CN1328158C - Prepn process of nanometer BN and B-C-N capsule or nanometer fullerene-like particle - Google Patents
Prepn process of nanometer BN and B-C-N capsule or nanometer fullerene-like particle Download PDFInfo
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- CN1328158C CN1328158C CNB2004100647681A CN200410064768A CN1328158C CN 1328158 C CN1328158 C CN 1328158C CN B2004100647681 A CNB2004100647681 A CN B2004100647681A CN 200410064768 A CN200410064768 A CN 200410064768A CN 1328158 C CN1328158 C CN 1328158C
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Abstract
The present invention relates to a preparation process of nanometer BN and B-C-N capsules or nanometer fullerene-like particles. Gas or solid containing nitrogen is used as a nitrogen source, gas or solid containing carbon is used as a carbon source, a nanometer 'catalyst' alloy particle containing boron of 20% to 70% or single boron is used as a boron source, the nitrogen source, the carbon source and the boron source generate reaction at 600 DEG C to 900 DEG (a tubular furnace) or under the excitation of microwave plasma to controllably grow BN nanometer particles, BN nanometer capsules or the mixture (being a B-C-N system when being filled with the carbon source) of the BN nanometer capsules and BN fullerene-like nanometer particles, wherein the BN nanometer capsules and the mixture of the BN nanometer capsules and BN fullerene-like nanometer particles are further prepared into corresponding pure BN fullerene-like nanometer particles (B-C-N fullerene-like nanometer particles thrugh after-treatment. The preparation process develops a new process for preparing high-purity fullerene-like nanometer particles, and is used for preparing various BN and B-C-N nanometer hollow structures.
Description
Technical field
The present invention relates to prepare the novel synthesis of BN and B-C-N fullerene-like nanoparticles and novel nanostructures such as intermediate product BN and B-C-N Nano capsule thereof.
Background technology
Since C60 found, carbon nano-structured (comprising soccerballene, nanotube, nano wire, nanometer ball, 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 graphite aspect structural similitude similarly, comprise that the BN nanostructure of a series of novelties of BN fullerene-like nanoparticles and BN Nano capsule also is found in succession.H-BN and B-C-N 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.The nanostructure (a kind of carbon nano-structured analogue) that is formed by h-BN and B-C-N shows stronger high temperature resistant, antioxidant property with carbon nano-structured comparing, and can provide the inertia protective layer to other nanostructures of its parcel.BN and B-C-N fullerene-like nanoparticles have big surface ratio again as a kind of hollow Nano particle, small particle size, mechanical property special etc. characteristics, in catalysis, inhale hydrogen, all there is application prospect in fields such as solid lubrication.And the BN and the B-C-N Nano capsule of magnetic material such as parcel Fe etc., be a kind of be nano magnetic material with inertia protective layer.Thereby BN and B-C-N soccerballene and Nano capsule are the novel materials that a class has important scientific value and wide application prospect.
Existing BN nanostructure synthetic technology comprises 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 thermal chemical vapor deposition method (Fan S.Set al.Mater.Lett.51,31 5 (2001)) etc.
In nanostructure was synthetic, technology was simple owing to having, low cost and other advantages has obtained extensive employing for chemical Vapor deposition process; It is low that the plasma enhanced vapor deposition method has temperature, and active high reaction characteristics also is the preparation method of nano material with specific advantages.The technology of the synthetic BN nano materials of method such as present employing vapour deposition process and the more existing documents of method and patent are reported for work.We strengthen chemical Vapor deposition process by using plasma, respectively with B
2H
6, N
2/ NH
3Be that template has prepared BN nano-tube array (Chinese patent application number: ZL 01113556.5) for B source and N source, with the aluminum oxide; Adopt FeB, NiB, CoB nano amorphous, the various BN nanostructure (Chinese patents of preparation about 1100 ℃ as precursor.Publication number: CN 1397491A).Qian Yitai etc. are in the presence of metals such as Zn, with NH
4BF
4, KBH
4Under high pressure take place solvent thermal reaction prepare BN nanotube and BN hollow structure (Y.T.Qian et.al.CHL 381,1-2, pp.74-79); With BCl
3And NaNH
3Under the normal temperature inert atmosphere, react, made the hollow structure (Y.T.Qian et.al.Solid State Communications 130 (2004) 537-540) that unformed BN constitutes.Y. Bando etc. makes precursor with B-N-O, prepared in reaction takes place under 1750 ℃ of argon gas stream that contain ammonia in a small amount diameter be 30-200nm the BN hollow structure (Chem.Eur.J.2004,10,3667-3672).
