CN108609588B - Preparation method of regular hexagonal boron nitride nanosheet - Google Patents
Preparation method of regular hexagonal boron nitride nanosheet Download PDFInfo
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- CN108609588B CN108609588B CN201810452773.1A CN201810452773A CN108609588B CN 108609588 B CN108609588 B CN 108609588B CN 201810452773 A CN201810452773 A CN 201810452773A CN 108609588 B CN108609588 B CN 108609588B
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
A preparation method of regular hexagonal boron nitride nanosheets comprises the steps of firstly, placing a treated copper foil in a quartz tube, then placing a magnetic boat filled with ammonia borane at the other end of the quartz tube, introducing nitrogen into the quartz tube at a speed of 100-; secondly, continuously keeping the calcination temperature, opening a gas inlet valve, and simultaneously respectively introducing nitrogen and ammonia into the quartz tube; thirdly, after the temperature is programmed to rise and the growth temperature of the boron nitride nanosheets is reached, the boron nitride nanosheets are kept at the growth temperature for 20-30min, at the moment, the nitrogen gas inlet valve is closed, meanwhile, the ammonia gas inlet valve is adjusted, and the flow of the ammonia gas is controlled to be 20-70 sccm; and finally, closing the ammonia gas inlet valve, quickly moving the quartz tube out of the heating equipment, and taking out the copper foil after the temperature of the quartz tube is reduced to room temperature.
Description
Technical Field
the invention relates to the field of preparation of nano materials, in particular to a preparation method of a regular hexagonal boron nitride nanosheet.
Background
Hexagonal boron nitride (h-BN) is a common layered material, has the appearance of white loose and soft powder, is also called white graphite, is generally prepared by synthesizing boron oxide and boric acid, and has ultrahigh chemical stability, thermal stability, low dielectric constant, high thermal conductivity, high heat resistance, excellent oxidation resistance and wave permeability. Therefore, many scientists have been attracted to intensive research on their synthesis and performance.
The boron nitride nanosheet well maintains the excellent performance of the massive boron nitride, but the performance of the boron nitride nanosheet is greatly related to the thickness and the shape of the layer. In order to obtain a boron nitride nanosheet of regular shape and ultra-thin thickness, various methods have been tried, such as in 2010, shahana Chatterjee et al, "Chemical vapor deposition of boron nitride on metallic substrates via decaboranes/ammoniaracterises", which first produced a boron nitride film of 2-5 layers on a copper foil (Cu) on a large scale, by a thermal catalytic vapor deposition method, first placing a Cu substrate in the center of a tube furnace, and then placing the Cu substrate on an Ar-H furnace2calcining at 600 deg.C for 20min under mixed gas atmosphere, programming to 1000 deg.C, and adding ammonia borane (NH)3-BH3) By Ar-H2and blowing the mixed gas flow to the reaction area, forming a few layers of boron nitride after 30-60min, wherein the growth of the boron nitride nanosheets can be ensured by the similar lattice parameter of the Cu foil and the BN.
In 2009, Chunyi Zhi et al, "Large-Scale contaminationthe method comprises the steps of selecting dimethyl formamide (DMF) as a strong polar solvent, realizing liquid phase ultrasonic stripping of Boron Nitride Nanosheets by utilizing strong interaction of polar DMF molecules and BN surfaces to obtain 0.01mg/mL of dispersion liquid, and finally carrying out centrifugation and drying treatment to obtain milligram-grade (0.5-1mg) Nanosheets, wherein the size of a product is reduced compared with that of an initial sample, and most of the thickness is distributed at 2-10 nm. In 2011, Coleman et al published in the Science journal on different solvents for layered h-BN, M0S2、WS2The article of ultrasonic-assisted peeling effect indicates that a solvent (mainly an organic solvent) plays a functional role in the peeling process of a layered material, and meanwhile, the solvent has strong polarity, good dispersibility and certain surface tension, has certain hydrogen bond cohesive energy density in a specific range, reduces the peeling energy of the layered material and further realizes peeling.
In addition, Lee et al, "Scalable extrusion processes for high purity soluble boron nitride nanoparticles-assisted pellet milling", add sodium hydroxide solution (NaOH) to improve the process before ball-milling stripping, strip from the surface of parent boron nitride powder through the combined action of mechanical shear force and chemical intercalation to prepare nanosheets, the stripping efficiency reaches 18%, the nanosheets obtained are hydroxylated during the stripping process, and a plurality of stable nanosheet dispersions can be formed.
