CN1397491A - Nano structure of boron nitride and boron carbonide and its preparing process - Google Patents

Nano structure of boron nitride and boron carbonide and its preparing process Download PDF

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CN1397491A
CN1397491A CN 02138035 CN02138035A CN1397491A CN 1397491 A CN1397491 A CN 1397491A CN 02138035 CN02138035 CN 02138035 CN 02138035 A CN02138035 A CN 02138035A CN 1397491 A CN1397491 A CN 1397491A
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nanostructure
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胡征
霍开富
付继江
王喜章
陈懿
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Nanjing University
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Nanjing University
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Abstract

A BN or BC nanostructure is prepared from N or C contained gas or solid, and B-contained alloy particles as catalyst chosen from Fe-B, Ni-B, Co-B, Fe-Ni-B, Fe-Co-B, Ni-Co-B, etc through reaction at 1000-1300 deg.C in tubular furnace.

Description

Boron nitride and norbide nanostructure and preparation method thereof
One, technical field
The present invention relates to novel nanostructures such as the BN of BN and BC nanotube, nano wire, soccerballene and other nanoparticle of parcel and BC Nano capsule.The present invention also relates to adopt the nanoparticle of boracic to make catalyzer and provide B source, gas phase or solid phase precursor to provide nitrogenous source, carbon source to carry out the novel method that prepared in reaction comprises BN, BC and B-C-N class nanostructure.
Two, background technology
Since C60 found, carbon nano-structured (comprising soccerballene, nanotube, nano wire, nanometer ball, green onion, Nano capsule etc.) was because its great scientific value and potential application prospect have caused people's extensive interest and attention.Theoretical and experimental study all shows carbon nano-structured performance with a series of excellences, as good chemistry and thermostability, high physical strength, special electric property and the field emission characteristic of excellence etc.At present, people have developed the multiple technologies route and have synthesized this class nanostructure, as arc discharge method, laser evaporation method and thermal chemical vapor deposition method etc.
A series of important carbon nano-structured and discoveries character have excited people to explore the interest of new system.Hexagonal boron nitride (h-BN) and norbide and graphite aspect structural similitude, similarly, the BN of a series of novelties and BC nanostructure also are found in succession.H-BN and BC are a kind of semiconductor materials, have good physics and chemical property, and as high temperature resistant, anti-oxidant, resistance to chemical attack, good thermal conductivity, wave and high dielectric properties also are a kind of field emmision materials of excellent property simultaneously.BN and BC nanostructure---a kind of carbon nano-structured analogue by h-BN and BC form also has some unusual character.For example: the BN nanotube has unique electrical property.The electroconductibility that is different from carbon nanotube depends on the characteristics of its caliber and helicity, the electroconductibility of BN nanotube and caliber and very little (the X.Blas é of helicity relation, et al.Europhys.Lett.28 (1994), 335), when it manages radius greater than 0.6nm, the BN nanotube is a kind of wide-band-gap semiconductor material with single band gap, band gap width～5.5ev (Phys.Rev.B 49 (7) 5081).The BN structure is carried out that carbon mixes and the BC nanostructure is carried out nitrogen mix, its electrical properties can be along with the variation of composition modulation (X.Blas é, et al.Appl.Phys.Lett.70 (1997) 197) continuously.Compare with carbon nano-structured, BN and BC nanostructure show stronger high temperature resistant, antioxidant property, can provide the inertia protective layer to other nanostructures of its parcel.Thereby boron nitride and norbide nanostructure are the novel materials that a class has important scientific value and wide application prospect.
Existing BN and BC nanostructure synthetic technology comprise arc discharge method (N.G.Chopra, et al.Science 269 (1995) 966), laser evaporation method (D.Bolberg et al.Appl.Phys.Lett.69 (1996) 2045), carbon nanotube method of substitution (W.Han et al.Appl.Phys.Lett.73 (1998) 3085) and chemical Vapor deposition process (Fan S.S et al.Mater.Lett.51,315 (2001), Mcllroy D.N.et.al..J.Mater.Sci.Lett 18 (1999) 1513) etc.