CN1397491A is the previous work of applicant, and BN nanostructure form relatively mixes, and fullerene-like nanoparticles is arranged, also nanotube, nano wire are arranged, and is difficult to separate, and influences the application prospect of this class material.
Summary of the invention
The method or the technology that the purpose of this invention is to provide a kind of BN of preparation and B-C-N fullerene-like nanoparticles.The object of the invention also is, obtains BN and the B-C-N Nano capsule and the fullerene-like nanoparticles of different grain size and wall thickness by CONTROL PROCESS condition, reaction times, boracic catalyst particle size and boron-containing quantity.
Whole process of the present invention realizes in two steps, at first synthesizes the intermediate product that comprises BN and/or B-C-N Nano capsule, obtains the BN and/or the B-C-N fullerene-like nanoparticles of complete or opening then by aftertreatment.Specifically, prepare boracic solid phase precursor in advance, comprise " catalyzer " alloy or the pure boron nanoparticle of boracic, as Fe-B, Ni-B, Co-B, Fe-Ni-B, Fe-Co-B, Ni-Co-B, B simple substance etc.In the first step reaction, will contain the reaction of boron particles and nitrogenous (can select the part carbon containing) gas mixture, form Nano capsule with core-shell structure (Core-ShellStructure), according to preparation condition difference, diameter does not wait at 20-200nm.Use two kinds of methods and all can finish this reaction: a. chemical Vapor deposition process (CVD), b. plasma chemical vapor deposition (MWCVD).In the reaction of second step is the stoning process of package structure.Also can finish: 1. high-temperature roasting, 2. pickling by dual mode.By above two steps, can obtain BN and/or B-C-N fullerene-like nanoparticles.Comprehensive: the present invention is a nitrogenous source with nitrogenous gas or solid, nanocatalyst alloy particle or pure boron with boracic 20～70% are done the boron source, in 700-900 ℃ of tube furnace or under microwave plasma excitated, reacted 1-5 hour, controllable growth BN Nano capsule, or the mixture of BN Nano capsule and fullerene-like nanoparticles; Be under the condition of carbon source existence at carbonaceous gas or solid simultaneously, the mixture of growth B-C-N Nano capsule or B-C-N Nano capsule and fullerene-like nanoparticles.The present invention is that (J.Mater.Chem.13 (2003) 2024 for Q.Wu, Z.Huet al. for our the VLS reaction mechanism of the expansion that proposes; K.F.Huo, Z.Hu et al., J.Phys.Chem.B 107 (2003) 11316; K.F.Huo, Z.Hu et al., Appl.Phys.Lett.80 (2002) 3611; J.J.Fu, ..., Z.Hu et al., Nanotechnology 15 (2004) 727) practical application aspect nanoparticle: the N atom among the gas phase precursor NH3/N2 with in " catalyzer " drop chemical reaction takes place from the B atom in the Fe-B nanometer " catalyzer ", when the BN species that generate reach supersaturation in " catalyzer " drop, just separate out, form the BN Nano capsule of parcel form on its surface.The intermediate product that comprises the BN Nano capsule is again by high-temperature roasting (1400 ℃), and its core deviates to form the BN fullerene-like nanoparticles from shell; Another kind of removing in the kernel method, the core that contains metal catalyst is dissolved in the acid solution, and last shell forms hollow BN fullerene-like nanoparticles.The generting machanism of B-C-N fullerene-like nanoparticles is identical, and increase carbon containing gas phase or other raw material get final product in the raw material.
The present invention is with the main difference that existing fullerene-like nanoparticles synthetic method is compared, be by the synthetic hollow fullerene nanostructure of two steps of " XianCheng's shell; stoning again ", can prepare simple fullerene-like nanoparticles, and control the product form by granularity and the reaction conditions of regulating raw material.
The details of the inventive method is:
1, device required for the present invention mainly contains body of heater, gas distributing system and vacuum system three parts composition, 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 control the growth of BN and B-C-N 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 B-C-N 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 boracic nanoparticle high temperature in the growth room, also can regulate vacuum tightness and reacting gas pressure in the growth room simultaneously.
2, the B-contained nano-catalyst alloy particle of the present invention's employing is mainly Fe-B, Ni-B, Co-B, Fe-Ni-B, Fe-Co-B, Ni-Co-B, B simple substance etc.Its general formula is Fe
xB
100-x, Ni
yB
100-yCo
zB
100-zFe
aNibB
100-a-bFe
aCobB
100-a-b, x, y, z get 30-80, a+b gets 30-80.The boron simple substance nanoparticle that the present invention adopts is the unformed boron of particle diameter 20-80nm.
