CN104528671B - A kind of preparation method of porous boron nitride nanofiber - Google Patents
A kind of preparation method of porous boron nitride nanofiber Download PDFInfo
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- CN104528671B CN104528671B CN201510026727.1A CN201510026727A CN104528671B CN 104528671 B CN104528671 B CN 104528671B CN 201510026727 A CN201510026727 A CN 201510026727A CN 104528671 B CN104528671 B CN 104528671B
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Abstract
The present invention is the preparation method of a kind of porous boron nitride nanofiber, and the method mainly uses three-step synthesis method: the first step, with boric acid and tripolycyanamide as raw material, and Hydrothermal Synthesis melamine hypoboric acid precursor powder；Second step, uses freeze-drying, is lowered the temperature by the hydrothermal solution of melamine hypoboric acid presoma liquid nitrogen quick freeze, is subsequently dried, synthesizes melamine hypoboric acid nanofiber；3rd step, under protective atmosphere, high temperature pyrolysis melamine hypoboric acid nanofiber obtains porous boron nitride nanofiber.Freeze Drying Technique of the present invention achieves melamine hypoboric acid molecular crystal and separates out rapidly nucleation during cooling, avoid growing up of crystal, prepared porous boron nitride fibre diameter has reached nanometer scale, and purity is high, pattern is homogeneous, draw ratio is high, specific surface area is big.
Description
Technical field
Technical scheme relates to boron nitride nanometer material technology synthesis field, a kind of porous boron nitride nanofiber
Synthetic method.
Background technology
The molecular formula of hexagonal boron nitride crystal is BN, is a kind of by the similar graphite of nitrogen (N) atom with boron (B) atomic building
Layer structure material, there is excellent electrical insulating property, high temperature resistant, antioxidation, resistance to chemical attack, thermal conductivity are high, by extensively
For the high-tech area such as machinery, metallurgy, electronics, Aero-Space.
Porous hexagonal nanometer boron nitride fiber is a class by being mutually communicated or to constitute the boron nitride nanometer of network structure fine in blind bore hole
Dimension material.Porous boron nitride nanofiber integrates the advantage of porous boron nitride and nanofiber, not only has big specific surface
Long-pending, abundant pore space structure, and there is mechanical property, chemical stability and the antioxygenic property of excellence, thus process at water,
The aspects such as selective gas absorption and catalyst carrier have broad application prospects.
In recent years, a lot of work are devoted to control synthesizing porous BN structural material.2002, C.Tang et al. used platinum conduct
It is 789m that catalyst auxiliary has synthesized specific surface area2Collapse BN nanotube (C.C.Tang, Y.Bando, X.X.Ding, the S. of/g
R.Qi,D.J.Golberg,J.Am.Chem.Soc.,2002,124,14550-14551).2012, D.Cui et al. used
NH4BF4,NaN3Being raw material with sulfur powder, having synthesized specific surface area in autoclave is 215m2The BN hollow micron ball (G. of/g
Lian,X.Zhang,S.Zhang,D.Liu,D.Cui,Q.Wang,Energy Environ.Sci.,2012,5,7072-7080)。
2013, Q.Weng et al. have employed boric acid and tripolycyanamide as presoma, and at 1000 DEG C, specific surface area is prepared in ammonification
Up to 1488m2The porous BN micro belt of/g (Q.Weng, X.Wang, C.Zhi, Y.Bando, D.Golberg, ACS Nano,
2013,7,1558-1565).Subsequently, Australia Y.Chen et al. reports porous BN nanometer sheet grinding in terms of water process
Study carefully.They use diboron trioxide and guanidine hydrochloride to be that to be at high temperature prepared for specific surface area be 1427m to raw material2Porous BN of/g is received
Rice sheet (W.Lei, D.Portehault, D.Liu, S.Qin, Y.Chen, Nat.Commun., 2013,4,1777).Hereafter, Shandong
University D.Cui et al. uses solvent-thermal method, with H4BF4,NaN3For raw material, CS2For catalyst, prepare straight in autoclave
Superfine nano porous BN fiber (G.Lian, X.Zhang, H.Si, J.Wang, D.Cui, Q.Wang, the ACS of footpath about 8nm
Appl.Mater.Interfaces,2013,5,12773-12778).Said method also exists that preparation is complicated, productivity is low, cost is high,
Need to use the shortcomings such as toxic chemical, be not suitable for large-scale production.The synthetic method of a kind of porous hexagonal boron nitride fiber is (specially
Profit ZL201210475879.6) with boric acid and tripolycyanamide as raw material, use two-step synthesis method, first use hydrothermal synthesis of stephanoporate
The presoma of hexagonal boron nitride fiber, then under protective atmosphere, high temperature pyrolysis obtains nitride porous boron fibre.But this side
The fibre diameter that method obtains is 0.2-7 micron, a length of 20-200 micron, and draw ratio is 2-1000, pattern heterogeneity.To mesh
Till before, also there is no a kind of diameter of preparing in the green of nitride porous boron fibre of nanometer scale, the method for low cost.
