CN102849694A - Preparation method of batch preparation of boron nitride nanotube - Google Patents
Preparation method of batch preparation of boron nitride nanotube Download PDFInfo
- Publication number
- CN102849694A CN102849694A CN2012104001748A CN201210400174A CN102849694A CN 102849694 A CN102849694 A CN 102849694A CN 2012104001748 A CN2012104001748 A CN 2012104001748A CN 201210400174 A CN201210400174 A CN 201210400174A CN 102849694 A CN102849694 A CN 102849694A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- nitride nano
- boron
- tube
- gas
- 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
Abstract
The invention relates to a method for batch preparation of boron nitride nanotubes. The method comprises the steps of sufficiently mixing a boron source, a transition metal compound and alkaline-earth metal compounds; heating the mixture to 1000-1100 DEG C under the protection of nitrogen or argon; stopping supplying a protective gas, beginning supplying a mixture gas of the nitrogen and the argon, reacting and continuing to heat to 1200-1400 DEG C, keeping the temperature for 0.5-4 hours, stopping the supply of the gas after the heat preservation, closing the gas inlet and the gas outlet and decreasing the temperature to the room temperature so as to obtain white rough products, heating the rough products in the air to 600 DEG C and subsequently pickling and drying. The diameter of the prepared boron nitride nanotube is 50-300nm, and the length can be more than 100 microns. By introducing an alkaline-earth metal as a catalyst, a great quantity of boron nitride nanotubes can grow at a lower temperature; the cost is lower, the material resource is wide, the preparation process is simple, and the batch production can be realized easily.
Description
Technical field
The invention belongs to field of inorganic nano material, be specifically related to the preparation method that a kind of batch prepares boron nitride nano-tube.
Background technology
Boron nitride nano-tube is similar to carbon nanotube, can regard that the carbon atom in the carbon nanotube is replaced the product that replaces by boron and nitrogen-atoms as.Boron nitride nano-tube not only has mechanical property and the heat-conductive characteristic that can compare favourably with carbon nanotube, but also have excellent oxidation-resistance, chemical stability and thermostability, this is applied in the nano composite material so that boron nitride nano-tube becomes desirablely at structured material.Boron nitride nano-tube is stable wide bandgap material, and electric property does not change with caliber and chirality, and this is for the electric property of carbon nanotube mutability, and the application of boron nitride nano-tube in electron device has larger advantage.In addition, boron nitride nano-tube also has preferably hydrogen storage property, negative ray emitting performance and biocompatibility, and these advantages can make boron nitride nano-tube at the energy, and electroluminescence and bio-medical field have potential using value.
Boron nitride nanometer tube preparation method commonly used has arc discharge method, laser ablation method, template, mechanical ball milling method, CVD and thermal decomposition method etc., but these methods exist productive rate low, purity is low, and preparation temperature is high, and cost height or complex process are difficult to the shortcomings such as industrialization, the resulting boron nitride nano-tube defective that comes in every shape is also more, and this is seriously restricting the widespread use of boron nitride nano-tube.
Summary of the invention
The object of the invention is to solve the problems of the prior art, provide that a kind of productive rate is high, purity is high, preparation condition is gentle, cost is low, the preparation method of the simple boron nitride nano-tube of technique, and this preparation method is easy to amplify, and can reach the purpose of batch production.
Technical scheme of the present invention is: a kind of batch prepares the method for boron nitride nano-tube; it is characterized in that: with the boron source; transistion metal compound and alkaline earth metal compound fully mix; mixture is heated to 1000～1100 ℃ under nitrogen or argon shield; stop to pass into shielding gas; the mixed gas that begins to pass into ammonia or nitrogen and hydrogen reacts and continues to be heated to 1200～1400 ℃; be incubated 0.5～4 hour; what stop gas after insulation finishes passes into and cools the temperature to room temperature; obtain white crude product; crude product is heated to 600 ℃ in air after, through pickling; dry acquisition caliber is 50～300nm; length can reach the boron nitride nano-tube more than 100 microns.
The mol ratio of boron, transition metal, alkaline-earth metal is 1:0.01～0.09:0.03～0.27 in the boron source that described mixture comprises.
Described boron source is boron powder or boron oxide or boric acid.
Described transistion metal compound is oxide compound or the oxyhydroxide of Fe or Co or Ni.
Described alkaline earth metal compound is oxide compound or the oxyhydroxide of Ca or Ba or Sr.