Although various methods are available for preparing the boron nitride nanosheets, no method can realize accurate control of the morphology of the boron nitride nanosheets, and therefore, the invention provides a preparation method for preparing the hexagonal boron nitride nanosheets with regular shapes.
disclosure of Invention
Although the existing preparation methods of the boron nitride nanosheets are various, no method can realize accurate control of the morphology of the boron nitride nanosheets, and therefore, the inventor successfully obtains the method for preparing the regular hexagonal boron nitride nanosheets through long-time research and a large number of experiments by combining with related documents.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a regular hexagonal boron nitride nanosheet comprises the following steps:
(a) placing the treated copper foil in a quartz tube, then placing a magnetic boat containing ammonia borane at the other end of the quartz tube, introducing nitrogen into the quartz tube at the speed of 100-;
(b) Continuously keeping the calcination temperature, opening a gas inlet valve, simultaneously respectively introducing nitrogen and ammonia gas into the quartz tube, wherein the flow of the nitrogen gas is adjusted to be 50-250sccm, the flow of the ammonia gas is 100-160sccm, and then adjusting a temperature-raising program to start programmed temperature raising of the quartz tube;
(c) After the temperature is programmed to rise, the growth temperature of the boron nitride nanosheets is reached, the boron nitride nanosheets are kept at the temperature for growth for 20-30min, at the moment, the nitrogen gas inlet valve is closed, meanwhile, the ammonia gas inlet valve is adjusted, and the flow of ammonia gas is controlled to be 20-70 sccm;
(d) And after the growth is finished, closing the ammonia gas inlet valve, quickly moving the quartz tube out of the heating equipment, directly exposing the copper foil with the boron nitride nanosheets to the air, and taking out the copper foil after the temperature of the quartz tube is reduced to the room temperature.
Further, the treated copper foil in the step (a) is obtained by placing the copper foil in dilute nitric acid for washing, then washing with deionized water, repeating the steps for 3-5 times, and then drying with nitrogen; here, the copper foil must not be washed with hydrochloric acid, and the chloride ions in hydrochloric acid greatly inhibit the regular growth of boron nitride.
Further, the temperature programming in step (b) is to heat the temperature to 950-; the inventor finds that the temperature-raising program has an important influence on the regular growth of boron nitride through a large number of experiments, and related literature researches show that the boron nitride nanosheets with regular shapes are difficult to prepare due to the influence of factors such as the sizes of boron atoms and nitrogen atoms, so that the invention makes a great contribution to the prior art.
Further, step (d) is followed by a process of substrate transfer using conventional methods.
Compared with the prior art, the invention has the following beneficial technical effects:
The hexagonal boron nitride with the regular hexagonal shape is successfully prepared by adjusting the process for preparing the boron nitride nanosheet, and the method is low in cost, simple to operate, excellent in repeatability and suitable for popularization and production.
Drawings
FIG. 1 is a TEM photograph of a regular hexagonal boron nitride nanosheet prepared according to the present invention;
FIG. 2 is a TEM photograph of a regular hexagonal boron nitride nanosheet prepared according to the present invention;
FIG. 3 is a TEM photograph of a regular hexagonal boron nitride nanosheet prepared according to the present invention;
FIG. 4 is an XRD pattern of a regular hexagonal boron nitride nanosheet prepared in accordance with the present invention.
Detailed Description
in order to make the technical features, objects and advantages of the present invention more clearly apparent, the technical solutions of the present invention are described in detail, and it should be noted that the embodiments described herein are not intended to limit the present invention, but only to explain the present invention, and those skilled in the art can make simple changes without departing from the spirit of the present invention, and they are within the scope of the present invention as claimed.
for subsequent use, the copper foil is treated by soaking the copper foil in dilute nitric acid for 0.5-1min, then taking out the copper foil, washing the copper foil with deionized water, repeating the process for 3 times, and then drying the copper foil with nitrogen.
Example 1
(a) Placing the treated copper foil in a quartz tube, then placing a magnetic boat filled with ammonia borane at the other end of the quartz tube, introducing nitrogen into the quartz tube at a speed of 100sccm to drive the gas, closing an air valve after 5min to stop introducing the nitrogen, and then quickly heating one end of the quartz tube with the copper foil to 800 ℃ to calcine for 45 min;
(b) Continuously keeping the calcination temperature, opening a gas inlet valve, and simultaneously respectively introducing nitrogen and ammonia gas into the quartz tube, wherein the flow rate of the nitrogen gas is adjusted to 50sccm, the flow rate of the ammonia gas is 100sccm, then adjusting a temperature rise program, and starting to perform temperature rise program on the quartz tube, wherein the temperature rise is firstly performed to 950 ℃ at a speed of 5 ℃/min, and then is performed to 1010 ℃ at a speed of 1 ℃/min;
(c) After the temperature is programmed to rise, the growth temperature of the boron nitride nanosheets is reached, the boron nitride nanosheets are kept at the growth temperature for 30min, at the moment, the nitrogen gas inlet valve is closed, meanwhile, the ammonia gas inlet valve is adjusted, and the flow of ammonia gas is controlled to be 20 sccm;
(d) and after the growth is finished, closing the ammonia gas inlet valve, quickly moving the quartz tube out of the heating equipment, directly exposing the copper foil with the boron nitride nanosheets to the air, and taking out the copper foil after the temperature of the quartz tube is reduced to the room temperature.