In carbon nano-structured synthesizing, technology is simple owing to having, low cost and other advantages has obtained extensive employing for chemical Vapor deposition process.Adopt technology and the also existing documents of method of synthetic BN of chemical gaseous phase depositing process and BC nanostructure to report for work at present.Using plasmas such as Hu Zheng strengthen chemical Vapor deposition process, respectively with B 2H 6, N 2/ NH 3For B source and N source, with the aluminum oxide is that template has prepared BN and BC nano-tube array (Chinese patent CNl312217A); Tsing-Hua University's model is kept kind the grade with ferric oxide (Fe 2O 3) powder is catalyzer, respectively with solid-state indefiniteness boron (B) and NH 3Be B source and N source, reaction obtains BN nanotube (Fan S.S et al.Mater.Lett.51 (2001) 315) under 1300 ℃.Deepak etc. are catalyzer with metallic iron (Fe) powder, respectively with boric acid (HBO 3) and ammonia (NH 3) gas is B source and N source, 1000 ℃ down reaction obtaining BN (Deepak F.L.et al., Chem.Phys.Lett, 353 (2002) 345).Mcllroy etc. are with C 2B 10H 12Being boron source and carbon source, is that catalyzer has synthesized BC nano wire (Mcllroy D.N.et al.Appl.Phys.Lett 79 (2001) 1540) in 1100 ℃ with iron under action of plasma.Mark etc. are with 6,6 '-(CH 2) 6(B 10H 13) 2Being boron source and carbon source, is that template has prepared BC nano-tube array (Mark.J et al.Chem.Mater.12 (2000) 280) with the aluminum oxide.Oku T.et al. etc. are with boric acid (HBO 3) and urea (CO (NH 2) 2) mixture of Silver Nitrate synthesized the BN Nano capsule (T.Oku et al.J.Mater.Chem 10 (2000) 255) of parcel silver in 700 ℃ of hydrogen atmospheres.Kitahara etc. are catalyzer with cobalt (Co), are that boron source and nitrogenous source are in 800 ℃ of boron nitride nanometer capsules (Kitahara K.DiamondRelat.Mater.10 (2001) 1210) that obtain wrapping up cobalt with boron powder and ammonia respectively.Terrones etc. are catalyzer with the cobalt metal powder, in 900-1000 ℃ of following pyrolysis CH 3CN: BCl 3Obtain B-C-N nanofiber (Terrones.M et al.Chem.Phys.Lett.257 (1996) 576).
The document that above-mentioned chemical gaseous phase depositing process prepares BN and BC nanostructure can be divided into two big classes, and a class is Vapor-Liquid-Solid (VLS) growth mechanism (X.C.Wu et al.Chem.Phys.Lett.336,53 (2001).Principal feature is: one, appropriate catalyst must be arranged, and catalyzer is in liquid state during nanostructure growth, so need suitable temperature.It two must have precursor nitrogenous, boracic, and precursor constantly enters catalyzer by dissociating or reacting after generating the target product species on catalyzer drop surface, separates out, generates nanostructure reach supersaturation in the catalyzer drop after.Another kind of is template control growing method, for example, adopts porous alumina formwork, and reactant reacts under the space constraint effect in template duct and generates specific nanostructure (B.Konstantin et al.Chem.Mater.12 (2000) 2500).
Three, summary of the invention
The novel method or the new technology path that the purpose of this invention is to provide a kind of BN of preparation and BC nanostructure, and prepare BN and BC nanostructure with property with this, comprise the BN of BN and BC nanotube, nano wire, soccerballene and parcel B nanoparticle and BC Nano capsule etc.Specifically, make nanometer " catalyzer " alloy that contains the required constituent element of portion of product earlier, it is own that the product constituent element partly derives from " catalyzer ", and part derives from gas phase (or solid phase) precursor.For example, from gas phase precursor NH 3/ N 2In the N atom with in " catalyzer " drop chemical reaction takes place from the B atom in the Fe-B nanometer " catalyzer ", when reaching supersaturation in " catalyzer " drop, the BN species that generate, under different condition, form the BN nanostructure of variform just so that liquid-solid interface can minimum mode be separated out from certain crystal face.
The object of the invention also is, by the CONTROL PROCESS condition, and boracic catalyst particle size and boron-containing quantity and obtain the BN and the BC Nano capsule of the rich nano wire of rich nanotube, BN and BC, BN and BC soccerballene and parcel B and the boron-containing alloy etc. of BN and BC.
The present invention is with the main difference that existing VLS class methods are compared, present method has been introduced respectively provides product required constituent element respectively from gas phase (or solid phase) precursor and two channels of " catalyzer " alloy, and this crucial innovation link of chemical reaction generation target product takes place in the catalyzer drop.And in the document in the VLS class growth method the required species of product only provide by precursor, catalyzer only works dissociate precursor and transmission medium.This difference makes present method have many new characteristics.