3, available compound solid state reaction (Hu Zheng etc., Chinese patent ZL 96117127.8), mechanical ball milling (P.Ruuskanen
Et al.J.Non-cryst.Solids 224 (1998) 36) or liquid phase reaction methods such as (Z.Hu et al, J.Chem.Soc.:Chem.Commun. (1995) 247) prepare above-mentioned B-contained nano-catalyst alloy particle.
4, the present invention generates BN and the B-C-N nanostructure is carried out under 700-900 ℃, perhaps generates under nitrogen atmosphere plasma reaction condition.
5, the invention provides BN and the B-C-N Nano capsule of BN and B-C-N fullerene-like nanoparticles and parcel Fe-B, Ni-B, Co-B, B etc.Fullerene-like nanoparticles provided by the present invention is polyhedral hollow nanostructured, is generally multilayer, and by the reaction conditions difference, external diameter is in 20-200 nm scope, and thickness of pipe is in 5-30 nm scope; The BN and the B-C-N Nano capsule of parcel Fe-B, Ni-B, Co-B, B nano particle, yardstick is consistent with fullerene-like nanoparticles, the about 20-200 nanometer of diameter, wherein BN and B-C-N shell have the laminate structure that is formed by h-BN, B-C-N.Fullerene-like nanoparticles comprises that also opening is nano-hollow sphere structured.
6, CONTROL PROCESS condition can obtain BN and the B-C-N Nano capsule and the fullerene-like nanoparticles of different grain size and wall thickness.Mainly be size, catalyzer boron-containing quantity, the particle diameter of control Nano capsule and fullerene-like nanoparticles by the control catalyst particle; By the conditioned reaction gas flow, and reaction times length, different wall Nano capsule and fullerene-like nanoparticles obtained.
7, the present invention prepares the method for BN fullerene-like nanoparticles, is earlier the boracic nanoparticle that makes to be placed above-mentioned growth room, and roasting is warmed up to 700-900 ℃ about 3 hours then under 500-700 ℃, argon atmosphere, feeds N
2/ NH
3(4%NH
3) gas mixture carries out nitrogenizing reaction and obtain containing the intermediate product of BN Nano capsule.The BN Nano capsule is passed through pyroprocessing under 1350-1450 ℃ of (typical case is as 1400 ℃) inert atmosphere, perhaps 1-3M hydrochloric acid or vitriolization are further reacted and are obtained the BN fullerene-like nanoparticles again.
8, the present invention prepares the method that the present invention prepares the B-C-N fullerene-like nanoparticles, is 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 700-900 ℃ then, feeds N
2/ NH
3(4%NH
3) and CH
4React Deng gaseous state C source gas mixture and obtain the B-C-N Nano capsule.The B-C-N Nano capsule is passed through pyroprocessing under 1350-1450 ℃ of (typical case is as 1400 ℃) inert atmosphere, perhaps mineral acid treatment such as 1-3M hydrochloric acid or sulfuric acid are further reacted and are obtained the B-C-N fullerene-like nanoparticles again.Gaseous state C source can also be C
6H
6, C
2H
2Or C
2H
4Acid-treated temperature is about 40-70 ℃ of 2M, 12-24 hour acid treatment time.
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, developed a kind of method for preparing single BN or B-C-N fullerene-like nanoparticles.And condition control product forms such as granularity that can be by regulating raw material, temperature of reaction, airshed, reaction times.
2, the present invention's " XianCheng's shell, stoning again " reaction mechanism provides new approaches for synthetic other nanometer cage structure.
3, from the photo that amplifies as seen, the present invention has especially developed a kind of method for preparing purity height, single form BN or B-C-N fullerene-like nanoparticles.
Description of drawings
Fig. 1: the grow thermal chemical vapor deposition reaction unit synoptic diagram of BN and B-C-N zero-dimension nano structure of the present invention:
(1) stopping valve; (2) mass flowmeter; (3) High Temperature Furnaces Heating Apparatus; (4) thermopair; (5) temperature controller; (6) corundum crucible; (7) filter screen; (8) vacuumometer; (9) vacuum pump;
Fig. 2:: the grow plasma enhanced chemical vapor deposition reaction unit synoptic diagram of BN and B-C-N zero-dimension nano structure of the present invention:
(1) stopping valve; (2) mass flowmeter; (3-1) silica tube; (4-1) water coolant; (5-1) microwave radiation; (6-1) microwave plasma source; (7) filter screen; (8) vacuumometer; (9) vacuum pump;
Fig. 3: use the inventive method with Fe
75B
25The nanometer microparticle catalytic agent is at the HRTEM photo of 850 ℃ of BN Nano capsules that make.
