CN101348242A - Method for preparing boron nitride nanotube by magnesium reduction - Google Patents
Method for preparing boron nitride nanotube by magnesium reduction Download PDFInfo
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- CN101348242A CN101348242A CNA2008101196926A CN200810119692A CN101348242A CN 101348242 A CN101348242 A CN 101348242A CN A2008101196926 A CNA2008101196926 A CN A2008101196926A CN 200810119692 A CN200810119692 A CN 200810119692A CN 101348242 A CN101348242 A CN 101348242A
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Abstract
The invention provides a method for preparing a borazon nano pipe by the magnesium-thermic reduction, belonging to the inorganic nano material field. In the prior method for preparing the borazon nano pipe, the problems of low yield and high cost exist. The method of the invention comprises the following steps that : (1) under argon shield, according to the mol ratio of 1:1-3:0.01-0.1, borazon, magnesium and ferrous salt are ground, mixed and screened; (2) under argon shield, the screened mixture is heated, and at a temperature of between 900 and 1,200 DEG C, argon gas is closed and the ammonia gas is filled, and when the temperature reaches between 1,200 and 1,600 DEG C, the temperature is maintained for 1 to 5h; (3) after the temperature decreases to the room temperature, the mixture is immersed in nitric acid, the product obtained has impurities removed, and the borazon nano pipe is obtained. The method of the invention has the advantages of simple process, easy control and amplification of reaction, low cost, high yield and uniform size and high purity of the prepared borazon nano pipe.
Description
Technical field
The invention belongs to field of inorganic nano material, be specifically related to a kind of method that adopts magnesium reduction process to prepare boron nitride nano-tube.
Background technology
Hexagonal boron nitride and graphite are isoelectronic specieses, have very similar laminate structure.The same with carbon nanotube, boron nitride also can form the respective tubular nanostructure.Boron nitride nano-tube also has good chemical stability and thermostability except having high-modulus and the high-strong toughness that energy and carbon nanotube compare favourably.In addition, boron nitride nano-tube has and the distinct electric property of carbon nanotube, show as broad-band gap semi-conductor (～5.5eV), its electric property and caliber, helicity and tube wall number are irrelevant.The exclusive characteristic of boron nitride nano-tube makes it at aspects such as Nano semiconductor device, nano heterogeneous ceramic, hydrogen storage materials the application prospect that has temptation be arranged, and has caused the extensive interest of Chinese scholars.
The method for preparing boron nitride nano-tube mainly contains arc process, laser ablation method, presoma pyrolysis method, carbon nanotube template, ball milling-annealing method, chemical Vapor deposition process etc.Though obtained some successes and progress aspect preparing at boron nitride nano-tube in recent years, as a whole, also exist output, productive rate lower, easily bring impurity into, product structure and microscopic appearance size are difficult to problems such as control.Chemical Vapor deposition process is the method that relatively effectively prepares a large amount of boron nitride nano-tubes at present, owing to adopt different initiator and reaction process condition, products therefrom has different characteristics.As adopt the growth stimulant of Aquo Systems such as water or hydrochloric acid as boron nitride nano-tube, the nanotube size span that obtains is bigger, be generally about tens to 200 nanometers, and mostly be ring shape nanotube, and the infringement to reaction vessel and equipment at high temperature of moisture or sour gas is very big, influences the work-ing life of equipment and causes preparation cost to improve; With the catalyzer of magnesium oxide-iron protoxide as the preparation boron nitride nano-tube, adopt certain technology can obtain higher degree, the uniform boron nitride nano-tube of size, the mass-produced potentiality of realization are arranged, but this method needs expensive high purity boron powder as the boron source, and to adopt the extremely unsettled iron protoxide of chemical property be catalyzer, so preparation cost is higher.Up to now, has the low-cost preparation method of high yield, high purity, the uniform boron nitride nano-tube of size still in the middle of exploring.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and provide a kind of productive rate height, purity height, size even, surperficial no significant defect and the method for preparing boron nitride nano-tube with low cost.
Method provided by the present invention is in argon shield atmosphere, is the boron source with the boron trioxide, and magnesium is reductive agent, is catalyzer with a kind of in iron protochloride, ferrous sulfate or the Ferrox, and ammonia is a nitrogenous source, makes boron nitride nano-tube, and concrete steps are as follows:
1) under argon shield, with boron oxide, magnesium and ferrous salt, 1: 1 in molar ratio～3: 0.01～0.1 place the mortar ground and mixed after, cross 300 eye mesh screens;
2) mixture after sieving in the step 1) is heated under the argon shield condition, when temperature reaches 900～1200 ℃, stop to feed argon gas and feed ammonia, when waiting to reach 1200～1600 ℃ of design temperatures, constant temperature 1～5 hour;
3) constant temperature is reduced to room temperature after finishing, and with the products therefrom nitric acid dousing, removes the impurity that contains magnesium, iron, obtains boron nitride nano-tube.