The present invention is achieved through the following technical solutions:
1 device required for the present invention mainly contains body of heater, gas distributing system and vacuum system three parts and forms, the relation of its each several part is as follows with effect: the reaction chamber that (1) is made by alundum tube or stainless steel tube places in the tube furnace, be placed with the quartz boat that contains B catalyst and place the reaction chamber center, the temperature of vitellarium can be regulated and control, and is beneficial to the growth of BN and BC nanostructure.(2) gas distributing system is made up of gas circuit and mass flowmeter, is connected to an end of growth room, utilizes it can regulate kind, flow and the proportioning of BN and BC nanostructure growth chamber gas.(3) vacuum system, utilize it can be before heating up in the growth room applying argon gas and vacuumizing repeatedly, get rid of oxidized possibility under the catalyst nanoparticles high temperature in the growth room, also can regulate vacuum tightness and reacting gas pressure in the growth room simultaneously.
The B-contained nano-catalyst alloy particle that 2 the present invention adopt is mainly Fe-B, Ni-B, Co-B, Fe-Ni-B, Fe-Co-B, Ni-Co-B etc.Its general formula is Fe xB 100-x, Ni yB 100-yCo zB 100-zFe aNi bB 100-a-bFe aCo bB 100-a-b, x, y, z get 30-80, a+b gets 30-80.
3 can use compound solid state reaction (Hu Zheng etc., Chinese patent ZL96117127.8), mechanical ball milling (P.Ruuskanenet al.J.Non-cryst.Solids 224 (1998) 36) or liquid phase reaction methods such as (Z.Hu et al, J.Chem.Soc.:Chem.Commnun. (1995) 247) prepares above-mentioned B-contained nano-catalyst alloy particle.
4 the present invention prepare the method for BN and BC nanostructure and carry out under high temperature 1000-1300 ℃.
5 BN provided by the invention and BC nanostructure comprise BN and BC nanotube, BN and BC nano wire, BN and BC soccerballene and wrap up BN and the BC Nano capsule of Fe-B, Ni-B, Co-B, B etc.Nanotube provided by the present invention is generally multilayer, and external diameter is 20-100nm, thickness of pipe 5-10nm; Nanowire diameter is 5-60nm; Soccerballene is polyhedral hollow nanostructured, and yardstick is 40-400nm; The BN and the BC Nano capsule of parcel Fe-B, Ni-B, Co-B, B nano particle, about 40～240 nanometers of yardstick, wherein BN and BC shell have laminate structure that is formed by h-BN, B-C or the radial structure that is formed by h-BN, B-C nanofiber.
6, CONTROL PROCESS condition, BN and the BC Nano capsule of the rich nano wire of the rich nanotube of acquisition BN and BC, BN and BC, BN and BC soccerballene and parcel B etc.Mainly be by control boracic nanoparticle particle diameter and contain the amount and the temperature of reaction of the precursor of B amount, nitrogenous or carbon, obtain the BN and the BC Nano capsule of BN and BC nanotube, BN and BC nano wire, BN and BC soccerballene and parcel B and boron-containing alloy.
7 the present invention prepare the method for BN rice structure, are earlier the B-contained nano-catalyst particle that makes to be placed above-mentioned growth room, and roasting is 3 hours under 500-700 ℃, argon atmosphere, is warmed up to 1000-1300 ℃ then, feeds N 2/ NH 3(10%NH 3) gas mixture carries out nitrogenizing reaction and obtain, and also can feed N simultaneously 2/ NH 3And B 2H 6Gas.
8 the present invention prepare the method for BC nanostructure, are earlier the B-contained nano-catalyst particle that makes to be placed above-mentioned growth room, and roasting is 3 hours under 500-700 ℃, argon atmosphere, is warmed up to 1000-1200 ℃ then, feeds CH 4Gas carries out carburizing reagent and obtains, and also can feed N simultaneously 2/ NH 3(10%NH 3) and gaseous state or solid carbon-contg precursor, thereby obtain the BCN nanostructure.Gaseous state C source refers to it can also is C 6H 6, C 2H 2Or C 2H 4, solid-state N source is ammonium chloride (NH 4Cl) or urea (CO (NH 2) 2), solid-state C source is gac or powdered graphite.
9, also can be solid-state, solid-state N source be ammonium chloride (NH to the N source among the present invention 4Cl) or urea (CO (NH 2) 2); It is gac or powdered graphite that the C source also can be solid-state, solid-state C source.
Characteristics of the present invention are as follows:
1. inherit and expanded the scientific meaning of VLS class growth method, by introduce " from the gas phase precursor and two channels of ' catalyzer ' alloy provide the required constituent element of product respectively and chemical reaction takes place generate target product " this important innovations link the catalyzer drop, develop into the novel method that a kind of gas-liquid-solid phase reaction prepares nanostructure.Make multiple BN and BC nanostructure with this method, comprised BN and the BC Nano capsule of nanotube, nano wire, soccerballene and parcel B.
