CN107572490A - A kind of preparation method of controlledly synthesis boron nitride nanosheet - Google Patents
A kind of preparation method of controlledly synthesis boron nitride nanosheet Download PDFInfo
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- CN107572490A CN107572490A CN201710811088.9A CN201710811088A CN107572490A CN 107572490 A CN107572490 A CN 107572490A CN 201710811088 A CN201710811088 A CN 201710811088A CN 107572490 A CN107572490 A CN 107572490A
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Abstract
The present invention is a kind of preparation method of controlledly synthesis boron nitride nanosheet.This method comprises the following steps：By metal magnesium powder and boron oxide according to mixing, in Yan Portland grinding obtain pale white mixture；It is positioned over again in high temperature process furnances, 750 850 DEG C is raised to from normal temperature under nitrogen protection atmosphere, is incubated 1 1.5h；Then atmosphere is changed under ammonia atmosphere, 1,200 1400 DEG C, is incubated 2 10h, then is cooled to room temperature, obtains white solid product；Finally by washing, drying, boron nitride nanosheet powder is finally obtained.The present invention is not high to equipment requirement, reduces energy consumption and production cost.Product is purified by simple salt pickling, easily operated.
Description
Technical field
The present invention relates to hexagonal nanometer boron nitride material technology synthesize field, the six of specially a kind of pure phase uniform particle sizes
The controllable synthesis method of square boron nitride nanosheet.
Background technology
The molecular formula of hexagonal boron nitride crystal is BN, is isoelectronic species with graphite, has the layer structure of similar graphite, tool
There are excellent electrical insulating property, high-temperature flame-proof, heat conductivity, chemical inertness, high-lubricity etc., be widely used in machinery, smelting
The sciemtifec and technical spheres such as gold, electronics, Aero-Space.
Boron nitride nanosheet has the two-dimensional nanostructure of similar graphene, by multilayer hexagonal boron nitride stratiform folded structures
Form.Boron nitride nanosheet has the mechanical property to be compared favourably with graphene and heat-conductive characteristic, and with than graphene more
Superior chemical stability, heat endurance, unique UV luminescent characteristics etc..Meanwhile boron nitride nanosheet is typical wide taboo
Carrying semiconductor material, its band gap width are 5-6eV, are to prepare insulating electronic device film, high temperature power device, nano composite material
And the ideal material of ultra-violet light-emitting element.
In recent years, researcher constantly seeks the synthetic method of energy-saving and environment friendly to prepare boron nitride nanosheet, including
Mechanical phonograph recorder separation, chemical vapour deposition technique, solid state reaction method etc..But due to the limitation of preparation method, products therefrom amount is non-
It is often few, and major defect be present, this seriously constrains hexagonal boron nitride and further developed in research and application field.
D.Pacil é etc. first reported the synthesis of two-dimentional boron nitride nanometer material, using micromechanics partition method, obtain about 10
The boron nitride nanosheet of atomic layer, the method is although simple and easy, but randomness is whard to control greatly, yields poorly and product defect
It is more.Zhi Chunyi et al. utilizes the method similar to chemical vapor deposition, has obtained large-sized hexagonal boron nitride nanosheet, and
And its effect as additive in the polymer is have studied, the method for preparing hexagonal boron nitride is enriched, but obtained production
Object amount is few, can not industrialized production.Xu Li is strong et al. to have invented a kind of preparation side of high-specific surface area boron nitride ultrathin nanometer piece
Method, it uses solid phase method, is boron source using boron oxide, and hydrazine hydrochloride, ammonium chloride or ammonium bromide are nitrogen source, metallic zinc, iron or
Nickel is reducing agent, is prepared for hexagonal boron nitride nanosheet in a mild condition, but its thickness is difficult to control, and low yield.
The present invention relates to a kind of method of easy controlledly synthesis hexagonal boron nitride nanosheet, have simple to operate, raw material is cheap, thickness
It is controllable, be adapted to industrialized production the characteristics of, products obtained therefrom crystallinity and purity are all higher.