Example 2
A preparation method of a regular hexagonal boron nitride nanosheet comprises the following steps:
(a) placing the treated copper foil in a quartz tube, then placing a magnetic boat filled with ammonia borane at the other end of the quartz tube, introducing nitrogen into the quartz tube at a speed of 500sccm for expelling gas, closing an air valve after 2min, stopping introducing the nitrogen, then quickly heating one end of the quartz tube with the copper foil to 900 ℃, and calcining for 30 min;
(b) Continuously keeping the calcination temperature, opening a gas inlet valve, and simultaneously respectively introducing nitrogen and ammonia gas into the quartz tube, wherein the flow rate of the nitrogen gas is adjusted to 250sccm, the flow rate of the ammonia gas is 160sccm, then adjusting a temperature-raising program, and starting to perform temperature-raising program on the quartz tube, wherein the temperature is raised to 1000 ℃ at the speed of 10 ℃/min, and then is raised to 1050 ℃ at the speed of 5 ℃/min;
(c) After the temperature is programmed to rise, the growth temperature of the boron nitride nanosheets is reached, the boron nitride nanosheets are kept at the growth temperature for 20min, at the moment, the nitrogen gas inlet valve is closed, meanwhile, the ammonia gas inlet valve is adjusted, and the flow of ammonia gas is controlled to be 70 sccm;
(d) and after the growth is finished, closing the ammonia gas inlet valve, quickly moving the quartz tube out of the heating equipment, directly exposing the copper foil with the boron nitride nanosheets to the air, and taking out the copper foil after the temperature of the quartz tube is reduced to the room temperature.
example 3
a preparation method of a regular hexagonal boron nitride nanosheet comprises the following steps:
(a) placing the treated copper foil in a quartz tube, then placing a magnetic boat filled with ammonia borane at the other end of the quartz tube, introducing nitrogen into the quartz tube at a speed of 200sccm for expelling gas, closing an air valve after 4min, stopping introducing the nitrogen, then quickly heating one end of the quartz tube with the copper foil to 850 ℃, and calcining for 26 min;
(b) continuously keeping the calcination temperature, opening a gas inlet valve, and simultaneously respectively introducing nitrogen and ammonia gas into the quartz tube, wherein the flow rate of the nitrogen gas is adjusted to be 150sccm, the flow rate of the ammonia gas is 120sccm, then adjusting a temperature-raising program, and starting to perform temperature-raising program on the quartz tube, wherein the temperature is raised to 960 ℃ at a speed of 7 ℃/min, and then raised to 1050 ℃ at a speed of 4 ℃/min;
(c) After the temperature is programmed to rise, the growth temperature of the boron nitride nanosheets is reached, the boron nitride nanosheets are kept at the temperature for growth for 25min, at the moment, the nitrogen gas inlet valve is closed, meanwhile, the ammonia gas inlet valve is adjusted, and the flow of ammonia gas is controlled to be 50 sccm;
(d) and after the growth is finished, closing the ammonia gas inlet valve, quickly moving the quartz tube out of the heating equipment, directly exposing the copper foil with the boron nitride nanosheets to the air, and taking out the copper foil after the temperature of the quartz tube is reduced to the room temperature.
comparative example 1
The other conditions were the same as in example 1, except that the temperature raising procedure was different, and the temperature was raised directly from 850 ℃ to 1050 ℃ at a rate of 5 ℃/min using a single-stage temperature raising, and it was found from the TEM photograph that the obtained boron nitride nanosheets were not regular hexagonal in shape.
Claims (2)
1. a preparation method of regular hexagonal boron nitride is characterized by comprising the following steps: the method comprises the following steps:
(a) Placing the treated copper foil in a quartz tube, then placing a magnetic boat containing ammonia borane at the other end of the quartz tube, introducing nitrogen into the quartz tube at the speed of 100-;
(b) continuing to maintain the calcination temperature, opening a gas inlet valve, and simultaneously respectively introducing nitrogen and ammonia gas into the quartz tube, wherein the flow rate of the nitrogen gas is adjusted to 50-250sccm, the flow rate of the ammonia gas is 100-;
(c) After the temperature is programmed to rise, the growth temperature of the boron nitride nanosheets is reached, the boron nitride nanosheets are kept at the temperature for growth for 20-30min, at the moment, the nitrogen gas inlet valve is closed, meanwhile, the ammonia gas inlet valve is adjusted, and the flow of ammonia gas is controlled to be 20-70 sccm;
(d) And after the growth is finished, closing the ammonia gas inlet valve, quickly moving the quartz tube out of the heating equipment, directly exposing the copper foil with the boron nitride nanosheets to the air, and taking out the copper foil after the temperature of the quartz tube is reduced to room temperature to obtain the hexagonal boron nitride with a regular hexagonal shape, wherein the thickness of the hexagonal boron nitride is 2-5 layers, and the side length of the hexagonal boron nitride is 1-4 microns.
2. The method of claim 1, wherein: the treated copper foil in the step (a) is obtained by placing the copper foil in dilute nitric acid for washing, then washing with deionized water, repeating the steps for 3-5 times, and then drying with nitrogen.
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