2. the technological line of preparation nanostructure provided by the invention helps exploring some novel double elements or multicomponent compound nano structure, might obtain innovation and breakthrough at aspects such as exploitation new system, discovery new texture, announcement new capabilities.
3. the present invention provides new selection for the nanostructure (poisonous as precursor or be difficult to obtain system) of some system of preparation.
Four, description of drawings Fig. 1: the grow testing apparatus synoptic diagram of BN and BC nanostructure of the present invention.
(1) source of the gas; (2) pressure maintaining valve; (3) flow stabilizing valve; (4) mass flowmeter; (5) stop,threeway; (6) vacuum system; (7) O type shack; (8) growth room; (9) quartz boat; (10) beds; (11) heating and temperature controlling system; (12) acetone or water; (13) reaction back gas leads to stink cupboard.Fig. 2: use the inventive method with Fe 75B 25The nanometer microparticle catalytic agent is at the HRTEM photo of 1200 ℃ of BN nanotubes that make.Fig. 3: use the inventive method with Ni 70B 30The nanometer microparticle catalytic agent is at the TEM photo of 1300 ℃ of BN nanotubes that make.Fig. 4: use the inventive method with Fe 50B 50The nanometer microparticle catalytic agent is at the TEM photo of 1300 ℃ of BN nanotubes that make.Fig. 5: use the inventive method with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at the TEM photo of 1000 ℃ of BN nanotubes that make.Fig. 6: use the inventive method with Fe 70B 30The nanometer microparticle catalytic agent is at the TEM photo of 1000 ℃ of BN nanotubes that make.Fig. 7: use the inventive method with Fe 50B 50The nanometer microparticle catalytic agent is at the HRTEM photo of 1100 ℃ of BN nano wires that make.Fig. 8: use the inventive method with Ni 70B 30The nanometer microparticle catalytic agent is at TEM photo Fig. 9 of 1300 ℃ of BN nano wires that make: with the inventive method with Co 75B 25The nanometer microparticle catalytic agent is at TEM photo Figure 10 of 1300 ℃ of BN nano wires that make: with the inventive method with Fe 60Co 20B 20The nanometer microparticle catalytic agent is at the HRTEM photo of 1200 ℃ of BN nano wires that make.Figure 11: use the inventive method with Fe 35Ni 35B 30The nanometer microparticle catalytic agent makes BN nano wire HRTEM photo at 1200 ℃.Figure 12: use the inventive method with Co 35Ni 35B 30The nanometer microparticle catalytic agent makes BN nano wire HRTEM photo at 1200 ℃.Figure 13: use the inventive method with Fe 50B 50The nanometer microparticle catalytic agent is at the TEM photo of 1100 ℃ of preparation BN soccerballene nanoparticles.Figure 14: use the inventive method with Ni 70B 30The nanometer microparticle catalytic agent is at the HRTEM photo of 1300 ℃ of preparation BN soccerballene nanoparticles.Figure 15: use the inventive method with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at the HRTEM photo of 1000 ℃ of preparation BN soccerballene nanoparticles.Figure 16: use the inventive method with Co 75B 25The nanometer microparticle catalytic agent is at the HRTEM photo of 1300 ℃ of preparation BN soccerballene nanoparticles.Figure 17: use the inventive method with Fe 50B 50The nanometer microparticle catalytic agent is at the TEM photo of the BN Nano capsule of 1000 ℃ of preparation parcel B.Figure 18: use the inventive method with Fe 50B 50The nanometer microparticle catalytic agent is at the HRTEM photo of the BN Nano capsule of 1000 ℃ of preparation parcel B.Figure 19: use the inventive method with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at the HRTEM photo of the BN Nano capsule of 1000 ℃ of preparation parcel B.Figure 20: use the inventive method with Co 75B 25The nanometer microparticle catalytic agent is at the HRTEM photo of the BN Nano capsule of 1300 ℃ of preparation parcel B.Figure 21: use the inventive method with Co 35Ni 35B 30The nanometer microparticle catalytic agent is at the TEM photo of the BN Nano capsule of 1000 ℃ of preparation parcel B.Figure 22: use the inventive method with Co 35Ni 35B 30The nanometer microparticle catalytic agent is at the HRTEM photo of the BN Nano capsule of 1000 ℃ of preparation parcel B.Figure 23: use the inventive method with Fe 75B 25The nanometer microparticle catalytic agent is at the TEM photo of 1000 ℃ of preparation BCN nanotubes.Figure 24: use the inventive method with Fe 50B 50The nanometer microparticle catalytic agent is at the TEM photo of 1300 ℃ of preparation BCN nanotubes.