Fig. 4: use the inventive method with Ni
70B
30The nanometer microparticle catalytic agent is at the TEM photo of 900 ℃ of BN Nano capsules that make.
Fig. 5: use the inventive method with Co
75B
25The nanometer microparticle catalytic agent is at the HRTEM photo of 900 ℃ of B-C-N Nano capsules that make.
Fig. 6: use the inventive method with Fe
70B
30The TEM photo of the BN Nano capsule that the nanometer microparticle catalytic agent makes under plasma exciatiaon.
Fig. 7: use the inventive method with Fe
50B
50The nanometer microparticle catalytic agent is at the TEM photo of 750 ℃ of BN fullerene-like nanoparticles that make and BN Nano capsule mixture.
Fig. 8: use the inventive method with Fe
35Ni
35B
30The nanometer microparticle catalytic agent is at the TEM photo of 800 ℃ of BN nanoparticles that make
Fig. 9: use the inventive method with Fe
70B
30The nanometer microparticle catalytic agent is 750 ℃ of reactions, again the TEM and the HRTEM photo of the BN fullerene-like nanoparticles that makes through peracid treatment
Figure 10: use the inventive method with Co
35Ni
35B
30The nanometer microparticle catalytic agent is 900 ℃ of reactions, again the HRTEM photo of the BN fullerene-like nanoparticles that makes through peracid treatment
Figure 11: use the inventive method with Co
75B
25The nanometer microparticle catalytic agent is 900 ℃ of reactions, again the TEM photo of the B-C-N fullerene-like nanoparticles that makes through peracid treatment
Figure 12: use the inventive method with Fe
50B
50(Figure 12 a) and BN fullerene-like nanoparticles (Figure 12 b) TEM photo at the BN Nano capsule of 900 ℃ of preparation diameter 20-50nm in the nanometer microparticle catalytic agent.
Figure 13: use the inventive method with Co
35Ni
35B
30Deng the nanometer microparticle catalytic agent 900 ℃ the reaction and through the B-C-N fullerene-like nanoparticles TEM of prepared diameter 50-200nm such as peracid treatment photo.Wherein (Figure 13 a), the BN fullerene-like nanoparticles of 60-150nm (Figure 13 b), the BN fullerene-like nanoparticles of 60-150nm (Figure 13 c), diameter are the BN fullerene-like nanoparticles (Figure 13 d) of 60-150nm to the BN fullerene-like nanoparticles of 40-120nm.
Figure 14: use the inventive method with Ni
70B
30The BN class fullerene-like nanoparticles hollow ball TEM photo for preparing the about 200nm of diameter Deng the nanometer microparticle catalytic agent in 900 ℃ of reactions and process pyroprocessing.Diameter is the BN fullerene-like nanoparticles (seeing Figure 14 c, 14d) of 80-350nm.The BN fullerene-like nanoparticles of 80-350nm (seeing Figure 14 a, 14b).
Figure 15: prepare the boron nanoparticle with the inventive method, and prepare BN Nano capsule and fullerene-like nanoparticles as the boron source.(Figure 15 a), diameter is about the BN Nano capsule (Figure 15 b) of the parcel B of 100nm to the B nanoparticle of diameter 40-100, and diameter is the BN fullerene-like nanoparticles (Figure 15 C) of 100-150nm.
Figure 16: with the XRD spectra of the BN fullerene-like nanoparticles of the inventive method preparation.
Figure 17: with the EDS spectrogram of the BN fullerene-like nanoparticles of the inventive method preparation.
Embodiment
Embodiment 1: with Fe
75B
25The nanometer microparticle catalytic agent is at 850 ℃ of preparation BN Nano capsules.
KBH by 1mol/L
4FeSO with 0.1mol/L
4Liquid phase reaction makes the Fe of about 40 nanometers of median size
75B
25Nanoparticle.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 10 ℃ of per minutes under argon atmosphere is warmed up to 850 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 850 ℃.Covered a crystallization BN layer in the Fe-B nanoparticle surface, obtaining diameter is the BN Nano capsule (see figure 3) of the parcel Fe-B of 30-100nm.
It is ammonium chloride (NH that N source in the present embodiment also can be solid-state, solid-state N source
4Cl) or urea (CO (NH
2)
2) obtain identical product.
Embodiment 2: with Ni
70B
30The nanometer microparticle catalytic agent is at 900 ℃ of preparation BN Nano capsules.
