in one area; the needle-shaped structure is formed from inside to outside, and the width of the needle-shaped structure is increased from the size of a central nanometer to a plurality of millimeters at the periphery; therefore, the formation of the acicular black phosphorus with different sizes is promoted by increasing the nucleation sites from inside to outside, and then the black phosphorus nanobelt can be prepared by mechanical or liquid phase stripping; the preparation method of the black phosphorus nanobelt material provided by the invention is simple and safe to operate, has high product quality, fills the blank of the existing nanobelt material preparation method, and lays a foundation for researching one-dimensional nanomaterials.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any value between the two ends can be selected, and since the steps and methods used are the same as those of the embodiments, the preferred embodiments and effects thereof are described in the present invention for the sake of avoiding redundancy, but once the basic inventive concept is known, those skilled in the art may make other changes and modifications to the embodiments. 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 should be noted that various improvements and modifications can be made by those skilled in the art without departing from the principle and spirit of the invention, and these improvements and modifications are also within the scope of the invention.
Claims (7)
1. The preparation method of the black phosphorus nanobelt material is characterized by comprising the following steps of:
s1, taking red phosphorus, iodine and tin as raw materials, carrying out heat treatment by temperature programming to 612-628 ℃ under a sealed condition, and then cooling to room temperature in sections to prepare needle-shaped black phosphorus;
s2, preparing the needle-shaped black phosphorus prepared by the S1 into the black phosphorus nanobelt material by a mechanical or liquid phase stripping method.
2. The method for preparing a black phosphorus nanobelt material according to claim 1, wherein in S1, the mass ratio of red phosphorus, iodine and tin is 10:0.8-2: 0.8-2.
3. The method as claimed in claim 1, wherein in S1, the temperature programming is performed by raising the temperature to 612-.
4. The method as claimed in claim 1, wherein in S1, the step cooling is performed by cooling to 480-488 ℃ at a cooling rate of 0.25-0.32 ℃/min, maintaining the temperature for 112-128min, cooling to 108-126 ℃ at a cooling rate of 0.8-1.3 ℃/min, and naturally cooling to room temperature.
5. The method for preparing the black phosphorus nanobelt material according to claim 1, wherein in S1, after cooling to room temperature, the product is sequentially washed with acetone and absolute ethyl alcohol for a plurality of times and dried to obtain the needle-shaped black phosphorus.
6. The method of claim 1, wherein in step S1, red phosphorus, iodine and tin are weighed in a nitrogen atmosphere, mixed and sealed in a quartz tube.
7. The black phosphorus nanobelt material prepared by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110009539.3A CN112645295A (en) | 2021-01-05 | 2021-01-05 | Black phosphorus nanobelt material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110009539.3A CN112645295A (en) | 2021-01-05 | 2021-01-05 | Black phosphorus nanobelt material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112645295A true CN112645295A (en) | 2021-04-13 |
Family
ID=75367395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110009539.3A Pending CN112645295A (en) | 2021-01-05 | 2021-01-05 | Black phosphorus nanobelt material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112645295A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113479857A (en) * | 2021-08-03 | 2021-10-08 | 陕西科技大学 | Crystal red phosphorus II type nanobelt material and preparation method thereof |
| CN115010103A (en) * | 2022-04-20 | 2022-09-06 | 贵州民族大学 | Preparation method of purple phosphorus nanobelt material |
| CN115124008A (en) * | 2022-06-29 | 2022-09-30 | 西安热工研究院有限公司 | Purple phosphorus nano long belt and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460910A (en) * | 2015-11-19 | 2016-04-06 | 浙江大学 | A constant-temperature large-scale preparing method of belt-shaped black phosphorus |
| CN107055497A (en) * | 2017-03-20 | 2017-08-18 | 中国科学技术大学先进技术研究院 | A kind of two-dimentional black phosphorus material and preparation method thereof |
| CN110205674A (en) * | 2019-06-16 | 2019-09-06 | 深圳市中科墨磷科技有限公司 | A method of two-dimentional black phosphorus crystal is prepared by raw material of white phosphorus |
| CN111170291A (en) * | 2020-01-21 | 2020-05-19 | 上海交通大学 | Method for quickly preparing black phosphorus at low cost |