Described acid is hydrochloric acid.
The reaction that this preparation method may exist is exemplified below (with the B powder, ferric oxide and calcium oxide are example):
2NH
3=N
2+3H
2
Fe
2O
3+3H
2=2Fe+3H
2O
N
2=2N
*
B+N
*=BN
Reaction process is as follows: at first, ammonia is decomposed into active nitrogen-atoms and hydrogen, and hydrogen is with Fe
2O
3Be reduced to simple substance Fe; active nitrogen-atoms and active B atom are dissolved among the simple substance Fe; rising along with temperature; B powder and active N atom being dissolved to saturated and separating out the BN film on the top layer in simple substance Fe; and wrap up gradually and lifting Fe particle; but because the drop of Fe is relatively poor for the wettability of BN; in the process of parcel; the Fe particle of melting can descend and shake off the parcel of BN film gradually, and the BN film is raised gradually, and the Fe particle of melting separates gradually with BN film top; B and N atom continue dissolving and separate out; the BN formation tubulose that grows tall gradually, in this reaction, Fe
2O
3Nucleation centre is provided and accelerates the decomposition of ammonia, CaO provides steric hindrance, so that the simple substance Fe uniform particles that forms is distributed among the CaO, at high temperature can be because of the agglomeration inactivation, and CaO may also have the function of activated b atom.In the process of boron nitride nano-tube growth, some Fe particle can be trapped in the nanotube because have little time to shake off the parcel of BN film.The boron nitride nano-tube of gained has Bamboo-shaped and cylindric two kinds of patterns.
Beneficial effect of the present invention is: by the introducing of catalyzer alkaline-earth metal, can grow under the lower temperature that a large amount of calibers are that 50～300nm, length reach more than 100 microns, pipe shaft is uniform and smooth, pattern with Bamboo-shaped for leading and a small amount of columned boron nitride nano-tube being arranged, this preparation method's cost is lower, raw material sources are extensive, preparation process is simple, be easy to realize batch production, productive rate can reach more than 85%, purity is greater than 85wt%, has widely industrial application value.
Description of drawings
Fig. 1 is the SEM photo of the prepared boron nitride nano-tube of embodiment 1.
Fig. 2 is the TEM photo of the prepared boron nitride nano-tube of embodiment 1.
Embodiment
Further introduce the present invention below by specific embodiment, but embodiment can not be construed as limiting the invention.
Embodiment 1
Take by weighing the amorphous B powder of 5 grams, 1.45 gram Fe
2O
3, 1.27 gram CaO are tiled on the aluminum oxide porcelain plate after fully mixing, and place in the tube furnace, are filled with argon shield and begin and heat up, and argon flow amount is 300ml/min, when being warming up to 1000 ℃, stops to pass into argon gas, begins to pass into NH
3, NH
3Flow is 150ml/min, and continue to be heated to 1300 ℃, be incubated 4 hours, insulation stops to pass into any gas after finishing, and closes tube furnace and advances, the air outlet is cooled to room temperature naturally, obtain white crude product, crude product is heated to 600 ℃ carries out oxide treatment in air, it is that the hydrochloric acid of 38wt% soaked suction filtration 6 hours that the crude product after the oxidation is put into concentration, washing, can obtain 9.9 gram BN nanotube dust after the drying, its productive rate is about 90% as the purity of 87%, BN nanotube take the B powder as benchmark, prepared boron nitride nano-tube is many walls nanotube, average caliber is 150nm, and length is greater than 100 microns, and pipe shaft is uniform and smooth.
Embodiment 2
Take by weighing 7 gram B
2O
3, 0.42 gram Co
2O
3, 0.78 gram BaO is tiled on the aluminum oxide porcelain plate after fully mixing, and places in the tube furnace, is filled with argon shield and begins and heat up, and argon flow amount is 300ml/min, when being warming up to 1100 ℃, stops to pass into argon gas, begins to pass into NH
3, NH
3Flow is 200ml/min, and continues to be heated to 1400 ℃, is incubated 3 hours, insulation stops to pass into any gas after finishing, close the tube furnace inlet, outlet, naturally be cooled to room temperature, obtain white crude product, crude product is heated to 600 ℃ carries out oxide treatment in air, it is that the hydrochloric acid of 36wt% soaked suction filtration, washing 12 hours that crude product after the oxidation is put into concentration, can obtain 4.3 gram BN nanotube dust after the drying, with B
2O
3Powder is that its productive rate of benchmark is that the purity of 85%, BN nanotube is about 85%, and prepared boron nitride nano-tube is many walls nanotube, and average caliber is 180nm, and length is greater than 100 microns, and pipe shaft is uniform and smooth.
