CN102874776B - Method for preparing boron nitride nanotubes with pipe diameters less than 100 nanometers in batch - Google Patents
Method for preparing boron nitride nanotubes with pipe diameters less than 100 nanometers in batch Download PDFInfo
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- CN102874776B CN102874776B CN201210400173.3A CN201210400173A CN102874776B CN 102874776 B CN102874776 B CN 102874776B CN 201210400173 A CN201210400173 A CN 201210400173A CN 102874776 B CN102874776 B CN 102874776B
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- boron nitride
- cao
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Abstract
The invention relates to a method for preparing boron nitride nanotubes with pipe diameters less than 100 nanometers in batch. The method comprises the following steps of: soaking amorphous boron powder, a transition metal oxide and CaO into 36-38 percent by weight of hydrochloric acid and stirring; after the transition metal oxide and the CaO are dissolved, adding an alkaline solution till precipitates appear; filtering, washing with water and drying to obtain a mixture of the precipitates and the amorphous boron powder; heating the mixture to 1,000-1,100 DEG C under the protection of nitrogen gas or argon gas, and stopping introducing protective gas; introducing mixed gas of ammonia gas or nitrogen gas and hydrogen gas for reacting, and continuously heating to 1,200-1,400 DEG C; preserving heat for 0.5-4 hours; lowering the temperature to the room temperature to obtain a white rough product; and heating the rough product to 600 DEG in the air, washing with acid and drying to obtain boron nitride nanotubes which are 3-100 nanometers in tube diameter and are dozen of microns in length. The method has the advantages of low cost, wide raw material source and easiness in realizing batch production.
Description
Technical field
The invention belongs to field of inorganic nano material, be specifically related to the batch preparation that a kind of caliber is less than the boron nitride nano-tube of 100 nanometers.
Background technology
Boron nitride nano-tube is similar to carbon nanotube, can regard that the carbon atom in carbon nanotube is replaced by boron and nitrogen-atoms the product replacing as.Boron nitride nano-tube not only has mechanical property and the heat-conductive characteristic that can compare favourably with carbon nanotube, but also there is excellent oxidation-resistance, chemical stability and thermostability, it is desirable at structured material that this becomes boron nitride nano-tube, is applied in nano composite 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 good 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.
Conventional boron nitride nanometer tube preparation method has arc discharge method, laser ablation method, template, mechanical ball milling method, CVD and thermal decomposition method etc., for template, mechanical ball milling method, these methods such as CVD and thermal decomposition method not only exist productive rate low, purity is low, and preparation temperature is high, and the high or complex process of cost is difficult to the shortcomings such as industrialization, and the boron nitride nano-tube caliber of preparing is all larger, more than exceeding 100 nanometers; And use arc discharge method, laser ablation methods etc., can obtain thinner boron nitride nano-tube, but cost is high, and productive rate is low, and purity is also lower.High-quality boron nitride nano-tube be difficult to preparation, make to its further research become difficulty, 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, one is provided, and not only productive rate is high, purity is high, preparation condition is gentle, cost is low, technique is simple, prepare the diameter of boron nitride nano-tube of gained below 100 nanometers, and this preparation method is easy to amplify, can reach the object of batch production.
Technical scheme of the present invention is: a kind of caliber is less than the batch preparation of the boron nitride nano-tube of 100 nanometers, it is characterized in that: by unformed boron powder, in the hydrochloric acid of transition metal oxide and CaO immersion 36～38wt%, also stir, after transition metal oxide and CaO dissolving, add basic solution until there is precipitation, again after filtration, washing, be dried the mixture being precipitated with unformed boron powder, after being heated to 1000～1100 ℃ under nitrogen or argon shield, mixture stops passing into shielding gas, then passing into ammonia or nitrogen reacts with the mixed gas of hydrogen and continues to be heated to 1200～1400 ℃, be incubated 0.5～4 hour, then cool the temperature to room temperature, obtain white crude product, pickling after crude product is heated to 600 ℃ in air, dry, obtaining caliber is 3～100 nanometers, length is the boron nitride nano-tube of tens of microns.
Described unformed boron powder, transition metal oxide and CaO three's mol ratio is 1:0.01～0.08:0.03～0.3.
Described transition metal oxide is the oxide compound of Fe or Co or Ni.
Described alkali lye is ammoniacal liquor or sodium hydroxide or potassium hydroxide solution.