Wherein, the ferrous salt described in the step 1) is a kind of in iron protochloride, ferrous sulfate or the Ferrox.
Principle of the present invention is that MAGNESIUM METAL is reduced to pure boron with boron trioxide under the argon shield condition, and generates magnesium oxide; Simultaneously, the ferrous salt decomposition obtains iron protoxide; At high temperature, pure boron and magnesium oxide reaction in generate gasiform boron nitride presoma; Under the katalysis of iron protoxide, boron nitride presoma and ammonia gas react generate boron nitride nano-tube.
The present invention compared with prior art has following beneficial effect:
The inventive method avoids using expensive high purity boron powder to be the boron source, and the extremely unsettled iron protoxide of chemical property is a catalyzer, thereby preparation cost is cheap relatively, preparation technology is simple, good reproducibility, reaction is easy to control and amplifies, gained boron nitride nano-tube output is big, be easy to purify, size evenly, the microtexture no significant defect.
Description of drawings
Fig. 1 is the stereoscan photograph of the prepared boron nitride nano-tube of the present invention.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
The model of employed horizontal pipe stove is CVD (G) 06/45/1 in the embodiment of the invention, and the scanning electron microscope model is FEI nanoSEM 200.
Embodiment 1
1) under argon shield, after boron oxide, magnesium and iron protochloride placed agate mortar fully to grind in 1: 1: 0.1 in molar ratio reactant is mixed fully, crosses 300 eye mesh screens;
2) mixture after sieving in the step 1) is packed into aluminium sesquioxide porcelain boat and place the flat-temperature zone of horizontal pipe stove feeds the 50sccm argon gas, begins to heat up, when temperature reaches 900 ℃, close argon gas and feed the 50sccm ammonia and continue to heat up, when waiting to reach 1200 ℃, constant temperature 5 hours;
Close inlet mouth and venting port simultaneously when 3) constant temperature finishes, cool to room temperature with the furnace, product is a platinum sponge shape block in the porcelain boat, high resilience, and the impurity after product that contains magnesium, iron with the nitric acid flush away is the white powder of homogeneous, weight does not obviously change.
Embodiment 2
1) under argon shield, after boron oxide, magnesium and ferrous sulfate placed agate mortar fully to grind in 1: 2: 0.05 in molar ratio reactant is mixed fully, crosses 300 eye mesh screens;
2) mixture after sieving in the step 1) is packed into aluminium sesquioxide porcelain boat and place the flat-temperature zone of horizontal pipe stove feeds the 100sccm argon gas, begins to heat up, when temperature reaches 1100 ℃, close argon gas and feed the 100sccm ammonia and continue to heat up, when waiting to reach 1400 ℃, constant temperature 2 hours;
Close inlet mouth and venting port simultaneously when 3) constant temperature finishes, cool to room temperature with the furnace, product is a platinum sponge shape block in the porcelain boat, high resilience, and the impurity after product that contains magnesium, iron with the nitric acid flush away is the white powder of homogeneous, weight does not obviously change.
Embodiment 3
1) under argon shield, after boron oxide, magnesium and Ferrox placed agate mortar fully to grind in 1: 3: 0.01 in molar ratio reactant is mixed fully, crosses 300 eye mesh screens;
2) mixture after sieving in the step 1) is packed into aluminium sesquioxide porcelain boat and place the flat-temperature zone of horizontal pipe stove feeds the 200sccm argon gas, begins to heat up, when temperature reaches 1200 ℃, close argon gas and feed the 200sccm ammonia and continue to heat up, when waiting to reach 1600 ℃, constant temperature 1 hour;
Close inlet mouth and venting port simultaneously when 3) constant temperature finishes, cool to room temperature with the furnace, product is a platinum sponge shape block in the porcelain boat, high resilience, and the impurity after product that contains magnesium, iron with the nitric acid flush away is the white powder of homogeneous, weight does not obviously change.
Respectively embodiment 1,2 and 3 prepared white powders are carried out scanning electron microscopic observation and find that product is the one dimension tubular structure, does not find that there is obvious filling thing (as shown in Figure 1) pipe shaft inside.Transmission electron microscope results shows that product is many walls nanotube, and external diameter is between 40～60nm, and is interior between 10～30nm, length 10～30 μ m, and gained boron nitride nano-tube surface clean does not have coverture, finds that seldom there is weighting material pipe shaft inside.The energy loss spectroscopy analysis revealed, boron in the product: the nitrogen-atoms ratio is 1: 1, illustrates that the purity of 1-dimention nano pipe in the product is very high.
Claims (2)
1, a kind of method of preparing boron nitride nanotube by magnesium reduction is characterized in that, may further comprise the steps:
1) under the argon shield condition,, after 1: 1 in molar ratio～3: 0.01～0.1 ground and mixed, crosses 300 eye mesh screens with boron oxide, magnesium and ferrous salt;
2) mixture after sieving in the step 1) is heated under the argon shield condition, when temperature reaches 900～1200 ℃, stop to feed argon gas and feed ammonia, when treating that temperature reaches 1200～1600 ℃, constant temperature 1～5 hour;
3) constant temperature is reduced to room temperature after finishing, and products therefrom is removed impurity with nitric acid dousing, obtains boron nitride nano-tube.