| CN111254494A (en) * | 2020-03-27 | 2020-06-09 | 李旻鸶 | Preparation method for realizing cheap black phosphorus single crystal by using low-purity red phosphorus |
| US10676357B1 (en) * | 2019-03-22 | 2020-06-09 | The Florida International University Board Of Trustees | Bipolar exfoliation of black phosphorous into phosphorene |
-
2021
- 2021-01-05 CN CN202110009539.3A patent/CN112645295A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460910A (en) * | 2015-11-19 | 2016-04-06 | 浙江大学 | A constant-temperature large-scale preparing method of belt-shaped black phosphorus |
| CN107055497A (en) * | 2017-03-20 | 2017-08-18 | 中国科学技术大学先进技术研究院 | A kind of two-dimentional black phosphorus material and preparation method thereof |
| US10676357B1 (en) * | 2019-03-22 | 2020-06-09 | The Florida International University Board Of Trustees | Bipolar exfoliation of black phosphorous into phosphorene |
| CN110205674A (en) * | 2019-06-16 | 2019-09-06 | 深圳市中科墨磷科技有限公司 | A method of two-dimentional black phosphorus crystal is prepared by raw material of white phosphorus |
| CN111170291A (en) * | 2020-01-21 | 2020-05-19 | 上海交通大学 | Method for quickly preparing black phosphorus at low cost |
| CN111254494A (en) * | 2020-03-27 | 2020-06-09 | 李旻鸶 | Preparation method for realizing cheap black phosphorus single crystal by using low-purity red phosphorus |
Non-Patent Citations (2)
| Title |
|---|
| MING ZHAO, ET AL: "Understanding the growth of black phosphorus crystals" * |
| 尤凯熹;范涛健;葛颜绮;张晗;: "二维纳米材料黑磷的光电特性研究进展" * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113479857A (en) * | 2021-08-03 | 2021-10-08 | 陕西科技大学 | Crystal red phosphorus II type nanobelt material and preparation method thereof |
| CN113479857B (en) * | 2021-08-03 | 2023-06-23 | 陕西科技大学 | Crystal red phosphorus II type nano belt material and preparation method thereof |
| CN115010103A (en) * | 2022-04-20 | 2022-09-06 | 贵州民族大学 | Preparation method of purple phosphorus nanobelt material |
| CN115124008A (en) * | 2022-06-29 | 2022-09-30 | 西安热工研究院有限公司 | Purple phosphorus nano long belt and preparation method and application thereof |
| CN115124008B (en) * | 2022-06-29 | 2024-03-08 | 西安热工研究院有限公司 | Purple phosphorus nanometer long belt and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112645295A (en) | Black phosphorus nanobelt material and preparation method thereof | |
| Dai et al. | The octa-twin tetraleg ZnO nanostructures | |
| US6890505B2 (en) | Fine carbon wires and methods for producing the same | |
| Bai et al. | Synthesis of ZnO nanowires by the hydrothermal method, using sol–gel prepared ZnO seed films | |
| Xi et al. | Preparation of β-MnO2 nanorods through a γ-MnOOH precursor route | |
| Popuri et al. | VO2 (A): Reinvestigation of crystal structure, phase transition and crystal growth mechanisms | |
| CN113174634B (en) | Crystal red phosphorus nanowire and preparation method thereof | |
| Wang et al. | Hydrothermal synthesis of single-crystalline hexagonal prism ZnO nanorods | |
| Cao et al. | Synthesis and characterization of MgF2 and KMgF3 nanorods | |
| CN111593402A (en) | Two-dimensional ferromagnetic material Fe3GeTe2 and Co-doped Fe3-xCoxGeTe2 single crystal growth method | |
| Yao et al. | Synthesis of differently shaped C70 nano/microcrystals by using various aromatic solvents and their crystallinity-dependent photoluminescence | |
| CN112960660A (en) | Black phosphorus nanobelt material and preparation method thereof | |
| Yan et al. | Solution growth of nano-to microscopic ZnO on Zn | |
| Yan et al. | A solution-phase approach to the chemical synthesis of ZnO nanostructures via a low-temperature route | |
| Tang et al. | Facile synthesis of Bi2S3 nanowire arrays | |
| Xing et al. | Microwave-assisted hydrothermal synthesis of biocompatible silver sulfide nanoworms | |
| Yu et al. | Multi-morphology PbS: frame–film structures, twin nanorods, and single-crystal films prepared by a polymer-assisted solvothermal method | |
| CN110894298B (en) | Preparation method of MOFs nano material and derivative thereof | |
| Zakharova et al. | Synthesis and characterization of V3O7⋅ H2O nanobelts | |
| US20220402824A1 (en) | Method of preparing bscco-based materials | |
| Ahmed et al. | Low temperature growth of ZnO nanotubes for fluorescence quenching detection of DNA | |
| CN113800476A (en) | Ultrasonic preparation method of nano metal oxide | |
| Zhong et al. | Effect of annealing on the structure and photoluminescence of Eu-Doped ZnO nanorod ordered array thin films | |
| Zhu et al. | Microwave-hydrothermal synthesis and structural characterization of PX-phase single-crystalline PbTiO3 nanowires by electron microscopy | |
| CN110835109B (en) | Novel two-dimensional layered semiconductor material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |