CN101580236A - Method for preparing boron nitride nanotubes by annealing of inorganic boracic precursor - Google Patents
Method for preparing boron nitride nanotubes by annealing of inorganic boracic precursor Download PDFInfo
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- CN101580236A CN101580236A CNA2009100627229A CN200910062722A CN101580236A CN 101580236 A CN101580236 A CN 101580236A CN A2009100627229 A CNA2009100627229 A CN A2009100627229A CN 200910062722 A CN200910062722 A CN 200910062722A CN 101580236 A CN101580236 A CN 101580236A
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Abstract
The invention relates to a novel method for preparing boron nitride nanotubes by annealing of an inorganic boracic precursor, comprising annealing the inorganic boracic precursor for 5-50h at the temperature of 800-1200 DEG C to obtain boron nitride nanotubes. The beneficial effects of the invention comprise that 1) annealing reaction of the boracic precursor is adopted to prepare boron nitride nanotubes, boron element is sintered with catalyst to form porous solid, the problem that the yield and the purity of boron nitride nanotubes are low is solved, the preparation yield limit of boron nitride nanotubes is surmounted, the preparation process is simple, the product yield of boron nitride nanotubes is above 80% and the purity is above 85%; 2) the chemical property of the prepared inorganic boracic precursor is stable which is applicable to batch manufacturing boron nitride nanotubes with low cost and high purity; the reaction condition of preparing precursor is mild, the process is simple, and the energy consumption and the cost are low, which is applicable to industrialized production and the precursor can be directly used to prepare boron nitride nanotubes.
Description
Technical field
The present invention relates to stupalith and field of nano material preparation, the concrete novel method that relates to from a kind of preparing boron nitride nanotubes by annealing of inorganic boracic precursor.
Background technology
People such as nineteen ninety-five Chopra have successfully prepared boron nitride nano-tube by the plasma electric arc discharge method, have opened the research prelude of boron nitride nano-tube.Boron nitride nano-tube has high-modulus and the high-strong toughness that compares favourably with carbon nanotube, fabulous chemical stability and thermostability.In addition, boron nitride nano-tube shows as the semi-conductor of broad-band gap, about 5.5eV.These characteristics have attracted from multi-field research interest such as semiconducter device, nano heterogeneous ceramic, hydrogen storage materials boron nitride nano-tube.
The preparation method of boron nitride nano-tube mainly contains arc light method of fusion, pyrochemical process, carbon nanotube template, laser and fuses method etc.Though obtained some successes and progress aspect preparing at boron nitride nano-tube in recent years, normal yield is very low, is difficult to a large amount of preparations.
Aspect the chemosynthesis boron nitride nano-tube, having a large amount of reports to adopt various inorganic or organic boron-containing compounds is that initiator prepares boron nitride nano-tube, though because these raw material boracics do not have the catalysis that promotes to form boron nitride nano-tube, thereby need extra catalyst.
Summary of the invention
Problem to be solved by this invention is a kind of novel method that adopts the inorganic boracic catalyst precursor through annealing preparation boron nitride nano-tube that proposes at above-mentioned existing deficiency, this preparation technology is simple, do not need extra catalyst, resulting boron nitride nano-tube output is big, the purity height.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: a kind of method of preparing boron nitride nanotubes by annealing of inorganic boracic precursor, it is characterized in that the inorganic boracic catalyst precursor was annealed 5～50 hours down at 800～1200 ℃, promptly can obtain boron nitride nano-tube, described inorganic boracic catalyst precursor component is: rich boron shaped metal boride and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of institute's boracic (B) element and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654, described rich boron shaped metal boride is the diboride of IIA family alkali earth metal or thulium, four borides, hexaboride, in the dodecaboride any one or multiple mixing, annealing atmosphere are the mixed gas of ammonia or nitrogen and hydrogen.
Press such scheme, preferred rich boron shaped metal boride is MgB
2, MgB
4, MgB
6, CaB
6, SrB
6, BaB
6, YB
6, LaB
6Or CeB
6
Press such scheme, best rich boron shaped metal boride is CaB
6
Press such scheme, described transistion metal compound is oxide compound, oxyhydroxide, hydrochloride or the nitrate of transition metal, and transition metal is VB, VIB, VIIB or VIIIB group 4 transition metal element.
Press such scheme, described transition metal is preferably V, Mo, Mn, Fe, Co or Ni.
Press such scheme, described inorganic boracic catalyst precursor in air in 50～800 ℃ of temperature ranges 24 hours rate of weight loss and rate of body weight gain all less than 5wt.%.
Above-mentioned inorganic boracic catalyst precursor, can adopt to do and mix/reaction process, it is characterized in that including following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of institute's boracic (B) element and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) batch mixing process: load weighted raw material is added high speed mixer, mixed 3～10 minutes, it is mixed; (3) moulding process: compound is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 10～30 minutes; (4) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (5) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
The inorganic boracic catalyst precursor, can adopt ball milling/reaction process, it is characterized in that including following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of institute's boracic (B) element and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) mechanical milling process: adopt planetary ball mill that load weighted raw material is carried out ball milling, use stainless steel jar mill and stainless steel abrading-ball, ball milling 1～120 hour is revolved round the sun 100～300 rev/mins in 100～500 rev/mins of rotations; 3) moulding process: compound is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 10～30 minutes; (4) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (5) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
The inorganic boracic catalyst precursor, can adopt liquid-phase mixing/reaction process, it is characterized in that including following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of institute's boracic (B) element and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) dispersion process: load weighted raw material is poured in the beaker, is added distilled water or ethanol and mix 10～30 minutes, or mix 10～30 minutes ultrasonic again 5～20 minutes; (3) suction filtration and drying process: carry out suction filtration by circulation ability of swimming vacuum pump, and resulting filter cake was put into vacuum drying oven dry 5～24 hours, pulverize then; (4) moulding process: will pour in the steel die through the filter cake of super-dry and pulverizing, and utilize 500 tons of pressing machinees, pressurize 10～30 minutes; (5) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (6) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
The inorganic boracic catalyst precursor, can adopt liquid phase compound/reaction process, it is characterized in that including following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of institute's boracic (B) element and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) coating process: add the ammoniacal liquor of 25～28wt.% in load weighted raw material, mixed solution stirred 1～5 hour, left standstill 1～3 hour; (3) suction filtration and drying process: carry out suction filtration by circulation ability of swimming vacuum pump, and resulting filter cake was put into vacuum drying oven dry 5～24 hours, pulverize then; (4) moulding process: will pour in the steel die through the filter cake of super-dry and pulverizing, and utilize 500 tons of pressing machinees, pressurize 10～30 minutes; (5) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (6) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.Reaction formula is exemplified below: CaB
6+ Fe
3++ OH
-=CaB
6@Fe (OH)
3↓, that is: Fe
3+With OH
-Reaction forms Fe (OH)
3, parcel CaB
6Particle forms precipitation.
Rich boron shaped metal boride that the present invention is used and transistion metal compound and other reagent can be analytical reagent or chemically pure reagent.
Make inorganic boracic catalyst precursor by spreading chemical reaction certainly by metal boride and metal oxide in oxygen-containing atmosphere, the preparation feedback kick off temperature is 500～850 ℃, and the self-propagating reaction temperature is greater than 1000 ℃.Through after the self-propagating high-temperature reaction treatment, the presoma stable in properties of formation does not take place to decompose weightless in 800 ℃ and following air, and oxidation weight gain does not take place yet.Experiment shows, at 24 hours maximum rate of weight loss of 800 ℃ of insulations and maximum rate of body weight gain all less than 5wt.%.
Inorganic boracic catalyst precursor preparation feedback is exemplified below:
CaB
6+Co
2O
3＝2CoB+CaO+4B+O
2↑ (1)
As the formula (1), CaB
6Generate CoB, CaO, simple substance B and oxygen molecule with reaction.O wherein
2Because high temperature discharges, make from spreading product to be the porous honeycomb solid.Also may generate B in the reaction
2O
3, but because the presoma that makes does not almost have weightlessness in 50～800 ℃ of temperature ranges, and mass change shows the B of generation less than 5wt.% before and after the reaction
2O
3Amount seldom.
CaB
6+6NH
3→BN+Ca+9H
2↑ (2)
CoB+NH
3→BN+Co+3/2H
2↑ (3)
B+NH
3→BN+3/2H
2↑ (4)
Annealing generates the possible reaction of boron nitride nano-tube suc as formula shown in (2)～(4).CaB
6With NH
3Reaction forms boron nitride nano-tube, Ca and hydrogen (formula (2)).Similarly, CoB, B and ammonia have all formed boron nitride nano-tube (formula (3), (4)).Wherein Ca, Co also may with NH
3Reaction generates Ca
3N
2, CoN.
According to nanotube VLS catalytic growth mechanism, the catalyst alloy that is evenly distributed in the annealing reaction system [Co-Ca] is or/and constitute the running balance system between the particle of multicomponent alloy system [Co-Ca-B-N], gas phase B and N atom and the solid phase boron nitride three.Work as CaB
6With NH
3Reaction constantly produces B, N atomic time, does in metal alloy particle under the effect of catalyzer and shape template, and balance moves to the boron nitride direction.The formation of boron nitride, originally become the shell structure of the multilayer type that is similar to soccerballene in the granules of catalyst surface growth, because the shape of catalyst particle can not be constant fully, cause the solid phase boron nitride of catalyst pellets sub-surface to be grown and extension, thereby formed many walls boron nitride nano-tube towards certain direction.
Beneficial effect of the present invention is:
1) adopt inorganic boracic catalyst precursor annealing reaction to prepare boron nitride nano-tube, earlier together boron and sintering of catalyst, form the vesicular solid, not only solved the difficult problem that the boron nitride nano-tube productive rate is little, purity is low, also broken through the restriction that boron nitride nano-tube prepares output, preparation technology is simple, and the boron nitride nano-tube product yield reaches more than 80%, and purity is greater than 85%.
2) prepared inorganic boracic catalyst precursor chemical property is stable, be applicable to low-cost batch preparations high purity nitrogenize boron nano-tube material, the reaction conditions of preparation presoma is relatively gentleer, process is simple and convenient, energy consumption is low, with low cost, be fit to suitability for industrialized production, presoma does not need can be directly used in the preparation boron nitride nano-tube through purifying.
Description of drawings
Fig. 1. the XRD spectra of boron nitride nano-tube.
Fig. 2. the SEM photo of boron nitride nano-tube.
Fig. 3. the TEM photo of boron nitride nano-tube.
Fig. 4. the FTIR figure of boron nitride nano-tube.
Embodiment
Further introduce the present invention below by embodiment, but embodiment can not be construed as limiting the invention.
With six calcium boride (CaB
6) be the boron source, cobalt oxide (Co
2O
3) introduce inorganic boron source presoma preparation technology for catalyzer.The first step: batching.CaB
6, Co
2O
3All be analytical reagent, take by weighing 50.03g CaB
6, 50.25g Co
2O
3, wherein mol ratio B: Co is 1: 0.21.Second step: batch mixing.With load weighted CaB
6And Co
2O
3Add high speed mixer (18000 rev/mins) and mixed 5 minutes, make it full and uniform.The 3rd step: moulding.Compound is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 15 minutes, moulding is taken out.The 4th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 12 minutes down at 750 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 5th step: pulverize.Reacted material is added abundant the pulverizing 5 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 97.65g, mass loss rate is 2.6%, sealing, stored for future use.
Embodiment 2 dry powder ball-milling technologies
With six calcium boride (CaB
6) be the boron source, nickelous chloride (NiCl
2) introduce inorganic boron source presoma preparation technology for catalyzer.The first step: batching.CaB
6, NiCl
2Be analytical reagent all, take by weighing 50.04g CaB
6, 40.09g NiCl
2, wherein mol ratio B: Ni is 1: 0.11.Second step: ball milling.Pour confected materials into stainless steel jar mill, adopt the stainless steel abrading-ball, adjust the ball mill parameter, 500 rev/mins in autobiography revolves round the sun 250 rev/mins ball milling 12 hours.The 3rd step: moulding.The ball milling material is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 13 minutes, moulding is taken out.The 4th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 8 minutes down at 850 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 5th step: pulverize.Reacted material is added abundant the pulverizing 5 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 86.68g, mass loss rate is 3.8%, sealing, stored for future use.
Embodiment 2 only is used one of them embodiment of inorganic boracic catalyst precursor of the present invention, and each cited in technical solution of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Embodiment 3 liquid phases are disperseed from spreading technology
With Barium hexaboride (BaB
6) be the boron source, ferric oxide (Fe
2O
3) introduce inorganic boron source presoma preparation technology for catalyzer.The first step: batching.BaB
6, Fe
2O
3All be analytical reagent, take by weighing 60.03g BaB
6, 35.09g Fe
2O
3, wherein mol ratio B: Fe is 1: 0.24.Second step: disperse.Load weighted material is poured in the 1000ml beaker, added 500ml distilled water, stirred 20 minutes, ultrasonic 10 minutes, material is uniformly dispersed in distilled water.The 3rd step: suction filtration.Mixed solution is carried out suction filtration by circulation ability of swimming vacuum pump.The 4th step: drying.Resulting filter cake was put into 80 ℃ of vacuum drying ovens dry 8 hours.The 5th step: pulverize.The filter cake that drying is good adds high speed mixer (18000 rev/mins) and mixed 5 minutes.The 6th step: moulding.Compound is poured in the steel die, utilized 500 tons of pressing machine pressurizes 18 minutes, moulding is taken out.The 7th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 10 minutes down at 800 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 8th step: pulverize.Reacted material is added abundant the pulverizing 5 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 92.34g, mass loss rate is 3.1%, sealing, stored for future use.
Embodiment 3 only is used one of them embodiment of inorganic boracic catalyst precursor of the present invention, and each cited in technical solution of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Embodiment 4 is compound from spreading technology
With six calcium boride (CaB
6) be the boron source, iron nitrate (Fe (NO
3)
39H
2O) introduce inorganic boron source presoma preparation technology for catalyzer.The first step: batching.CaB
6, Fe (NO
3)
39H
2O is an analytical reagent, takes by weighing 30.12g CaB
6, 83.89gFe (NO
3)
39H
2O, wherein mol ratio B: Fe is 1: 0.12.Second step: reaction coats.Load weighted material is poured in the 1000ml beaker, and adding the 30.15ml massfraction is 25～28wt.% ammoniacal liquor, stirs 2 hours, leaves standstill 1 hour.The 3rd step: washing suction filtration.Carry out suction filtration by circulation ability of swimming vacuum pump, obtain filter cake.The 4th step: drying.Resulting filter cake was put into 80 ℃ of vacuum drying ovens dry 10 hours.The 5th step: pulverize.The filter cake that drying is good adds high speed mixer (18000 rev/mins) and mixed 7 minutes.The 6th step: moulding.Compound is poured in the steel die, utilized 500 tons of pressing machine pressurizes 20 minutes, moulding is taken out.The 7th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 16 minutes down at 850 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 8th step: pulverize.Reacted material is added abundant the pulverizing 7 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 44.81g, mass loss rate is 3.9%, sealing, stored for future use.
Embodiment 4 only is used one of them embodiment of inorganic boracic catalyst precursor of the present invention, and each cited in technical solution of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
With lanthanum hexaborane (LaB
6) be the boron source, nickel oxide (NiO) is introduced inorganic boron source presoma preparation technology for catalyzer.The first step: batching.LaB
6, NiO is analytical reagent, takes by weighing 40.21g LaB
6, 57.56g NiO, wherein mol ratio B: Ni is 1: 0.651.Second step: batch mixing.With load weighted LaB
6Add high speed mixer (18000 rev/mins) with NiO and mixed 5 minutes, make it full and uniform.The 3rd step: moulding.Compound is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 17 minutes, moulding is taken out.The 4th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 9 minutes down at 800 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 5th step: pulverize.Reacted material is added abundant the pulverizing 6 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 94.15g, mass loss rate is 3.7%, sealing, stored for future use.
Embodiment 6 liquid phases are disperseed from spreading technology
With magnesium diboride (MgB
2) be the boron source, ferric oxide (Fe
2O
3) introduce inorganic boron source presoma preparation technology for catalyzer.The first step: batching.MgB
2, Fe
2O
3All be analytical reagent, take by weighing 30.07g MgB
2, 40.21g Fe
2O
3, wherein mol ratio B: Fe is 1: 0.38.Second step: disperse.Load weighted material is poured in the 500ml beaker, added 300ml distilled water, stirred 15 minutes, ultrasonic 10 minutes, material is uniformly dispersed in distilled water.The 3rd step: suction filtration.Mixed solution is carried out suction filtration by circulation ability of swimming vacuum pump.The 4th step: drying.Resulting filter cake was put into 80 ℃ of vacuum drying ovens dry 8 hours.The 5th step: pulverize.The filter cake that drying is good adds high speed mixer (18000 rev/mins) and mixed 5 minutes.The 6th step: moulding.Compound is poured in the steel die, utilized 500 tons of pressing machine pressurizes 16 minutes, moulding is taken out.The 7th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 10 minutes down at 800 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 8th step: pulverize.Reacted material is added abundant the pulverizing 7 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 67.85g, mass loss rate is 3.5%, sealing, stored for future use.
Embodiment 6 only is used one of them embodiment of inorganic boracic catalyst precursor of the present invention, and each cited in technical solution of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Embodiment 7 dry powder ball-milling technologies
With Barium hexaboride (BaB
6) and magnesium diboride (MgB
2) be the boron source, cobalt oxide (Co
2O
3) introduce inorganic boron source presoma preparation technology for catalyzer.The first step: batching.BaB
6, MgB
2, Co
2O
3Be analytical reagent all, take by weighing 25.03g BaB
6, 25.12g MgB
2, 86.69g Co
2O
3, wherein mol ratio B: Co is 1: 0.57.Second step: ball milling.Pour confected materials into the steel ball ball grinder, adjust the ball mill parameter, 500 rev/mins in autobiography revolves round the sun 250 rev/mins ball milling 12 hours.The 3rd step: moulding.The ball milling material is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 16 minutes, moulding is taken out.The 4th step: reaction.The material of moulding is put into retort, do not need sealing.Retort is inserted in the process furnace of argon shield, be incubated 10 minutes down at 800 ℃, naturally cooling is opened a jar taking-up product, and outward appearance is that black is cellular.The 5th step: pulverize.Reacted material is added abundant the pulverizing 7 minutes in the high speed mixer (18000 rev/mins), weighing, quality is 130.23g, mass loss rate is 4.8%, sealing, stored for future use.
Embodiment 7 only is used one of them embodiment of inorganic boracic catalyst precursor of the present invention, and each cited in technical solution of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Embodiment 8:
Get 100.20 gram CaB
6With 79.54 gram Co
2O
3Prepare 179.40 gram presomas according to embodiment 1 step reaction, in 800 ℃ of annealing 48 hours, keeping the ammonia gas flux was 2.5L/min, cools to room temperature with the furnace, took out product, obtained white powder 127.3 grams through purification, with CaB
6For benchmark calculates its yield is 89.5%.
The X-ray diffraction analysis (XRD) of gained sample with XD-5A type x-ray powder diffraction instrument (30kV, 20mA go into=1.5406
), 2 θ are 10-80 ° of scope.Observe pattern with the scanning electronic microscope (SEM) of JSM-5510LV model, method for making sample is directly to adopt the product powder distribution on the double faced adhesive tape and be bonded on the sample copper platform and observe behind the metal spraying.Study its microstructure with JEM 2100 type transmission electron microscopes (TEM), sample is ultra-sonic dispersion in dehydrated alcohol, is added drop-wise on the copper mesh.Infrared spectroscopy (FTIR) is with the sample preparation of KBr pressed disc method, adopts Impact 420 class infrared spectrometer to carry out the mapping of infrared spectra.
Accompanying drawing 1 has provided the XRD spectra of boron nitride nano-tube sample.Meet finely with JCPDS standard card number (NO.85-1068) hexagonal boron nitride crystalline XRD diffraction peak.By each crystal face d value of XRD, calculating the product lattice constant is a=0.2487nm, c=0.6748nm, and with standard card a=0.2510 nm, c=0.6690nm conforms to substantially, shows that product is the hexagonal boron nitride structure.
Accompanying drawing 2 is SEM photos of boron nitride nano-tube sample, and scale length is represented 1 μ m in the photo.By photo as seen, greater than 5 μ m, external diameter is even greater than generally for the boron nitride nanometer length of tube that is obtained, and external diameter is less than 50nm.The content of boron nitride nano-tube can estimate from photo that its content is greater than 85wt.%, and other has a spot of boron nitride fragment and fragment impurity.
Accompanying drawing 3 is representational TEM photos of boron nitride nano-tube sample, and wherein scale length is represented 100nm among Fig. 1 a, and scale length is represented 300nm among Fig. 1 b.As seen, the nanotube external diameter is about 20～30nm from Fig. 1 a, and wall thickness is about 5～10nm, and this is the main pattern that constitutes nanotube.As seen, corrugated nanotube external diameter is about 100nm from Fig. 1 b, and wall thickness is about 10～25nm, also has boron nitride hollow cone, heavy wall boron nitride nano-tube and boron nitride thin slice and fragment in addition, and these all are typical less important patterns, and content is less in sample.
Accompanying drawing 4 is the FTIR spectrogram of boron nitride nano-tube sample.As shown in the figure, significantly infrared absorption peak lays respectively at 3431,1380 and 804cm
-1The absorption peak at three places.Be positioned at 1381cm
-1And 804cm
-1Absorption peak, then respectively because the outer flexural vibration of face of the N-B-N key in TO vibration modes and the boron nitride in the face of B-N key in the boron nitride.Hence one can see that, and product is a boron nitride.And be positioned at 3431cm
-1The absorption peak at place is because the O-H and the N-H key chattering of sample surfaces planar water.
Embodiment 9:
Get 9.03 gram MgB
2With 4.82 gram Fe
2O
3Prepare 13.85 gram presomas according to embodiment 6 step reaction, in 1200 ℃ of annealing 5 hours, keeping the ammonia gas flux was 1.5L/min, cools to room temperature with the furnace then, took out product, obtained white powder 8.31 grams, with MgB
2For benchmark calculates its yield is 85.2%.Product is analyzed through XRD, SEM, TEM and FTIR, proves that product is purer boron nitride nano-tube, and boron nitride nano-tube content is more than 80%, the about 20 μ m of pipe range, diameter 20～40nm, even thickness.
Embodiment 10:
Get 85.00 gram LaB
6Prepare 106.10 gram precursors with 20.85 gram NiO according to embodiment 5 step reaction, in 1000 ℃ of annealing 20 hours, keep nitrogen/hydrogen gas mixture (mol ratio N then
2: H
2=1: 3～10) flux is 0.5L/min, cools to room temperature with the furnace, takes out product, obtains white powder 56.89 grams, with LaB
6For benchmark calculates its yield is 91.6%.Product is analyzed through XRD, SEM, TEM and FTIR, proves that product is purer boron nitride nano-tube, and boron nitride nano-tube content is about more than 80%, pipe range 30～120 μ m, diameter 10～20nm, even thickness.
Claims (10)
1, a kind of method of preparing boron nitride nanotubes by annealing of inorganic boracic precursor, it is characterized in that the inorganic boracic catalyst precursor was annealed 5～50 hours down at 800～1200 ℃, promptly can obtain boron nitride nano-tube, described inorganic boracic catalyst precursor component is: rich boron shaped metal boride and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of contained boron and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654, described rich boron shaped metal boride is the diboride of IIA family alkali earth metal or thulium, four borides, hexaboride, in the dodecaboride any one or multiple mixing, annealing atmosphere are the mixed gas of ammonia or nitrogen and hydrogen.
2, by the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that rich boron shaped metal boride is MgB
2, MgB
4, MgB
6, CaB
6, SrB
6, BaB
6, YB
6, LaB
6Or CeB
6
3, by the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 2, it is characterized in that rich boron shaped metal boride is CaB
6
4, press the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that described transistion metal compound is oxide compound, oxyhydroxide, hydrochloride or the nitrate of transition metal, transition metal is VB, VIB, VIIB or VIIIB group 4 transition metal element.
5, by the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 4, it is characterized in that described transition metal is preferably V, Mo, Mn, Fe, Co or Ni.
6, by the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that described inorganic boracic catalyst precursor in air in 50～800 ℃ of temperature ranges 24 hours rate of weight loss and rate of body weight gain all less than 5wt.%.
7, press the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that the inorganic boracic catalyst precursor, adopt to do and mix/the reaction process preparation, include following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of contained boron and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) batch mixing process: load weighted raw material is added high speed mixer, mixed 3～10 minutes, it is mixed; (3) moulding process: compound is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 10～30 minutes; (4) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (5) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
8, press the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that the inorganic boracic catalyst precursor, adopt ball milling/reaction process preparation, include following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of contained boron and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) mechanical milling process: adopt planetary ball mill that load weighted raw material is carried out ball milling, use stainless steel jar mill and stainless steel abrading-ball, ball milling 1～120 hour is revolved round the sun 100～300 rev/mins in 100～500 rev/mins of rotations; 3) moulding process: compound is poured in the steel die, utilized 500 tons of pressing machinees, pressurize 10～30 minutes; (4) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (5) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
9, press the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that the inorganic boracic catalyst precursor, adopt liquid-phase mixing/reaction process preparation, include following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of contained boron and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) dispersion process: load weighted raw material is poured in the beaker, is added distilled water or ethanol and mix 10～30 minutes, or mix 10～30 minutes ultrasonic again 5～20 minutes; (3) suction filtration and drying process: carry out suction filtration by circulation ability of swimming vacuum pump, and resulting filter cake was put into vacuum drying oven dry 5～24 hours, pulverize then; (4) moulding process: will pour in the steel die through the filter cake of super-dry and pulverizing, and utilize 500 tons of pressing machinees, pressurize 10～30 minutes; (5) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (6) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
10, press the method for the described preparing boron nitride nanotubes by annealing of inorganic boracic precursor of claim 1, it is characterized in that the inorganic boracic catalyst precursor, adopt liquid phase compound/the reaction process preparation, include following steps: (1) blending process: by rich boron shaped metal boride of proportioning raw materials weighing and transistion metal compound, the mol ratio B of the amount of contained transition metal M in the amount of contained boron and the transistion metal compound in the described rich boron shaped metal boride: M is 1: 0.106～0.654; (2) coating process: add the ammoniacal liquor of 25～28wt.% in load weighted raw material, mixed solution stirred 1～5 hour, left standstill 1～3 hour; (3) suction filtration and drying process: carry out suction filtration by circulation ability of swimming vacuum pump, and resulting filter cake was put into vacuum drying oven dry 5～24 hours, pulverize then; (4) moulding process: will pour in the steel die through the filter cake of super-dry and pulverizing, and utilize 500 tons of pressing machinees, pressurize 10～30 minutes; (5) reaction process: will go up the step gains and put into retort, and insert in the process furnace, and be incubated 1～60 minute down in 500～850 ℃; (6) crushing process: the reaction products therefrom adds high speed mixer, pulverizes to get final product in 3～10 minutes under 5000～18000 rev/mins of conditions.
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| CN101786884A (en) * | 2010-02-10 | 2010-07-28 | 武汉工程大学 | Preparation method of boron nitride nano-tube |
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| CN101786611B (en) * | 2010-02-09 | 2012-03-21 | 武汉工程大学 | Method for preparing boron nitride nanotube by Fe3BO6 ammoniation |
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| CN107673318A (en) * | 2016-08-01 | 2018-02-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nano-tube and its batch preparation |
| CN109821533A (en) * | 2019-02-25 | 2019-05-31 | 吉林大学 | A kind of transition metal boride catalyst, preparation method and applications |
| CN112320770A (en) * | 2020-08-19 | 2021-02-05 | 耐尔泰科株式会社 | Preparation method and device of nano material |
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