Summary of the invention
The technical problem to be solved is: relatively costly for current porous boron nitride technology of preparing, need to use poisonous
Raw material, yield poorly, the deficiency with the nanofiber of high length-diameter ratio can not be obtained, it is provided that a kind of diameter is many less than 100 nanometers
Hole boron nitride nanometer fiber green, low cost, high yield and high-quality preparation method.Lyophilization skill of the present invention
Art achieves melamine hypoboric acid molecular crystal presoma and separates out rapidly nucleation during cooling, it is to avoid growing up of crystal, institute
The porous boron nitride fibre diameter of preparation has reached nanometer scale, and purity is high, pattern is homogeneous, draw ratio is high, specific surface area is big.
The technical scheme is that
The preparation method of a kind of porous boron nitride nanofiber, comprises the steps:
(1) tripolycyanamide and boric acid being dissolved in water, prepare the mixed solution of tripolycyanamide-boric acid-water, its concentration is every milliliter
Water contains 0.005-0.05 gram of tripolycyanamide and 0.005-0.5 gram of boric acid, adds the reaction with reflux after stirring 1-3 hour
Device, preheats 80-95 DEG C and makes it dissolve and be incubated 2-15 hour；Subsequently solution being cooled to 15-30 DEG C, rate of cooling is per minute
1-50 DEG C, there is precipitate to separate out, keep this temperature to place 5-10 hour, be filtrated to get solid sediment；
(2) precipitate obtained in step (1) is put in 75-95 DEG C of drying baker, be incubated 3-8 hour, obtain white solid
Body；
(3) being added to the water by the white solid obtained in step (2), its concentration is that every milliliter of water adds 0.005-0.01 gram in vain
Color solid, preheats 70-90 DEG C and makes it dissolve and be incubated 2-4 hour；
(4) by the solution addition sprayer unit of preparation in step (3), through being sprayed to equipped with in the container of liquid nitrogen, solution is fast
Quickly cooling is frozen and is obtained white solid；In freezer dryer, vacuum freezing is drained subsequently, and the retention time is 48-72 hour, obtains white
Color floccule；
(5) White Flocculus that will obtain in step (4), 900-1500 DEG C of heat treatment under protective atmosphere, heating rate is
1-20 DEG C per minute, temperature retention time is 2-6 hour, at protective atmosphere borehole cooling.Obtain white solid matter and be porous boron nitride
Nanofiber.
Protective atmosphere described in previous step (5) is argon or nitrogen.
When protective atmosphere in previous step (5) is argon or nitrogen, gas flow rate is 50-500 milliliter/per minute.