The reaction that this preparation method may exist is exemplified below (with unformed boron powder, ferric oxide and calcium oxide are example):
Fe
2O
3+6HCl=2FeCl
3+3H
2O
FeCl
3+3OH
-=Fe(OH)
3+3Cl
-
2Fe(OH)
3=Fe
2O
3+3H
2O
CaO+2HCl=CaCl
2+H
2O
CaCl
2+2OH
-=Ca(OH)
2+2Cl
-
Ca(OH)
2=CaO+H
2O
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: first, and Fe
2o
3generate respectively corresponding salt FeCl with CaO and hydrochloric acid reaction
3and CaCl
3, add alkaline liquid until alkali lye excessive after, FeCl
3and CaCl
3with the OH in solution
-reaction generates respectively flocks Fe (OH)
3with micro-soluble material Ca (OH)
2, these two fully contacts with unformed boron powder in the process stirring, together adhered to one another, when putting into tube furnace after washing and drying and heating, and Fe (OH)
3and Ca (OH)
2be decomposed into again the Fe that particle is tiny
2o
3and CaO, ammonia is decomposed into active nitrogen-atoms and hydrogen simultaneously, and hydrogen is by Fe
2o
3be reduced to simple substance Fe, the Fe particle now generating is tiny, can reach nano level, these Fe particles are active centre of BN nanotube growth nucleation, active nitrogen-atoms and active B atom are dissolved in simple substance Fe, along with the rising of temperature, unformed boron powder and active N atom being dissolved in simple substance Fe is saturated and on top layer, separate out BN film, and wrap up gradually and lifting Fe particle, but because the drop of Fe is poor for the wettability of BN, in the process of parcel, the Fe particle of melting can decline and shake off the parcel of BN film gradually, and BN film is raised gradually, the Fe particle of melting is separation gradually with BN film top, B and N atom continue dissolve 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, and the simple substance Fe uniform particles forming is distributed in CaO, at high temperature can be because of 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 nanotube because have little time to shake off the parcel of BN film.For the control of boron nitride nano-tube caliber, key is the size of the grain diameter of catalyzer, by catalyzer being generated to the precipitation technological process that dehydration is reduced again, granules of catalyst can be controlled to nano level, make nucleation centre reach nano level, thereby the nanotube caliber growing is thinner, can reach below 100 nanometers, and due to precipitation and unformed boron powder adsorb mutually parcel, contact is good, the boron nitride nano-tube caliber generating is also more even, and this is also directly to add the oxyhydroxide of Fe and Ca but not reach the reason of similar effect.
Beneficial effect of the present invention is: by acid, dissolve the technique that the process of alkaline chemical precipitation thermal dehydration reduces catalyst particle size again, can grow easily that a large amount of calibers are less than that 100nm, length reach that tens of microns, pipe shaft are uniform and smooth, pattern with Bamboo-shaped for leading and having a small amount of columned boron nitride nano-tube, this preparation method's cost is lower, raw material sources are extensive, preparation condition is gentle, technological process is simple, be easy to realize batch production, productive rate can reach more than 85%, purity is greater than 90wt%, has industrial application value widely.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the prepared boron nitride nano-tube of embodiment 1.
Fig. 2 is the HRTEM photo of the prepared boron nitride nano-tube of embodiment 1.
Embodiment
Below by specific embodiment, further introduce the present invention, but embodiment can not be construed as limiting the invention.
Embodiment 1
Take 5 grams of amorphous boron powders, 1.45 grams of Fe
2o
3, 1.27 grams of CaO, pour into together in the hydrochloric acid of 38wt% and stir, and treat Fe
2o
3after dissolving with CaO, add strong aqua, until there is precipitation, after filtration, wash and be dried the mixture being precipitated with boron powder.The mixture obtaining is laid on aluminum oxide porcelain plate, is placed in tube furnace, be filled with argon shield and start and heat up, argon flow amount is 300ml/min, while being warming up to 1000 ℃, stops passing into argon gas, starts to pass into NH
3, NH
3flow is 150ml/min, and continue to be heated to 1300 ℃, be incubated 4 hours, after finishing, insulation stops passing into any gas, closing tube furnace enters, air outlet, naturally be cooled to room temperature, obtain white crude product, crude product is heated in air to 600 ℃ and carries out oxide treatment, it is that the hydrochloric acid of 38wt% soaks 6 hours that crude product after oxidation is put into concentration, through suction filtration, washing, after dry, can obtain 10.1 grams of BN nanotube dust, take boron powder as benchmark, its productive rate is 89%, the purity of BN nanotube is about 90%, average caliber is 30 nanometers, length is 90 microns, pipe shaft is uniform and smooth.