Five, embodiment embodiment 1 is with Fe 75B 25The nanometer microparticle catalytic agent is at 1200 ℃ of preparation BN nanotubes.
KBH by 1mol/L 4FeSO with 0.1mol/L 4Liquid phase reaction makes the Fe of about 40 nanometers of median size 75B 25Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1200 ℃.Stop applying argon gas, feed the N of 300SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1200 ℃.Obtain the degree of crystallinity high BN nanotube of diameter for about 20nm in the beds district.(see figure 2) embodiment 2 is with Ni 70B 30The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BN nanotubes.
KBH by 1mol/L 4NiCl with 0.1mol/L 2Liquid phase reaction makes the Ni of about 50 nanometers of median size 70B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 250SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain the BN nanotube of diameter for about 50nm in the beds district.(see figure 3) embodiment 3 is with Fe 70B 30The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BN nanotubes.
With anhydrous FeCl 3With KBH 4By after 1: 3.3 the mixed in molar ratio in planetary ball mill ball milling 8 hours, roasting 3 hours in argon atmospher then obtains the Fe that size of particles is about 20nm 70B 30Nanoparticle.The Fe-B nanoparticle that obtains is placed the alundum tube central zone, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 400SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain the BN nanotube (see figure 4) of diameter for about 80nm in Fe-B nanoparticle bed district.Embodiment 4 is with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at 1000 ℃ of preparation BN nanotubes.
KBH by 0.5mol/L 4The FeCl of reduction 0.1mol/L 2And NiCl 2Mixed solution (Fe 2+: Ni 2+=1: 1) make the Fe of about 35 nanometers of median size 35Ni 35B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 350SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 3 hours down at 1000 ℃.Obtain the BN nanotube (see figure 5) of diameter for about 20nm in the beds district.Embodiment 5 is with Fe 70B 30The nanometer microparticle catalytic agent is at 1200 ℃ of preparation BN nano wires.
Make the Fe of about 100 nanometers of median size by the method for mechanical ball milling by iron powder and boron powder 70B 30Particulate.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1200 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 3 hours down at 1200 ℃.Obtain the BN nanotube (see figure 6) of diameter for about 85nm in the beds district.Embodiment 6 is with Fe 50B 50The nanometer microparticle catalytic agent is at 1100 ℃ of preparation BN nano wires.
With anhydrous FeCl 3With KBH 4By after 1: 3.3 the mixed in molar ratio in planetary ball mill ball milling 8 hours, roasting 3 hours in argon atmospher then obtains the Fe that size of particles is about 30nm 50B 50Nanoparticle.The Fe-B nanoparticle that obtains is placed the alundum tube central zone, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1100 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1100 ℃.Obtain the degree of crystallinity high BN nano wire (see figure 7) of diameter for about 30nm in Fe-B nanoparticle bed district.Embodiment 7 is with Ni 70B 30The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BN nano wires.
KBH by 1mol/L 4NiCl with 0.1mol/L 2Liquid phase reaction makes the Ni of about 20 nanometers of median size 70B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain the degree of crystallinity high BN nano wire (see figure 8) of diameter for about 9nm in the beds district.Embodiment 8 is with Co 75B 25The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BN nano wires.
KBH by 1mol/L 4CoCl with 0.1mol/L 2Liquid phase reaction makes the Co of about 30 nanometers of median size 75B 25Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 150SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain the BN nano wire (see figure 9) of diameter for about 20nm in the beds district.Embodiment 9 is with Fe 60Co 20B 20The nanometer microparticle catalytic agent is at 1200 ℃ of preparation BN nano wires.
KBH by 1mol/L 4The FeCl of reduction 0.1mol/L 2And CoCl 2Mixed solution (Fe 2+: Co 2+=3: 1) make the Fe of about 20 nanometers of median size 60Co 20B 20Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1200 ℃.Stop applying argon gas, feed the N of 150SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 3 hours down at 1200 ℃.Obtain the degree of crystallinity high BN nano wire (see figure 10) of diameter for about 8nm in the beds district.Embodiment 10 is with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at 1000 ℃ of preparation BN nano wires.