The mechanism of the present invention: raw material tripolycyanamide and boric acid are dissolved in 80-95 DEG C of aqueous solution, separates out through cooling, filters and be dried
After obtain melamine hypoboric acid molecular crystal precursor powder (step 1,2)；Precursor powder is dissolved in 70-90 DEG C of aqueous solution,
During spraying subsequently and liquid nitrogen quickly cool down, melamine hypoboric acid molecular crystal quickly separates out nucleation from solution, it is to avoid
Growing up of crystal, defines white solid containing a large amount of melamine hypoboric acid nanofibers, freeze-dried makes white solid
In ice distillation, obtained cotton-shaped melamine hypoboric acid nanofiber (step 3,4)；In high-temperature heat treatment process subsequently,
Melamine hypoboric acid nanofiber decomposes, and discharges substantial amounts of CO2, NH3Deng gas, ultimately form porous boron nitride nanofiber (step
Rapid 5).
The invention has the beneficial effects as follows:
1. the product obtained by the inventive method is pure phase high length-diameter ratio boron nitride nanometer fiber.The diffraction of XRD spectra (Fig. 1)
Peak is clear, for staggered floor boron nitride, does not has the diffraction maximum of other dephasigns to occur；SEM and TEM figure (Fig. 2 and Fig. 3) display
The diameter about 20-50 nanometer of prepared boron nitride nanometer fiber, length about 10-30 micron, draw ratio is up to 200-1500,
Product morphology is homogeneous, purity about 95%.Fig. 4 is the high-resolution TEM figure of product, and display boron nitride nanometer fiber is porous knot
Structure.Fig. 5 shows absorption and the desorption isotherm of nitrogen under the porous boron nitride nanofiber low temperature that this method obtains.
2. the inventive method uses boric acid and tripolycyanamide to be raw material, obtains melamine hypoboric acid nanometer through atmospheric pressure reflux lyophilization
Fiber is as presoma, and at high temperature heating prepares, and overcomes the reaction under high pressure that existing porous boron nitride synthetic technology usually requires that
The particular/special requirements such as device, toxic raw materials or noble metal catalyst, reduce energy consumption and production cost, and method is nontoxic, reliable, suitable
Scale for porous boron nitride nanofiber synthesizes.
Raw material the most of the present invention is boric acid and tripolycyanamide, except distilled water is without other additives in preparation process, protects
Demonstrate,prove the purity of product.
4. the porous boron nitride nanofiber pattern of present invention synthesis is homogeneous, and diameter Distribution is 20-50 nanometer, a length of 10-30
Micron, draw ratio is up to 200-1500, and specific surface area is high.This diameter nanometer scale, have high-purity, high length-diameter ratio and
The nitride porous boron fibre of high-specific surface area can strengthen its heat conductivility as polymeric additive, it is possible at water process, selectivity
The aspect such as gas absorption and catalyst carrier is applied.Porous boron nitride nanofiber synthesized by the present invention compares patent
The micron order product of ZL201210475879.6 processes at water, gas absorption application aspect has the faster rate of adsorption and higher
Adsorption efficiency.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of porous boron nitride nanofiber in embodiment 1.
Fig. 2 is the scanning electron microscope diagram of porous boron nitride nanofiber in embodiment 1.
Fig. 3 is the transmission electron microscope figure of porous boron nitride nanofiber in embodiment 1.
Fig. 4 is the high resolution transmission electron microscopy figure of porous boron nitride nanofiber in embodiment 1.
Fig. 5 is the low temperature nitrogen adsorption and desorption isothermal line of porous boron nitride nanofiber in embodiment 1.
Detailed description of the invention
The present invention is further described with instantiation below in conjunction with the accompanying drawings.
The sprayer unit and the freezer dryer that use in the embodiment of the present invention are known device.