Embodiment 2
Take 5 grams of boron powder, 0.83 gram of Co
2o
3, 2.0 grams of CaO, pour into together in the hydrochloric acid of 37wt% and stir, treat Co
2o
3after dissolving with CaO, add strong aqua, until there is precipitation, after filtration, wash and be dried the mixture being precipitated with boron powder.The mixture obtaining is laid on aluminum oxide porcelain plate, is placed in tube furnace, be filled with argon shield and start and heat up, argon flow amount is 300ml/min, while being warming up to 1100 ℃, stops passing into argon gas, starts to pass into NH
3, NH
3flow is 200ml/min, and continue to be heated to 1400 ℃, be incubated 3 hours, after finishing, insulation stops passing into any gas, closing tube furnace enters, air outlet, naturally be cooled to room temperature, obtain white crude product, crude product is heated in air to 600 ℃ and carries out oxide treatment, it is that the hydrochloric acid of 37wt% soaks 12 hours that crude product after oxidation is put into concentration, through suction filtration, washing, after dry, can obtain 9.7 grams of BN nanotube dust, take boron powder as benchmark, its productive rate is 85%, the purity of BN nanotube is about 90%, average caliber is 40 nanometers, length is 80 microns, pipe shaft is uniform and smooth.
Embodiment 3
Take 5 grams of boron powder, 1.0 grams of NiO, 5 grams of CaO, pour into together in the hydrochloric acid of 36wt% and stir, and after NiO and CaO dissolve, add strong aqua, until there is precipitation, after filtration, wash and be dried the mixture being precipitated with boron powder.The mixture obtaining is laid on aluminum oxide porcelain plate, is placed in tube furnace, be filled with argon shield and start and heat up, argon flow amount is 500ml/min, while being warming up to 1000 ℃, stops passing into argon gas, starts to pass into NH
3, NH
3flow is 300ml/min, and continue to be heated to 1200 ℃, be incubated 4 hours, after finishing, insulation stops passing into any gas, closing tube furnace enters, air outlet, naturally be cooled to room temperature, obtain white crude product, crude product is heated in air to 600 ℃ and carries out oxide treatment, it is that the hydrochloric acid of 36wt% soaks 8 hours that crude product after oxidation is put into concentration, through suction filtration, washing, after dry, can obtain 9.8 grams of BN nanotube dust, take boron powder as benchmark, its productive rate is 86%, the purity of BN nanotube is about 90%, average caliber is 20 nanometers, length is 70 microns, 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 be realized the present invention, at this, do not enumerate embodiment.Bound value, the interval value of processing parameter of the present invention (as temperature, soaking time etc.) can be realized the present invention, at this, do not enumerate embodiment.
Claims (2)
1. a caliber is less than or equal to the batch preparation of the boron nitride nano-tube of 100 nanometers, it is characterized in that: by unformed boron powder, in the hydrochloric acid of transition metal oxide and CaO immersion 36～38wt%, also stir, after transition metal oxide and CaO dissolving, add basic solution until there is precipitation, again after filtration, washing, be dried the mixture being precipitated with unformed boron powder, after being heated to 1000～1100 ℃ under nitrogen or argon shield, mixture stops passing into shielding gas, then passing into ammonia or nitrogen reacts with the mixed gas of hydrogen and continues to be heated to 1200～1400 ℃, be incubated 0.5～4 hour, then cool the temperature to room temperature, obtain white crude product, pickling after crude product is heated to 600 ℃ in air, dry, obtaining caliber is 3～100 nanometers, length is the boron nitride nano-tube of tens of microns,
Described unformed boron powder, transition metal oxide and CaO three's mol ratio is 1:0.01～0.08:0.03～0.3;
Described transition metal oxide is the oxide compound of Fe or Co or Ni.
2. the batch preparation of boron nitride nano-tube according to claim 1, is characterized in that: described basic solution is ammoniacal liquor or sodium hydroxide or potassium hydroxide solution.
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| CN102874776B true CN102874776B (en) | 2014-04-23 |
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| 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 |
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| CN101348242A (en) * | 2008-09-05 | 2009-01-21 | 北京工业大学 | Method for preparing boron nitride nanotube by magnesium reduction |
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