KBH by 0.5mol/L 4The FeCl of reduction 0.1mol/L 2And NiCl 2Mixed solution (Fe 2+: Ni 2+=1: 1) make the Fe of about 25 nanometers of median size 35Ni 35B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 150SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 3 hours down at 1000 ℃.Obtain the degree of crystallinity high BN nano wire (see Figure 11) of diameter for about 10nm in the beds district.Embodiment 11 is with Co 35Ni 35B 30The nanometer microparticle catalytic agent is at 1000 ℃ of preparation BN nano wires.
KBH by 0.5mol/L 4The FeCl of reduction 0.1mol/L 2And NiCl 2Mixed solution (Fe 2+: Ni 2+=1: 1) make the Fe of about 20 nanometers of median size 35Ni 35B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 3 hours down at 1000 ℃.Obtain the degree of crystallinity high BN nano wire (see Figure 12) of diameter for about 8nm in the beds district.Embodiment 12 is with Fe 50B 50The nanometer microparticle catalytic agent is at 1100 ℃ of preparation BN soccerballene nanoparticles.
With anhydrous FeCl 3With KBH 4By after 1: 3.3 the mixed in molar ratio in planetary ball mill ball milling 8 hours, roasting 3 hours in argon atmospher then obtains the Fe that size of particles is about 20nm 50B 50Nanoparticle.The Fe-B nanoparticle that obtains is placed the alundum tube central zone, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1100 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1100 ℃.Obtain polyhedral BN soccerballene nanoparticle (seeing Figure 13) of the about 40-300nm of size at the alundum tube outlet area.Embodiment 13 is with Ni 70B 30The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BN soccerballene nanoparticles.
KBH by 1mol/L 4NiCl with 0.1mol/L 2Liquid phase reaction makes the Ni of about 20 nanometers of median size 70B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain polyhedral crystalline BN soccerballene nanoparticle (seeing Figure 14) of the about 45nm of size at the alundum tube outlet area.Embodiment 14 is with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at 1000 ℃ of preparation BN soccerballene nanoparticles.
KBH by 0.5mol/L 4The FeCl of reduction 0.1mol/L 2And NiCl 2Mixed solution (Fe 2+: Ni 2+=1: 1) make the Fe of about 35 nanometers of median size 35Ni 35B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 350SCCM 2/ NH 3(10%NH 3) gas mixture, the alundum tube outlet area obtain the size about 60nm polyhedral crystalline BN soccerballene nanoparticle (seeing Figure 15).Embodiment 15 is with Co 75B 25The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BN soccerballene nanoparticles.
KBH by 1mol/L 4CoCl with 0.1mol/L 2Liquid phase reaction makes the Co of about 30 nanometers of median size 75B 25Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 150SCCM 2/ NH 3(10%NH 3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain polyhedral crystalline BN soccerballene nanoparticle (seeing Figure 16) of the about 50nm of size at the alundum tube outlet area.Embodiment 16 is with Fe 50B 50The nanometer microparticle catalytic agent is at the BN Nano capsule of 1100 ℃ of preparation parcel B.
With anhydrous FeCl 3With KBH 4By after 1: 3.3 the mixed in molar ratio in planetary ball mill ball milling 8 hours, roasting 3 hours in argon atmospher then obtains the Fe that size of particles is about 20nm 50B 50Nanoparticle.The Fe-B nanoparticle that obtains is placed the alundum tube central zone, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1100 ℃.Stop applying argon gas, feed the NH of 100SCCM respectively 3/ N 2(10%NH 3), reacted 2 hours down at 1100 ℃.Obtain wrapping up the BN Nano capsule of B nano particle at the alundum tube outlet area, about 160 nanometers of yardstick, wherein the BN shell has the laminate structure (seeing Figure 17,18) that is formed by h-BN.Embodiment 17 is with Fe 35Ni 35B 30The nanometer microparticle catalytic agent is at the BN Nano capsule of 1000 ℃ of preparation parcel B.KBH by 0.5mol/L 4The FeCl of reduction 0.1mol/L 2And NiCl 2Mixed solution (Fe 2+: Ni 2+=1: 1) make the Fe of about 35 nanometers of median size 35Ni 35B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 350SCCM 2/ NH 3(10%NH 3) and the B of 20SCCM 2H 6/ Ar (10%B 2H 6) gas, obtain wrapping up the BN Nano capsule of B nano particle at the alundum tube outlet area, about 100～240 nanometers of yardstick, wherein the BN shell has the laminate structure that is formed by h-BN obtains wrapping up the B nano particle at the alundum tube outlet area BN Nano capsule, about 100～240 nanometers of yardstick, wherein the BN shell radial structure (seeing Figure 19) that has the laminate structure that forms by h-BN or form by the h-BN nanofiber.Embodiment 18 is with Co 75B 25The nanometer microparticle catalytic agent is at the BN Nano capsule of 1300 ℃ of preparation parcel B.