Embodiment 1
(1) tripolycyanamide and boric acid being dissolved in water, prepare the mixed solution of tripolycyanamide-boric acid-water, its concentration is every milliliter
Water contains 0.012 gram of tripolycyanamide and 0.018 gram of boric acid, then stirring 2 hours, adds the reactor with reflux, in advance
Heat 85 DEG C makes it dissolve and is incubated 5 hours；Subsequently solution is cooled to 25 DEG C with the speed of cooling per minute 1 DEG C, has white heavy
Shallow lake thing separates out, and keeps this temperature to place 8 hours, is filtrated to get solid sediment；
(2) precipitate obtained in step (1) is put in 95 DEG C of drying bakers, be incubated 8 hours, obtain white solid；
(3) being added to the water by the white solid obtained in step (2), wherein, every milliliter of water adds 0.006 gram of white solid,
Then preheating 85 DEG C makes it dissolve and is incubated 2 hours；
(4) being added in spraying kettle by the solution of preparation in step (3), through being sprayed to equipped with in the container of liquid nitrogen, solution is fast
Quickly cooling is frozen and is obtained white solid；Subsequently the container filling white solid is put into freezing in freezer dryer drain (temperature-50 DEG C,
20Pa), keep freezing to drain 72 hours, obtain White Flocculus.
(5) solid that will obtain in step (4), 1200 DEG C of heat treatments in argon gas atmosphere, heating rate is 10 DEG C per minute,
Temperature retention time is 4 hours, gas flow rate is 100 milliliters/and per minute, Temperature fall in argon gas atmosphere.Obtain product for many
Hole hexagonal boron nitride fiber.
Testing through XRD, it is staggered floor boron nitride that the diffraction maximum of Fig. 1 shows product, and does not has the diffraction maximum of other dephasigns to occur,
Illustrate that the purity through the porous boron nitride nanofiber prepared by the inventive method is high.Nitride porous is found out through SEM figure (Fig. 2)
Boron nanofiber has one-dimensional wire pattern, length about 10-30 micron, purity about 95%, illustrates that product morphology is homogeneous, purity
Height, yield is big；TEM figure (Fig. 3) display porous boron nitride nanofiber diameter is about 20-50 nanometer, and draw ratio is up to
200-1500, does not has impurity particle to be present in nanofiber, and purity is high；High-resolution TEM figure (Fig. 4) shows that boron nitride is received
Rice fiber is loose structure；By surveying BET (Fig. 5), the specific surface area that can calculate nitride porous boron fibre is 279.679
m2/ g, the boron nitride nanometer fiber prepared by explanation has high specific surface area.What the above collection of illustrative plates explanation present invention obtained is pattern
Phase homogeneous, pure, cavernous boron nitride nanometer fibrous material.
Embodiment 2, example 3
Change the concentration of step (1) tripolycyanamide in embodiment 1 into every milliliter of water respectively and contain 0.005 gram, 0.05 gram of tripolycyanamide,
Other operations is the most same as in Example 1, and the product obtained is with embodiment 1.
Embodiment 4, example 5
Change the concentration of step (1) boric acid in embodiment 1 into every milliliter of water respectively and contain 0.005 gram, 0.5 gram of boric acid, other each
Item operation is the most same as in Example 1, and the product obtained is with embodiment 1.
Embodiment 6
Change the concentration that white solid in step (3) in embodiment 1 is added to the water into every milliliter of water and contain 0.02 gram of white solid,
Other operations is the most same as in Example 1, obtains porous boron nitride nanofiber, and sem analysis shows obtained nitridation
The diameter of boron nanofiber about 50-100 nanometer, length about 10-30 micron.
Embodiment 7, example 8
Change the heat treatment temperature of step (5) in embodiment 1 into 1100 DEG C, 1300 DEG C respectively, other operations all with implement
Example 1 is identical, and the product obtained is with embodiment 1.