The content of the invention
It is an object of the invention to for insufficient present in current techniques, there is provided a kind of controlledly synthesis boron nitride nanosheet
Preparation method.This method uses boron oxide, magnesium powder as raw material, under suitable material proportion, by under two sections of different atmospheres
Sintering obtain product.Raw material of the present invention is cheap and easy to get, and preparation process is simple and convenient, can be produced in enormous quantities with high quality, gram
The existing boron nitride nanosheet of clothes prepares the shortcomings of products therefrom purity is low, size is uneven, thickness is thicker, raw material are expensive.
The technical scheme is that：
A kind of preparation method of controlledly synthesis boron nitride nanosheet, comprises the following steps：
(1) metal magnesium powder and boron oxide are mixed, grinding 1-5min is well mixed in Yan Portland obtains pale white mixture；
Wherein, mol ratio magnesium powder：Boron oxide=1~6:1；
(2) mix powder obtained in step (1) is positioned in high temperature process furnances, from normal temperature under nitrogen protection atmosphere
750-850 DEG C is raised to, heating rate is 10 DEG C/min, is incubated 1-1.5h；Then atmosphere is changed under ammonia atmosphere, with 10 DEG C/min
Heating rate be raised to 1200-1400 DEG C, be incubated 2-10h, then be cooled to room temperature, obtain white solid product；
(3) the product hydrochloric acid solution movement stirring 6-24h in step (2) is washed away into oxidation magnesium addition, then filtered, then use
Deionization is washed 2-3 times and obtains white powder；
(4) white powder in step (3) is incubated 10-15h in 70-90 DEG C of baking oven, finally obtains boron nitride nanometer
Piece powder.
The gas flow in nitrogen atmosphere or ammonia atmosphere in described step (3) is 50ml/min-100ml/
min。
The concentration of hydrochloric acid in described step (3) is 1~5M.
The present invention substantive distinguishing features be：
(1) present invention can as control reaction raw materials proportioning come accuracy controlling gained boron nitride nanosheet size with
Thickness, overcome the boron nitride nanosheet that the size that boron nitride nanosheet can not obtain needs as required is prepared in current techniques
Deficiency.Meanwhile the present invention is passed through two sections of gases in reaction is whole, i.e., normal temperature is warming up to 800 DEG C or so and insulation 1h first
Left and right is passed through nitrogen, and nitrogen is changed to ammonia, ammonia now participates in anti-as reacting gas again afterwards here as protection gas
Should；Boron nitride so can be generated using ammonia as nitrogen source and boric acid reactive magnesium；
(2) selection, reaction of the present invention by raw material, has obtained antifungin, and as a kind of brand-new presoma
Prepare boron nitride nanometer (from Fig. 8 a it can be seen that when 1400-2h is reacted, XRD peak positions be antifungin peak, Ran Housui
The increase in reaction time, the peak position intensity decreases of antifungin, boron nitride, magnesia peak position protrude, when reacting 10h, boric acid
Magnesium peak position all disappears, and obtains the mixing peak of boron nitride and magnesia.When with pickling deoxidation magnesium, obtaining pure boron nitride.Currently
In technology, in " a kind of preparation method of boron nitride nano-tube (CN103922295A) ", although and with metal magnesium powder and oxidation
It is raw material that boron, which is pressed, but due to experiment process is passed through pure gas using whole process, and be that one-step synthesis is direct and obtain
To boron nitride nano-tube, the boron nitride nanosheet of gained in this patent can not be obtained.
Beneficial effects of the present invention are：
1st, the product obtained by the inventive method is the hexagonal boron nitride nanosheet of pure phase.The diffraction of XRD spectra (Fig. 1) is strong
Degree is high, and clear sharp, occurs without other miscellaneous peaks, shows typical hexagonal boron nitride XRD spectral lines, prepared by surface
Product is the hexagonal boron nitride nanosheet of pure phase.The length of the prepared boron nitride nanosheet of SEM and TEM (Fig. 3 and Fig. 4) displays
400-600nm, width 500nm or so, thickness 10-25nm, the thickness of product, product shape can be controlled by the ratio of raw material
Looks are homogeneous, and crystallization degree is high, and defect is few, available for heat sink material, high polymer material filler, reach activeness and quietness, lifting heat
The purpose of stability, carrier as catalyst etc..Can be by controlling reactant ratio accuracy controlling boron nitride nanosheet to put down
For row in the area and thickness in (002) face, other produce the patent of boron nitride nanosheets without reference to controlledly synthesis problem, and can
To obtain large-size ultra-thin boron nitride nanosheet by increasing the accounting of magnesium powder.
2nd, raw material used in the present invention is magnesium powder and boron oxide powder, and the general chemical for belonging to industrialized production is former
Material, it is cheap and easy to get, it is nontoxic.
3rd, the present invention uses boron oxide metal magnesium powder is catalyst for raw material, is made by high-temperature tubular stove heat, pair sets
It is standby less demanding, reduce energy consumption and production cost.Product is purified by simple salt pickling, easily operated.
Brief description of the drawings
Fig. 1 is the XRD spectra of hexagonal boron nitride nanosheet in embodiment 1
Fig. 2 is the infrared spectrum of hexagonal boron nitride nanosheet in embodiment 1
Fig. 3 is the scanning spectrogram of hexagonal boron nitride nanosheet in embodiment 1
Fig. 4 is the transmission spectrum of hexagonal boron nitride nanosheet in embodiment 1
Fig. 5 is that the XRD of hexagonal boron nitride nanosheet in embodiment 1,2,3 contrasts spectrogram
Fig. 6 is the infrared contrast spectrogram of hexagonal boron nitride nanosheet in embodiment 1,2,3
Fig. 7 is that the scanning of hexagonal boron nitride nanosheet in embodiment 1,2,3 contrasts spectrogram, wherein, Fig. 7 a are Mg：B2O3=
1:Spectrogram under the multiplying power of material 10000 obtained when 1, Fig. 7 b are Mg：B2O3=3:Spectrum under the multiplying power of material 10000 obtained when 1
Figure, Fig. 7 c are Mg：B2O3=6:Spectrogram under the multiplying power of material 10000 obtained when 1；Fig. 7 d are Mg：B2O3=6:Obtained when 1
The multiplying power of material 40000 under spectrogram；
Fig. 8 be embodiment 1,4,5 in hexagonal boron nitride nanosheet XRD contrast spectrogram, wherein, Fig. 8 a be products therefrom not
Spectrogram through peracid treatment, Fig. 8 b are spectrogram of the products therefrom through peracid treatment.
Embodiment
Embodiment 1.
(1) 1.8g metal magnesium powders and 1.75g boron oxides are mixed into (mol ratio 3:1), grind 1 minute and mix in Yan Portland
Uniformly obtain pale white mixture；
(2) mix powder obtained in step (1) is positioned in high temperature process furnances, is raised to 800 DEG C from normal temperature, heating
Speed is 10 DEG C/min, is incubated 1h, and this process is nitrogen as being carried out under protection gas, and then atmosphere is changed to ammonia, with 10 DEG C/
Min heating rate is raised to 1400 DEG C, is incubated 10h, then is cooled to room temperature, obtains white solid product.Above gas flow is equal
For 100ml/min；
(3) it is the product in step (2) is miscellaneous with magnesia is washed away with 100ml, 1mol/L hydrochloric acid solution mechanical agitation 6h
Matter, then filtering are washed with deionized water 2-3 times and obtain white powder；
(4) white powder in step (3) is put into 80 DEG C of baking ovens, is incubated 12h, finally obtains boron nitride nanosheet powder
End.
Explanation：
Tested by XRD, the diffraction maximum of all indexings shows that the product is hexagonal boron nitride in Fig. 1, and diffraction maximum is clear
Clear, sharp, high intensity, illustrate that gained boron nitride has good crystallinity, product does not have dephasign, according to Scherrer formula fitting meter
It is about 15nm to calculate size of the gained perpendicular to (002) face.Fig. 2 is the infrared spectrum of product, in 1383cm shown in figure-1With
810cm-1There are B-N and the B-N-B vibration of two characteristic peaks, respectively hexagonal boron nitride in place respectively.As shown in Fig. 3 SEM, we
The boron nitride product of gained is ultra-thin hexagonal boron nitride chip architecture, and size is more homogeneous, the length of boron nitride nanosheet
400-600nm, width 500nm or so, thickness 15nm or so.Shown in Fig. 4 TEM, it may be said that bright hexagonal boron nitride nanosheet is thick
Spend that distributed area is narrower, and thin is only several layers of, thick place probably has ten several layers of.
Embodiment 2
The amount of magnesium powder in step (1) in embodiment 1 is changed into 0.6g, and (mol ratio of magnesium and boron oxide is 1:1), other are each
Item operation is same as Example 1, and obtained product is with embodiment 1, and products therefrom XRD such as Fig. 5, infrared such as Fig. 6, scanning figure are such as
Fig. 7.
Embodiment 3
The amount of magnesium powder in step (1) in embodiment 1 is changed into 3.6g, and (mol ratio of magnesium and boron oxide is 6:1), other are each
Item operation is same as Example 1, and obtained product is with embodiment 1, and products therefrom XRD such as Fig. 5, infrared such as Fig. 6, scanning figure are such as
Fig. 7.
Explanation：
By changing reactant ratio, find that the size and thickness of hexagonal boron nitride nanosheet can be regulated and controled.By Fig. 5 institutes
Show, the product that three kinds of reactant ratios obtain all has the characteristic peak of hexagonal boron nitride, but is calculated according to Scherrer formula fitting
Size of the gained perpendicular to (002) face respectively may be about 25nm, 14nm, 8nm.By its infrared comparison diagram (Fig. 6) it can be seen that three
Kind product all has two special vibration peaks of hexagonal boron nitride.Scanned by Fig. 7 in comparison diagram this it appears that three kinds of products
Size and thickness are significantly different, and with Mg proportion increase, the size of gained boron nitride nanosheet is increasing, and thickness is bright
It is aobvious to reduce (size here refers to the area parallel to (002) face), it is consistent with XRD comparison diagrams in Fig. 5.So as to illustrate, work as thing
Material proportioning is in mol ratio magnesium powder：Boron oxide=1~6:In the range of 1 ", with the increase of the mol ratio of magnesium powder, obtained nanometer
Piece gradually increases parallel to the area in (002) face, and thickness is gradually reduced, so as to realize the essence to nanometer sheet size and thickness
Quasi- regulation and control.
Embodiment 4
1400 DEG C of soaking times in step (2) in embodiment 1 are changed to 6h, other operations are same as Example 1, obtain
Product is the same as embodiment 1, XRD such as Fig. 8.
Embodiment 5
1400 DEG C of soaking times in step (2) in embodiment 1 are changed to 2h, other operations are same as Example 1, obtain
Product difference and embodiment 1, XRD such as Fig. 8.
Explanation：
Its Reaction Mechanisms can be deduced according to the XRD comparison diagrams (Fig. 8) of differential responses time products therefrom, with
The increase in reaction time, products therefrom first generate the mixed phase of antifungin and magnesia, with the increase antifungin in reaction time
As new presoma generate boron nitride, until all antifungins all consume generation boron nitride and magnesia mixture, pass through
Pickling obtains boron nitride pure phase.
Embodiment 6
1400 DEG C of insulations in step (2) in embodiment 1 are changed to 1200 DEG C, other operations are same as Example 1, obtain
Product difference and embodiment 1.
Embodiment 7
Milling time in step (1) in embodiment 1 is changed to 3 minutes, other operations are same as Example 1, produced
Thing is the same as embodiment 1.
Embodiment 8
Milling time in step (1) in embodiment 1 is changed to 5 minutes, other operations are same as Example 1, produced
Thing is the same as embodiment 1.