KBH by 1mol/L 4CoCl with 0.1mol/L 2Liquid phase reaction makes the Co of about 30 nanometers of median size 75B 25Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) and the B of 20SCCM 2H 6/ Ar (10%B 2H 6) gas, reacted 3 hours down at 1300 ℃.Obtain wrapping up the BN Nano capsule of B nano particle at the alundum tube outlet area, about 130 nanometers of yardstick, the wherein radial structure (seeing Figure 20) that forms of BN shell h-BN nanofiber.Embodiment 19 is with Co 35Ni 35B 30The nanometer microparticle catalytic agent is at the BN Nano capsule of 1000 ℃ of preparation parcel B.
KBH by 0.5mol/L 4The FeCl of reduction 0.1mol/L 2And NiCl 2Mixed solution (Fe 2+: Ni 2+=1: 1) make the Fe of about 20 nanometers of median size 35Ni 35B 30Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 100SCCM 2/ NH 3(10%NH 3) and the B of 20SCCM 2H 6/ Ar (10%B 2H 6) gas, reacted 3 hours down at 1000 ℃.Obtain wrapping up the BN Nano capsule of B nano particle at the alundum tube outlet area, about 200 nanometers of yardstick, the wherein radial structure (seeing Figure 21,22) that forms of BN shell h-BN nanofiber.Embodiment 20 is with Fe 75B 25The nanometer microparticle catalytic agent is at 1000 ℃ of preparation BCN nanotubes.
KBH by 1mol/L 4FeSO with 0.1mol/L 4Liquid phase reaction makes the Fe of about 40 nanometers of median size 75B 25Nanoparticle.Place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1000 ℃.Stop applying argon gas, feed the N of 200SCCM 2/ NH 3(10%NH 3) and the CH of 50SCCM 4Gas reacted 2 hours down at 1000 ℃.Obtain in the beds district diameter for about 20nm the BCN nanotube.(seeing Figure 23) embodiment 21 is with Fe 50B 50The nanometer microparticle catalytic agent is at 1300 ℃ of preparation BCN nanotubes.
With anhydrous FeCl 3With KBH 4By after 1: 3.3 the mixed in molar ratio in planetary ball mill ball milling 8 hours, roasting 3 hours in argon atmospher then obtains the Fe that size of particles is about 20nm 50B 50Nanoparticle.The Fe-B nanoparticle that obtains is placed the alundum tube central zone, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 250SCCM 2/ NH 3(10%NH 3) and the CO gas of 50SCCM, 1300 ℃ of reactions 2 hours down.Obtain the BCN nanotube (see Figure 24) of diameter for about 20nm in Fe-B nanoparticle bed district.Embodiment 22:BN nanostructure comprises that the condition main points of the BN Nano capsule of BN nanotube, BN nano wire, BN soccerballene and parcel Fe-B, Ni-B, Co-B, B are: the general growth conditions of nanotube is: earlier boracic (20～30%) nanocatalyst particles that makes is placed above-mentioned growth room, roasting is 3 hours under 500-700 ℃, argon atmosphere, be warmed up to 1000-1300 ℃ then, feed the N of 300-400SCCM simultaneously 2/ NH 3(10%NH 3) react and obtain, can control B-contained nano-catalyst size of particles and control BN nanotube caliber.Also can feed N simultaneously 2/ NH 3And B 2H 6Gas reacts and obtains at the B-contained nano-catalyst particle surface.Can get rich nanotube articles.Embodiment 23: the general growth conditions of nano wire is: earlier boracic (30～50%) nanocatalyst particles that makes is placed above-mentioned growth room, roasting is 3 hours under 500-700 ℃, argon atmosphere, be warmed up to 1000-1300 ℃ then, feed the N of 70-150SCCM simultaneously 2/ NH 3(10%NH 3) react and obtain, can control B-contained nano-catalyst size of particles and control the BN nanowire diameter.Also can feed N simultaneously 2/ NH 3And B 2H 6Gas reacts and obtains at the B-contained nano-catalyst particle surface.Can get rich nano wire goods.Embodiment 24: soccerballene is polyhedral hollow nanostructured, yardstick is 40-400nm, general growth conditions is: earlier boracic (20～50%) nanocatalyst particles that makes is placed above-mentioned growth room, roasting is 3 hours under 500-700 ℃, argon atmosphere, be warmed up to 1000-1300 ℃ then, feed the N of 100-400SCCM simultaneously 2/ NH 3(10%NH 3) be reflected at the reaction chamber exit and obtain.Can get rich polyhedral hollow nanostructured.Embodiment 25: the general growth conditions of the BN Nano capsule of parcel Fe-B, Ni-B, Co-B, B nano particle is: earlier boracic (20～50%) nanocatalyst particles that makes is placed above-mentioned growth room, roasting is 3 hours under 400-500 ℃, argon atmosphere, be warmed up to 500-1200 ℃ then, feed the N of 50-400SCCM simultaneously 2/ NH 3(10%NH 3) react and obtain, can control boron-containing quantity, temperature of reaction, N 2/ NH 3(10%NH 3) flow control BN layer thickness.Embodiment 26: earlier with the Fe that makes 60B 40Nanocatalyst particles (about 40nm) places above-mentioned growth room, and roasting is 3 hours under 500 ℃, argon atmosphere, is warmed up to 1200 ℃ then, and the CO gas that feeds 100SCCM simultaneously reacts and obtains, and diameter is the BC nano wire of 30nm.Can get rich Nano capsule goods.