Embodiment 3
Take by weighing 6.2 gram H
3BO
3, 0.4 gram Fe
2O
3, 1.48 gram Ca (OH)
2, be tiled on the aluminum oxide porcelain plate after fully mixing, place in the tube furnace, be filled with argon shield and begin and heat up, argon flow amount is 500ml/min, when being warming up to 1000 ℃, stops to pass into argon gas, begins to pass into NH
3, NH
3Flow is 300ml/min, and continues to be heated to 1200 ℃, is incubated 4 hours, insulation stops to pass into any gas after finishing, close the tube furnace inlet, outlet, naturally be cooled to room temperature, obtain white crude product, crude product is heated to 600 ℃ carries out oxide treatment in air, it is that the hydrochloric acid of 37wt% soaked suction filtration, washing 8 hours that crude product after the oxidation is put into concentration, can obtain 2.2 gram BN nanotube dust after the drying, with H
3BO
3Powder is that its productive rate of benchmark is that the purity of 88%, BN nanotube is about 85%, and prepared boron nitride nano-tube is many walls nanotube, and average caliber is 120nm, and length is greater than 100 microns, and pipe shaft is uniform and smooth.
Each raw material that the present invention is cited and the bound value of each raw material, interval value can both be realized the present invention, do not enumerate one by one embodiment at this.Bound value, the interval value of processing parameter of the present invention (such as temperature, soaking time etc.) can both be realized the present invention, do not enumerate one by one embodiment at this.
Claims (6)
1. a batch prepares the method for boron nitride nano-tube; it is characterized in that: with the boron source; transistion metal compound and alkaline earth metal compound fully mix; mixture is heated to 1000～1100 ℃ under nitrogen or argon shield; stop to pass into shielding gas; the mixed gas that begins to pass into ammonia or nitrogen and hydrogen reacts and continues to be heated to 1200～1400 ℃; be incubated 0.5～4 hour; what stop gas after insulation finishes passes into and cools the temperature to room temperature; obtain white crude product; crude product is heated to 600 ℃ in air after, through pickling; dry acquisition caliber is 50～300nm; length can reach the boron nitride nano-tube more than 100 microns.
2. the method for preparing boron nitride nano-tube according to claim 1, it is characterized in that: the mol ratio of boron, transition metal, alkaline-earth metal is 1:0.01～0.09:0.03～0.27 in the boron source that described mixture comprises.
3. the method for preparing boron nitride nano-tube according to claim 1, it is characterized in that: described boron source is boron powder or boron oxide or boric acid.
4. the method for preparing boron nitride nano-tube according to claim 1, it is characterized in that: described transistion metal compound is oxide compound or the oxyhydroxide of Fe or Co or Ni.
5. the method for preparing boron nitride nano-tube according to claim 1, it is characterized in that: described alkaline earth metal compound is oxide compound or the oxyhydroxide of Ca or Ba or Sr.