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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 2 hours down at 900 ℃.In the catalyst particle surface coverage one crystallization BN layer, obtain the BN Nano capsule of diameter for the parcel Ni-B of about 40-120nm.(see figure 4)
Embodiment 3: with Co
75B
25The nanometer microparticle catalytic agent is at 900 ℃ of preparation BN Nano capsules.
KBH by 1mol/L
4CoCl with 0.1mol/L
2Liquid phase reaction makes the Co of about 30 nanometers of median size
75B
25Nanoparticle.The Co-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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3/ C
2H
2(4%NH
3, 10%C
2H
2) gas mixture, reacted 2 hours down at 900 ℃.In the catalyst particle surface coverage one B-C-N layer, obtain the B-C-N Nano capsule of diameter for the parcel Ni-B of about 30-100nm.(see figure 5)
Embodiment 4: with Fe
70B
30The BN Nano capsule that the nanometer microparticle catalytic agent makes under plasma exciatiaon.
Make the Fe of median size 40-200nm by the method for mechanical ball milling by iron powder and boron powder
70B
30Particulate.Place the silica tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, open plasma source under low pressure hydrogen/argon atmosphere then, the beginning aura feeds the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 1 hour.In the catalyst particle surface coverage one BN layer, obtain the BN Nano capsule of diameter for the bag Fe-B of about 40-200nm.(shown in Figure 6).Co with the same particle size scope
75B
25, Ni
70B
30And under plasma exciatiaon, make the BN Nano capsule of same form.
Embodiment 5: with Fe
50B
50The nanometer microparticle catalytic agent is at 750 ℃ of BN fullerene-like nanoparticles that make and BN Nano capsule mixture
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 30-100 nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 750 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 750 ℃.Around former Fe-B nanocatalyst particles, obtaining diameter is the BN Nano capsule (see figure 7) of BN fullerene-like nanoparticles and the parcel Fe-B that diameter is 30-150nm of 20-50nm.
Embodiment 6: with Fe
35Ni
35B
30The nanometer microparticle catalytic agent is at the TEM photo of 800 ℃ of BN nanoparticles that make.
KBH by 0.5 mol/L
4Reduce the FeCl of 0.1 mol/L
2And NiCl
2Mixed solution (Fe
2+: Ni
2+=1: 1) make the Fe of about 25 nanometers of median size
35Ni
35B
30Nanoparticle.The Fe-Ni-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 10 ℃ of per minutes under argon atmosphere is warmed up to 800 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 2 hours down at 800 ℃.Obtain the BN nanoparticle (see figure 8) that diameter is 10-15nm in Fe-Ni-B nanoparticle bed district.
Embodiment 7: with Fe
50B
50The nanometer microparticle catalytic agent prepares the BN fullerene-like nanoparticles by acid treatment again 750 ℃ of nitrogenize.
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 30-100nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 750 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 750 ℃.Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Obtain diameter in the BN of 20-50nm fullerene-like nanoparticles (see figure 9).
Embodiment 8: with Co
35Ni
35B
30The nanometer microparticle catalytic agent prepares the BN fullerene-like nanoparticles by acid treatment again 900 ℃ of nitrogenize.
KBH by 0.5mol/L
4The FeCl of reduction 0.1mol/L
2And CoCl
2Mixed solution (Fe
2+: Ni
2+=1: 1) make the Co of about 25 nanometers of median size
35Ni
35B
30Nanoparticle.The Fe-Co-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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(10%NH
3) gas mixture, reacted 2 hours down at 900 ℃.Products therefrom was handled 24 hours in 50 ℃ of 2M hydrochloric acid.Obtain diameter in the BN of 20-40nm fullerene-like nanoparticles (see figure 10).
Embodiment 9: with Co
75B
25The nanometer microparticle catalytic agent prepares the B-C-N fullerene-like nanoparticles by acid treatment again 900 ℃ of reactions.
KBH by 1mol/L
4The CoCl of reduction 0.1mol/L
2Mixed solution (Fe
2+: Co
2+=3: 1) make 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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(10%NH
3) ethene of gas mixture and 50SCCM, 900 ℃ of reactions 3 hours down.Products therefrom was handled 16 hours in 70 ℃ of 2M hydrochloric acid.Obtain diameter at the B-C-N of 20-60nm fullerene-like nanoparticles (seeing Figure 11).
The gaseous state C source that the present invention can adopt can also be CH
4, C
2H
2Or C
2H
4Solid-state carbon source can also be used: use gac or Graphite Powder 99 art to place the alundum tube central zone with catalyzer.Heat up 850-900 ℃ again, with the N of 100 SCCM
2/ NH
3(10%NH
3) gas mixture reaction 3 hours.Obtain product much at one.