Embodiment 9,10
Changing step (5) protective atmosphere in embodiment 1 into nitrogen, other operations is the most same as in Example 1, the product obtained
With embodiment 1.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. a preparation method for porous boron nitride nanofiber, is characterized by comprise the steps:
(1) tripolycyanamide and boric acid are dissolved in water, prepare the mixed solution of tripolycyanamide-boric acid-water, its concentration is that every milliliter of water contains 0.005-0.05 gram of tripolycyanamide and 0.005-0.5 gram of boric acid, add the reactor with reflux after stirring 1-3 hour, preheat 80-95 DEG C and make it dissolve and be incubated 2-15 hour；Subsequently solution being cooled to 15-30 DEG C, rate of cooling is 1-50 DEG C per minute, has precipitate to separate out, and is incubated 5-10 hour, is filtrated to get solid sediment；
(2) precipitate obtained in step (1) is put in 75-95 DEG C of drying baker, be incubated 3-8 hour, obtain white solid；
(3) being added to the water by the white solid obtained in step (2), its concentration is that every milliliter of water adds 0.005-0.01 gram of white solid, preheats 70-90 DEG C and makes it dissolve and be incubated 2-4 hour；
(4) by the solution addition sprayer unit of preparation in step (3), through being sprayed to equipped with in the container of liquid nitrogen, solution quick freeze obtains white solid；In freezer dryer, vacuum freezing is drained subsequently, and the retention time is 48-72 hour, obtains White Flocculus；
(5) White Flocculus that will obtain in step (4); 900-1500 DEG C of heat treatment under protective atmosphere, heating rate is 1-20 DEG C per minute, and temperature retention time is 2-6 hour; at protective atmosphere borehole cooling, obtain white solid matter and be porous boron nitride nanofiber.
2. the preparation method of porous boron nitride nanofiber as claimed in claim 1, is characterized by that the protective atmosphere described in step (5) is argon or nitrogen.
3. the preparation method of porous boron nitride nanofiber as claimed in claim 1, is characterized by that the gas flow rate of the protective atmosphere in step (5) is 50-500 milliliter/per minute.
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| CN106116617B (en) * | 2016-06-20 | 2019-05-14 | 华南理工大学 | A kind of ultra-fine boron nitride porous fibre toughening WC composite material and preparation method |
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| CN109647369B (en) * | 2019-01-15 | 2022-03-25 | 浙江师范大学 | Porous carbon nano-catalyst, preparation method and application thereof |
| CN109704296B (en) * | 2019-02-22 | 2020-10-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible boron nitride nanobelt aerogel and preparation method thereof |
| CN110075899A (en) * | 2019-04-30 | 2019-08-02 | 河北工业大学 | A kind of preparation method for the bimetallic catalyst that porous boron nitride is nano-fibre supported |
| CN110629323B (en) * | 2019-10-14 | 2021-11-16 | 河北工业大学 | Method for synthesizing porous boron nitride fiber with high length-diameter ratio under assistance of organic solvent |
| CN110683573B (en) * | 2019-11-18 | 2022-02-08 | 河北工业大学 | Method for preparing indium oxide nanotube by using porous BN nano fiber as template |
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| CN111762763B (en) * | 2020-06-29 | 2022-10-11 | 中国科学院金属研究所 | Method for realizing microstructure regulation and control of boron nitride aerogel by inducing supramolecular morphology transformation through solvent |
| CN112342017B (en) * | 2020-11-06 | 2021-08-10 | 山东大学 | Ultra-long-life room temperature phosphorescent material and preparation method and application thereof |
| CN112877810B (en) * | 2021-02-01 | 2021-11-16 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
| CN112938911A (en) * | 2021-03-24 | 2021-06-11 | 云南华谱量子材料有限公司 | Preparation method of boron nitride nanosheet |
| CN114560717A (en) * | 2022-04-06 | 2022-05-31 | 中国科学院赣江创新研究院 | Preparation method and application of one-dimensional porous boron nitride fiber material |
| CN115138328A (en) * | 2022-08-02 | 2022-10-04 | 江苏大学 | Aluminum-doped boron nitride nanofiber monoatomic adsorbent and preparation method and application thereof |
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| CN102126709B (en) * | 2010-01-20 | 2013-04-03 | 中国科学院金属研究所 | Preparation method of boron nitride one-dimensional nanostructure macroscopic rope |
| CN102936138B (en) * | 2012-11-22 | 2014-01-15 | 河北工业大学 | Synthesis method of porous hexagonal boron nitride fiber |
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