6. the method for preparing boron nitride nano-tube according to claim 1, it is characterized in that: described acid is hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104001748A CN102849694A (en) | 2012-10-20 | 2012-10-20 | Preparation method of batch preparation of boron nitride nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104001748A CN102849694A (en) | 2012-10-20 | 2012-10-20 | Preparation method of batch preparation of boron nitride nanotube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102849694A true CN102849694A (en) | 2013-01-02 |
Family
ID=47396745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104001748A Pending CN102849694A (en) | 2012-10-20 | 2012-10-20 | Preparation method of batch preparation of boron nitride nanotube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102849694A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036096A (en) * | 2015-07-22 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing high-purity boron nitride nanotubes through reaction gas vortexes |
| CN105531223A (en) * | 2013-06-14 | 2016-04-27 | 耶迪特普大学 | A production method for the boron nitride nanotubes |
| CN107522179A (en) * | 2016-06-21 | 2017-12-29 | 张家港市山牧新材料技术开发有限公司 | A kind of method that gaseous oxygen compound prepares boron nitride nano-tube |
| CN107673318A (en) * | 2016-08-01 | 2018-02-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nano-tube and its batch preparation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587030A (en) * | 2004-07-08 | 2005-03-02 | 北京理工大学 | Process for preparing boron nitride nano tube |
| CN101348242A (en) * | 2008-09-05 | 2009-01-21 | 北京工业大学 | Method for preparing boron nitride nanotube by magnesium reduction |
| CN101513995A (en) * | 2009-04-01 | 2009-08-26 | 武汉工程大学 | Method for preparing boron nitride nano-tube |
| CN101633498A (en) * | 2009-09-01 | 2010-01-27 | 北京工业大学 | Preparation method of boron nitride nano tube with controllable dimension |
-
2012
- 2012-10-20 CN CN2012104001748A patent/CN102849694A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587030A (en) * | 2004-07-08 | 2005-03-02 | 北京理工大学 | Process for preparing boron nitride nano tube |
| CN101348242A (en) * | 2008-09-05 | 2009-01-21 | 北京工业大学 | Method for preparing boron nitride nanotube by magnesium reduction |
| CN101513995A (en) * | 2009-04-01 | 2009-08-26 | 武汉工程大学 | Method for preparing boron nitride nano-tube |
| CN101633498A (en) * | 2009-09-01 | 2010-01-27 | 北京工业大学 | Preparation method of boron nitride nano tube with controllable dimension |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105531223A (en) * | 2013-06-14 | 2016-04-27 | 耶迪特普大学 | A production method for the boron nitride nanotubes |
| CN105036096A (en) * | 2015-07-22 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing high-purity boron nitride nanotubes through reaction gas vortexes |
| CN105036096B (en) * | 2015-07-22 | 2017-07-21 | 哈尔滨工业大学 | A kind of method that utilization reacting gas vortex prepares high-purity boron nitride nano-tube |
| CN107522179A (en) * | 2016-06-21 | 2017-12-29 | 张家港市山牧新材料技术开发有限公司 | A kind of method that gaseous oxygen compound prepares boron nitride nano-tube |
| CN107673318A (en) * | 2016-08-01 | 2018-02-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nano-tube and its batch preparation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108545708B (en) | Preparation method of coralline hexagonal boron nitride micro-nano tube sheet composite structure | |
| CN100534675C (en) | Method for preparing spherical nano silver powder | |
| Nouroozi et al. | Synthesis and characterization of brush-like ZnO nanorods using albumen as biotemplate | |
| CN101899726B (en) | Method for preparing nano-carbon fibers | |
| KR101357628B1 (en) | Metal Nano Catalyst, Method for Preparing thereof and Carbon Nanotube Synthesized Using the Same | |
| US9468911B2 (en) | Catalyst for preparing chiral selective and conductive selective single-walled carbon nanotube, preparation method and application thereof | |
| CN103754878B (en) | The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ | |
| Zhang et al. | Novel binary of g-C3N4 coupling and Eu3+ doping co-modifying bidirectional dendritic BiVO4 heterojunctions with enhanced visible-light photocatalytic performance | |
| CN110104623B (en) | Preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies | |
| CN102849694A (en) | Preparation method of batch preparation of boron nitride nanotube | |
| CN107673318B (en) | Boron nitride nanotubes and batch preparation method thereof | |
| CN105000562A (en) | Preparation method of silicon carbide hollow sphere | |
| CN107640751A (en) | One-dimensional boron nitride nano material and preparation method thereof | |
| CN107335456B (en) | Carbon-doped modified graphite-phase carbon nitride photocatalyst and preparation method thereof | |
| CN109833847B (en) | Nickel oxide modified porous boron nitride adsorbent and preparation method thereof | |
| CN101941732A (en) | Mass production method of zinc oxide nanowires | |
| CN102874809A (en) | Silicon carbide composite powder and preparation process thereof | |
| CN101891184A (en) | Method for continuously synthesizing single-wall carbon nano tube by high temperature chemical vapor deposition method | |
| CN107352517B (en) | Preparation method of graphite-phase carbon nitride nano flower bunch with amorphous surface | |
| CN100369806C (en) | Method for synthesizing single shape boron nitride nano tube | |
| CN108928822B (en) | Method for preparing molybdenum carbide by gaseous reduction of molybdenum oxide | |
| CN102874776B (en) | Method for preparing boron nitride nanotubes with pipe diameters less than 100 nanometers in batch | |
| CN1208245C (en) | Preparation of boron nitride nano tube | |
| CN104495947B (en) | A kind of method preparing receiving bore croci | |
| CN107413358B (en) | Black phosphorus quantum dot/attapulgite nano composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130102 |