Plasma method growth B-C-N fullerene-like nanoparticles also can: open plasma source under low pressure hydrogen/argon atmosphere, use above-mentioned condition, the beginning aura feeds the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 1 hour.In the catalyst particle surface coverage B-C-N layer, obtain diameter and be the fullerene-like nanoparticles of about 40-200nm.
Embodiment 10: with Fe
70B
30The nanometer microparticle catalytic agent prepares average 50nm diameter BN fullerene-like nanoparticles by acid treatment again 850 ℃ of reactions.
KBH by 1mol/L
4FeSO with 0.1mol/L
4Liquid phase reaction makes the Fe of about 40 nanometers of median size
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 10 ℃ of per minutes under argon atmosphere is warmed up to 850 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 850 ℃.Covered a crystallization BN layer in the Fe-B nanoparticle surface, the BN Nano capsule that obtains diameter and be the parcel Fe-B of 30-60nm (is seen Figure 12 a).Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Obtain the BN fullerene-like nanoparticles (seeing Figure 12 b) of diameter average out to 50nm.
Embodiment 11: with Ni
70B
30The nanometer microparticle catalytic agent is 900 ℃ of reactions, again by the average about 80nm diameter BN fullerene-like nanoparticles of acid treatment preparation.
KBH by 1mol/L
4NiSO with 0.1mol/L
4Liquid phase reaction makes Fe
70B
30Nanoparticle.The Ni-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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 900 ℃.Covered a crystallization BN layer in the Co-B nanoparticle surface, obtaining diameter is the BN Nano capsule of the parcel Ni-B of 40-120nm.Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.The BN fullerene-like nanoparticles that obtains diameter and be 40-120nm (is seen Figure 13 a).
Embodiment 12: with Co
70B
30The nanometer microparticle catalytic agent is 900 ℃ of reactions, again by the average about 80nm diameter BN fullerene-like nanoparticles of acid treatment preparation.
KBH by 1mol/L
4CoSO with 0.1mol/L
4Liquid phase reaction makes Co
70B
30Nanoparticle.The Co-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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 900 ℃.Covered a crystallization BN layer in the Co-B nanoparticle surface, obtaining diameter is the BN Nano capsule of the parcel Co-B of 60-150nm.Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Obtaining diameter is the BN fullerene-like nanoparticles (seeing Figure 13 b) of 60-150nm.
Embodiment 13: with Fe
50B
50The nanometer microparticle catalytic agent is 900 ℃ of reactions, again by the average about 100nm diameter BN fullerene-like nanoparticles of the preparation of the pyroprocessing under the inert atmosphere.
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 30-100nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 900 ℃.Covered a crystallization BN layer in the Fe-B nanoparticle surface, obtaining diameter is the BN Nano capsule of the parcel Fe-B of 60-150nm.Products therefrom was handled 24 hours in 14000 ℃ of argon gas atmosphere.Obtaining diameter is the BN fullerene-like nanoparticles (seeing Figure 13 c) of 60-150nm.
Embodiment 14: with Fe
35Co
35B
30The nanometer microparticle catalytic agent is 900 ℃ of reactions, again by the average about 100nm diameter BN fullerene-like nanoparticles of the preparation of the pyroprocessing under the inert atmosphere.
KBH by 0.5mol/L
4The FeCl of reduction 0.1mol/L
2And CoCl
2Mixed solution (Fe
2+: Co
2+=1: 1) make the Fe of about 80 nanometers of median size
35Co
35B
30Nanoparticle.The Fe-Co-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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 900 ℃.Covered a knot product BN layer in the Fe-Co-B nanoparticle surface, obtaining diameter is the BN Nano capsule of the parcel Fe-B of 40-150nm.Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Products therefrom was handled 24 hours in 14000 ℃ of argon gas atmosphere, and obtaining diameter is the BN fullerene-like nanoparticles (seeing Figure 13 d) of 60-150nm.
With the deliquescent anhydrous FeCl of part
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 50-300nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 900 ℃.Covered a crystallization BN layer in the Fe-B nanoparticle surface, obtaining diameter is the BN Nano capsule of the parcel Fe-B of 80-350nm.Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Obtaining diameter is the BN fullerene-like nanoparticles (seeing Figure 14 a, 14b) of 80-350nm.The XRD spectra of BN fullerene-like nanoparticles is seen Figure 16, and the EDS spectrogram of BN fullerene-like nanoparticles is seen Figure 17.