Embodiment 27: the precursor among the present invention also can be gas phase CH 4, C 6H 6, C 2H 2, C 2H 4, CO or solid-state gac, powdered graphite, thereby obtain the BC nanostructure.Reaction conditions is with above-mentioned nitrogenous source conditional likelihood.
Embodiment 28: the pre-reaction material among the present invention can contain nitrogenous source and carbon source simultaneously, also can feed nitrogen-containing precursor respectively (as N 2, NH 3) and the carbon containing precursor (as CH 4), thereby obtain the BCN nanostructure.

Claims (8)

1, a kind of method of grow BN and BC nano structural material, it is characterized in that gas or solid with nitrogenous or carbon are nitrogenous source and carbon source, nanometer " catalyzer " alloy particle with boracic 20～70% is done the boron source, (1000-1300 ℃) growth BN nanostructure particle that reacts in tube furnace under the high temperature; The B-contained nano-catalyst alloy particle that adopts is mainly Fe-B, Ni-B, Co-B, Fe-Ni-B, Fe-Co-B, Ni-Co-B etc., and its general formula is Fe xB 100-x, Ni yB 100-yCo zB 100-zFe aNi bB 100-a-bFe aCo bB 100-a-b, x, y, z get 30-80, a+b gets 30-80.
2, the method for growth BN according to claim 1 and BC nano structural material, it is characterized in that by control boracic nanoparticle particle diameter and contain the B amount, gas or solid nitrogenous or carbon are nitrogenous source and carbon source flow and temperature of reaction, obtain BN and the BC Nano capsule of BN and BC nanotube, BN and BC nano wire, BN and BC soccerballene and parcel B etc.
3, the method for growth BN according to claim 1 and BC nano structural material, it is characterized in that with nitrogenous gas or solid be nitrogenous source, with carbonaceous gas or solid is carbon source, nanometer " catalyzer " alloy particle with boracic is the boron source, and growth B-C-N nanostructure reacts in tube furnace under the high temperature.
4,, it is characterized in that nanometer " catalyzer " alloy particle of boracic is meant FeB, NiB, CoB nanoparticle or two kinds, three kinds mixtures according to claim 1,2 or 3 described BN and BC nanostructure preparation method.
5, according to claim 1,2 or 3 described BN and BC nanostructure preparation method, it is characterized in that nanometer " catalyzer " alloy particle of boracic can be by solid phase method and liquid phase method preparation, size of particles is 20-100nm, boron-containing quantity is 20～70%.
6, ask described nanostructure preparation method according to right 1,2 or 3, it is characterized in that gasiform N source is N 2And NH 3, gaseous state C source refers to CH 4, C 6H 6, C 2H 2Or C 2H 4, solid-state N source is ammonium chloride (NH 4Cl) or urea (CO (NH 2) 2) solid-state C source is gac or powdered graphite.
7, the method for BN according to claim 1 and BC nano structural material, it is characterized in that gas or solid with nitrogenous or carbon are nitrogenous source and carbon source, gas with boracic is external boron source simultaneously, can obtain wrapping up the BN or the BC Nano capsule of B or boron-containing alloy nanoparticle.
8, the method for growth BN nano structural material according to claim 1 is characterized in that pre-reaction material can contain nitrogenous source and carbon source simultaneously, thereby obtains the BCN nanostructure.
CN 02138035 2002-07-29 2002-07-29 Nano structure of boron nitride and boron carbonide and its preparing process Pending CN1397491A (en)

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