2, method according to claim 1 is characterized in that, the ferrous salt described in the step 1) is a kind of in iron protochloride, ferrous sulfate or the Ferrox.
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| CNA2008101196926A CN101348242A (en) | 2008-09-05 | 2008-09-05 | Method for preparing boron nitride nanotube by magnesium reduction |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863664A (en) * | 2010-07-15 | 2010-10-20 | 武汉工程大学 | In situ compound ceramic powder of boron nitride nanotube and preparation method thereof |
| CN101718733B (en) * | 2009-12-09 | 2012-07-25 | 黑龙江大学 | Boron-nitrogen nanowire/semiconductor oxide composite and preparation method thereof |
| CN102849694A (en) * | 2012-10-20 | 2013-01-02 | 景德镇陶瓷学院 | Preparation method of batch preparation of boron nitride nanotube |
| CN102874776A (en) * | 2012-10-20 | 2013-01-16 | 景德镇陶瓷学院 | Method for preparing boron nitride nanotubes with pipe diameters less than 100 nanometers in batch |
| CN103803513A (en) * | 2014-03-13 | 2014-05-21 | 中国人民解放军国防科学技术大学 | Preparation method of boron nitride nanotube |
| CN103922295A (en) * | 2014-04-17 | 2014-07-16 | 河北工业大学 | Preparation method of boron nitride nano tube |
| CN108047447A (en) * | 2017-12-07 | 2018-05-18 | 黑龙江科技大学 | A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability |
| DE112013007154B4 (en) | 2013-06-14 | 2018-10-31 | Yeditepe Universitesi | Production process for boron nitride nanotubes |
| CN111204720A (en) * | 2020-02-10 | 2020-05-29 | 浙江硼矩新材料科技有限公司 | Batch preparation method of boron nitride nanotubes |
| CN113336202A (en) * | 2021-07-05 | 2021-09-03 | 南京大学 | High-purity boron nitride nanotube and preparation method thereof |
| CN114421093A (en) * | 2020-10-13 | 2022-04-29 | 湖南大学 | Flexible boron nitride nanotube inorganic diaphragm, preparation thereof and application thereof in lithium secondary battery |
-
2008
- 2008-09-05 CN CNA2008101196926A patent/CN101348242A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101718733B (en) * | 2009-12-09 | 2012-07-25 | 黑龙江大学 | Boron-nitrogen nanowire/semiconductor oxide composite and preparation method thereof |
| CN101863664A (en) * | 2010-07-15 | 2010-10-20 | 武汉工程大学 | In situ compound ceramic powder of boron nitride nanotube and preparation method thereof |
| CN101863664B (en) * | 2010-07-15 | 2012-08-29 | 武汉工程大学 | In situ compound ceramic powder of boron nitride nanotube and preparation method thereof |
| CN102849694A (en) * | 2012-10-20 | 2013-01-02 | 景德镇陶瓷学院 | Preparation method of batch preparation of boron nitride nanotube |
| CN102874776A (en) * | 2012-10-20 | 2013-01-16 | 景德镇陶瓷学院 | Method for preparing boron nitride nanotubes with pipe diameters less than 100 nanometers in batch |
| DE112013007154B4 (en) | 2013-06-14 | 2018-10-31 | Yeditepe Universitesi | Production process for boron nitride nanotubes |
| CN103803513A (en) * | 2014-03-13 | 2014-05-21 | 中国人民解放军国防科学技术大学 | Preparation method of boron nitride nanotube |
| CN103922295A (en) * | 2014-04-17 | 2014-07-16 | 河北工业大学 | Preparation method of boron nitride nano tube |
| CN103922295B (en) * | 2014-04-17 | 2015-11-04 | 河北工业大学 | A kind of preparation method of boron nitride nano-tube |
| CN108047447A (en) * | 2017-12-07 | 2018-05-18 | 黑龙江科技大学 | A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability |
| CN111204720A (en) * | 2020-02-10 | 2020-05-29 | 浙江硼矩新材料科技有限公司 | Batch preparation method of boron nitride nanotubes |
| CN114421093A (en) * | 2020-10-13 | 2022-04-29 | 湖南大学 | Flexible boron nitride nanotube inorganic diaphragm, preparation thereof and application thereof in lithium secondary battery |
| CN114421093B (en) * | 2020-10-13 | 2023-02-24 | 湖南大学 | Flexible boron nitride nanotube inorganic diaphragm, preparation thereof and application thereof in lithium secondary battery |
| CN113336202A (en) * | 2021-07-05 | 2021-09-03 | 南京大学 | High-purity boron nitride nanotube and preparation method thereof |
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Open date: 20090121 |