Embodiment 16: with Fe
50B
50The nanometer microparticle catalytic agent is 900 ℃ of reactions, again by average about 200nm diameter polyhedron BN complete hollow ball of soccerballene shape of the preparation of the pyroprocessing under the inert atmosphere and open hollow ball.
With the deliquescent anhydrous FeCl of part
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 50-300nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 900 ℃.Covered a crystallization BN layer in the Fe-B nanoparticle surface, obtaining diameter is the BN Nano capsule of the parcel Fe-B of 80-350nm.Products therefrom was handled 24 hours in 1400 ℃ of argon gas atmosphere, and obtaining diameter is the BN fullerene-like nanoparticles (seeing Figure 14 c, 14d) of 80-350nm.
Embodiment 17: with borine, hydrogen is raw material, reaction B nanoparticle under the condition of microwave plasma.
Utilize borine, hydrogen reacts under the condition of microwave plasma, makes the B nanoparticle of diameter 40-100.(see Figure 15 a)
Embodiment 18: 1100 ℃ of left and right sides nitrogenize, prepare the Nano capsule of the B of BN parcel with the B nanoparticle.
The B nanoparticle 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 10 ℃ of per minutes under argon atmosphere is warmed up to 1100 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 1100 ℃.Cover a crystallization BN layer in the B nanoparticle surface, obtained the BN Nano capsule that diameter is about the parcel B of 100nm.(seeing Figure 15 b)
Identical method prepares the Nano capsule of the B of B-C-N parcel.Reaction adds the ethene of 50SCCM simultaneously.
Embodiment 19: the BN Nano capsule that will wrap up B with acid wash removes nuclear, obtains the BN fullerene-like nanoparticles that diameter is about 100-150nm.
The BN Nano capsule of parcel B was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Obtaining diameter is the BN fullerene-like nanoparticles (seeing Figure 15 C) of 100-150nm.The B nanoparticle of diameter 40-100.(see Figure 15 a) diameter be about the BN Nano capsule of the parcel B of 100nm.(seeing Figure 15 b).
Embodiment 20: the general growth conditions of Nano capsule is: earlier boracic (30～50%) nanoparticle that makes is placed the growth room, be warmed up to 1000-1300 ℃, feed the N of 70-150 SCCM simultaneously
2/ NH
3(4%NH
3) react and obtain, can control boracic nanoparticle size and control BN Nano capsule diameter.Also can feed the B-C-N Nano capsule that carbonaceous gas growth skin is simultaneously.
Embodiment 21: fullerene-like nanoparticles is polyhedral hollow nanostructured, yardstick is 20-300nm, general growth conditions is: BN or B-C-N Nano capsule burn vehement (1400 ℃) down at high temperature again, and its core dissociates out from shell, and hollow shell forms fullerene-like nanoparticles; The core that perhaps contains boron is dissolved in the acid solution, and remaining hollow shell forms fullerene-like nanoparticles.
Embodiment 22: imitative example 2 is used Ni in the same way
70B
30The nanometer microparticle catalytic agent is at 900 ℃ of preparation B-C-N Nano capsules.
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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reaction adds the ethene of 50SCCM simultaneously.Reacted 2 hours down at 900 ℃.In the catalyst particle surface coverage one crystallization B-C-N layer, also obtain the BN Nano capsule of diameter for the parcel Ni-B of about 40-120nm.
Embodiment 23: imitative example 3 conditions are with Co
75B
25The nanometer microparticle catalytic agent is at 900 ℃ of preparation BN Nano capsules.
KBH by 1mol/L
4CoCl with 0.1mol/L
2Liquid phase reaction makes the Co of about 30 nanometers of median size
75B
25Nanoparticle.The Co-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 10 ℃ of per minutes under argon atmosphere is warmed up to 900 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3/ C
2H
2(4%NH
3, 10%C
2H
2) gas mixture, reaction adds the ethane of 50SCCM simultaneously, reacts 2 hours down at 900 ℃.In the catalyst particle surface coverage one B-C-N layer, obtain the B-C-N Nano capsule of diameter for the parcel Ni-B of about 30-100nm.
Embodiment 24: imitative example 4 conditions, and with Fe
70B
30The B-C-N Nano capsule that the nanometer microparticle catalytic agent makes under plasma exciatiaon.