Embodiment 9
Gas flow in step (2) in embodiment 1 is changed to 50ml/min, other operations are same as Example 1, obtain
Product is the same as embodiment 1.
Embodiment 10
Gas flow in step (2) in embodiment 1 is changed to 100ml/min, other operations are same as Example 1, obtain
To product with embodiment 1.
Embodiment 11
Pickling time in step (3) in embodiment 1 is changed to 12h, other operations are same as Example 1, obtain product
Together
Embodiment 1.
Embodiment 12
Pickling time in step (3) in embodiment 1 is changed to 24h, other operations are same as Example 1, obtain product
Together
Embodiment 1.
Unaccomplished matter of the present invention is known technology.
Claims (3)
- A kind of 1. preparation method of controlledly synthesis boron nitride nanosheet, it is characterized in that this method comprises the following steps：（1）Metal magnesium powder and boron oxide are mixed, grinding 1-5min is well mixed in Yan Portland obtains pale white mixture；Its In, mol ratio magnesium powder：Boron oxide=1 ~ 6:1；（2）By step（1）In obtained mix powder be positioned in high temperature process furnances, be raised under nitrogen protection atmosphere from normal temperature 750-850 DEG C, heating rate is 10 DEG C/min, is incubated 1-1.5h；Then atmosphere is changed under ammonia atmosphere, with 10 DEG C/min liter Warm speed is raised to 1200-1400 DEG C, is incubated 2-10h, then is cooled to room temperature, obtains white solid product；（3）By step（2）In product hydrochloric acid solution movement stirring 6-24h wash away oxidation magnesium addition, then filter, then spend from Son is washed 2-3 times and obtains white powder；（4）By step（3）In white powder 10-15h is incubated in 70-90 DEG C of baking oven, finally obtain boron nitride nanosheet powder End.
- 2. the preparation method of controlledly synthesis boron nitride nanosheet as claimed in claim 1, it is characterized in that described step（3）In Nitrogen atmosphere or ammonia atmosphere in gas flow be 50ml/min-100ml/min.
- 3. the preparation method of controlledly synthesis boron nitride nanosheet as claimed in claim 1, it is characterized in that described step（3）In The concentration of hydrochloric acid be 1 ~ 5M.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921637A (en) * | 2018-09-20 | 2020-03-27 | 中国科学院上海微***与信息技术研究所 | Preparation method of multilayer hexagonal boron nitride film |
| CN112661123A (en) * | 2021-01-19 | 2021-04-16 | 桂林理工大学 | Preparation method of double-layer strip-shaped boron nitride hierarchical structure and product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012115348A2 (en) * | 2011-02-23 | 2012-08-30 | 한국과학기술원 | High-quality hexagonal boron-nitride nanosheet using a multi-component low eutectic temperature system |
| CN103922295A (en) * | 2014-04-17 | 2014-07-16 | 河北工业大学 | Preparation method of boron nitride nano tube |
| CN106829888A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet powder and its magnanimity preparation method |
-
2017
- 2017-09-11 CN CN201710811088.9A patent/CN107572490A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012115348A2 (en) * | 2011-02-23 | 2012-08-30 | 한국과학기술원 | High-quality hexagonal boron-nitride nanosheet using a multi-component low eutectic temperature system |
| CN103922295A (en) * | 2014-04-17 | 2014-07-16 | 河北工业大学 | Preparation method of boron nitride nano tube |
| CN106829888A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet powder and its magnanimity preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921637A (en) * | 2018-09-20 | 2020-03-27 | 中国科学院上海微***与信息技术研究所 | Preparation method of multilayer hexagonal boron nitride film |
| CN110921637B (en) * | 2018-09-20 | 2022-09-23 | 中国科学院上海微***与信息技术研究所 | Preparation method of multilayer hexagonal boron nitride film |
| CN112661123A (en) * | 2021-01-19 | 2021-04-16 | 桂林理工大学 | Preparation method of double-layer strip-shaped boron nitride hierarchical structure and product |
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