Make the Fe of median size 40-200nm by the method for mechanical ball milling by iron powder and boron powder
70B
30Particulate.Place the silica tube central zone with this as catalyzer, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, open plasma source under low pressure hydrogen/argon atmosphere then, the beginning aura feeds the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 1 hour.In the catalyst particle surface coverage one BN layer, obtain the B-C-N Nano capsule of diameter for the bag Fe-B of about 40-200nm.Co with the same particle size scope
75B
25, Ni
70B
30And under plasma exciatiaon, make the B-C-N Nano capsule of same form.
Embodiment 25: imitative example 5 conditions, and with Fe
50B
50The nanometer microparticle catalytic agent is at 750 ℃ of BN fullerene-like nanoparticles that make and BN Nano capsule mixture.
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 30-100nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 750 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, feed the ethene of 50SCCM simultaneously, 750 ℃ of reactions 3 hours down.Around former Fe-B nanocatalyst particles, obtaining diameter is the BN fullerene-like nanoparticles of 20-50nm and the B-C-N Nano capsule of the parcel Fe-B that diameter is 30-150nm.
Embodiment 26: imitative example 6 conditions, and with Fe
35Ni
35B
30The nanometer microparticle catalytic agent is at 800 ℃ of B-C-N nanoparticles that make.
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.The Fe-Ni-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 10 ℃ of per minutes under argon atmosphere is warmed up to 800 ℃.Stop applying argon gas, feed the N of 100 SCCM
2/ NH
3(4%NH
3) gas mixture, feed near the ethane (also can insert solid active carbon the central section, product also is the B-C-N nanoparticle) of 50SCCM simultaneously, 800 ℃ of reactions 2 hours down.Obtain the B-C-N nanoparticle that diameter is 10-15nm in Fe-Ni-B nanoparticle bed district.
Embodiment 27: imitative example 7 conditions, and with Fe
50B
50The nanometer microparticle catalytic agent prepares the B-C-N fullerene-like nanoparticles by acid treatment again 750 ℃ of nitrogenize.
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 30-100nm
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 10 ℃ of per minutes under argon atmosphere is warmed up to 750 ℃.Stop applying argon gas, feed the N of 100SCCM
2/ NH
3(4%NH
3) gas mixture, reacted 3 hours down at 750 ℃.Products therefrom was handled 24 hours in 60 ℃ of 2M hydrochloric acid.Obtain diameter at the B-C-N of 20-50nm fullerene-like nanoparticles.
Claims (4)
1, the preparation method of a kind of BN or B-C-N Nano capsule or fullerene-like nanoparticles, it is characterized in that with nitrogenous gas or solid be nitrogenous source, nanocatalyst alloy particle with boracic 20～70% is done the boron source, in 700-900 ℃ of tube furnace or under microwave plasma excitated, reacted 1-5 hour, controllable growth BN Nano capsule, or the mixture of BN Nano capsule and fullerene-like nanoparticles; Be under the condition of carbon source existence at carbonaceous gas or solid simultaneously, the mixture of growth B-C-N Nano capsule or B-C-N Nano capsule and fullerene-like nanoparticles; The B-contained nano-catalyst alloy particle that adopts comprises Fe-B, Ni-B, Co-B, Fe-Ni-B, Fe-Co-B or Ni-Co-B, and its general formula is Fe
xB
100-x, Ni
yB
100-y, Co
zB
100-z, Fe
aNi
bB
100-a-bOr Fe
aCo
bB
100-a-b, x, y and z get 30-80, and a+b gets 30-80.
2,, it is characterized in that gasiform N source is N according to the preparation method of the described BN of claim 1 or B-C-N Nano capsule or fullerene-like nanoparticles
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.
3, according to the preparation method of claim 2 or 3 described BN or B-C-N Nano capsule or fullerene-like nanoparticles, the nanocatalyst alloy particle that it is characterized in that boracic is meant FeB, a kind of nanoparticle in NiB and the CoB nanoparticle or wherein two kinds or three kinds of mixtures.
4, according to the preparation method of claim 1 or 3 described BN or B-C-N Nano capsule or fullerene-like nanoparticles, it is characterized in that 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 30-100nm
50B
50Nanoparticle; With the Fe that obtains
50B
50Nanoparticle places the alundum tube central zone, applying argon gas and find time 3-5 time repeatedly then with mechanical pump, and the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 750 ℃; Stop applying argon gas, feed 100SCCM 4%NH
3N
2/ NH
3Gas mixture feeds the ethene of 50SCCM simultaneously, 750 ℃ of reactions 3 hours down; At former Fe
50B
50Around the Fe-B nanocatalyst particles, obtaining diameter is the BN fullerene-like nanoparticles of 20-50nm and the parcel Fe that diameter is 30-150nm
50B
50The B-C-N Nano capsule.
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