CN103030120B - Fabrication method of boron-carbon-nitrogen nanotube - Google Patents
Fabrication method of boron-carbon-nitrogen nanotube Download PDFInfo
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- CN103030120B CN103030120B CN201210593109.1A CN201210593109A CN103030120B CN 103030120 B CN103030120 B CN 103030120B CN 201210593109 A CN201210593109 A CN 201210593109A CN 103030120 B CN103030120 B CN 103030120B
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Abstract
The invention relates to a compound containing boron and nitrogen, and discloses a fabrication method for synthesizing a boron-carbon-nitrogen nanotube with a chemical vapour deposition method. The fabrication method comprises the steps that a nickel oxide-sodium chloride catalyst precursor is prepared and placed in a quartz boat; the quartz boat is placed in a constant temperature area of a horizontal tube furnace; hydrogen is supplied; the temperature is raised and kept; hydrogen is shut down; a gas mixture of nitrogen, methyl borate vapour and methane is continuously supplied to the tube furnace; a chemical vapour deposition reaction is conducted; boron-carbon-nitrogen nanotube-sodium chloride composite powder is prepared; the powder is put into a deionized water solution of sodium dodecyl benzene sulfonate; sodium chloride is dissolved completely through ultrasonic dispersion; a precipitate in the solution is filtered; washing and drying are conducted; and the purified boron-carbon-nitrogen nanotube is fabricated. The fabrication method overcomes the defects in the prior art that the boron and nitrogen doped carbon nanotube is poor in crystal form, and low in doping efficiency and purity, and the boron-carbon-nitrogen nanotube is difficult in purification and dispersion.
Description
Technical field
Technical scheme of the present invention relates to boracic and nitrogen compound, specifically the preparation method of boron-carbon nanotube.
Background technology
Boron-carbon nanotube can be regarded the product that part carbon atom in graphite network is replaced by boron or nitrogen-atoms as, and B-C-N ternary compound is between hexagonal boron nitride and graphite-structure.Though its morphological structure and carbon nanotube have similarity, it has than the more excellent mechanical property of carbon nanotube and electric property, has higher resistance of oxidation, and mechanical property and electric property be not subject to the impact of its diameter, only relevant with its composition.Therefore, boron-carbon nanotube has than the better physics of carbon nanotube and mechanical property, at matrix material, magneticsubstance, luminescent material and electronic material numerous areas, has a wide range of applications.Although boron-carbon nanotube has many advantageous properties, the bottleneck of restriction boron-carbon nanotube application is its preparation difficulty, and synthetic yield is lower, and building-up process is difficult to control.
In prior art, the main method of preparing boron-carbon nanotube has arc discharge method, plasma evaporation method, heated filament vapour deposition process and pyrolysis method, under different preparation conditions, by catalyzer, carbon source, boron source and nitrogenous source, prepared and come in every shape and the element different boron-carbon nanotube that distributes.CN101718731B discloses boron-carbon nanotube/semiconductor oxide composite and preparation method thereof, and wherein boron-carbon nanotube is by catalyzer, make in ammonia atmosphere containing boron material and carbon nanotube; CN100354202C has reported a kind of method of preparing at low temperatures boron-carbon nanotube, with KBH
4, NH
4cl, ZnBr
2with benzene be that starting material are prepared boron-carbon nanotube in stainless steel cauldron; CN101718732B has disclosed carbon doped boron-nitrogen nanotube/semiconductor oxide matrix material and preparation method thereof, wherein adopts catalyzer, synthetic in ammonia after grinding containing boron material and carbon nanotube, then purifies, obtains carbon doped boron-nitrogen nanotube after roasting.Although above-mentioned prior art adopts the whole bag of tricks to realize the synthetic of boron-carbon nanotube and controlled, the shortcoming existing is: the boron-carbon nanotube crystal formation for preparing (1) is poor, doping efficiency and purity low; (2) synthesis condition is harsher, is unsuitable for the volume production of boron-carbon nanotube; (3) purification of boron-carbon nanotube is large with dispersion difficulty.Therefore, find that a kind of synthesis route is simple, crystal formation good, productive rate and purity is high, purify and disperse easy boron-carbon nanotube preparation method significant for its widespread use of promotion.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that boron-carbon nanotube is provided, a kind of preparation method who synthesizes boron-carbon nanotube by chemical Vapor deposition process, preparing on nickel oxide-sodium-chlor catalyzer precursor basis, by chemical vapor deposition method, prepare boron-carbon nanotube-sodium-chlor powder, and then the acquisition boron-carbon nanotube of purifying, boron and nitrogen-doped carbon nanometer pipe poor crystal form in prior art have been overcome, doping efficiency and purity are low, and boron-carbon nanotube is purified and disperses the shortcoming that difficulty is large.
The present invention solves this technical problem adopted technical scheme: the preparation method of boron-carbon nanotube is a kind of preparation method who synthesizes boron-carbon nanotube by chemical Vapor deposition process, and concrete steps are as follows:
The first step, prepares nickel oxide-sodium-chlor catalyzer precursor
Be the ratio of nickelous nitrate: sodium-chlor=0.02～0.55:1 by weight, take Nickelous nitrate hexahydrate and the sodium-chlor of institute's expense, under induction stirring state, the sodium-chlor taking is dissolved in deionized water by the concentration of 50～80g/L, then the Nickelous nitrate hexahydrate taking is dissolved in above-mentioned deionized water, continue induction stirring until sodium-chlor and Nickelous nitrate hexahydrate dissolve completely, above-mentioned solution is placed in to Constant Temp. Oven in 60～90 ℃ of dry 48～96h, evaporate completely to moisture, then the nickelous nitrate and the sodium-chlor crystalline mixture that after dry, obtain are placed in to ball grinder, adopt planetary ball mill with speed ball milling 3～6h of 500～1000r/min, above-mentioned mixture after ball-milling processing is placed in to quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 180～240ml/min continues to pass into nitrogen and is warming up to 350～600 ℃ in this tube furnace, insulation 2～4h, make this tube furnace under the nitrogen atmosphere of 180～240ml/min flow velocity till cool to room temperature, make nickel oxide-sodium-chlor catalyzer precursor,
Second step, prepares boron-carbon nanotube-sodium-chlor composite powder
Nickel oxide-sodium-chlor catalyzer precursor that the first step is made is placed in quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 180～240ml/min passes into hydrogen and is warming up to 550～750 ℃ in this tube furnace, insulation 1.5～3.5h, then close hydrogen, by volume ratio, be nitrogen again: the gas mixture of methyl-borate steam: methane=4～8:0.5～1:1 continues to pass in this tube furnace with the flow velocity of 330～600ml/min, at 550～750 ℃, carry out chemical vapour deposition reaction 0.5～1.5h, close afterwards methyl-borate steam and methane and adjust nitrogen flow, make above-mentioned tube furnace under the nitrogen atmosphere of 180～240ml/min flow velocity till cool to room temperature, make thus boron-carbon nanotube-sodium-chlor composite powder, wherein the quality percentage composition of boron-carbon nanotube is 5.1～17.6%,
The 3rd step, purification boron-carbon nanotube
Boron-carbon nanotube-sodium-chlor composite powder second step being made by the concentration of 2～5g/L is put into the deionized water solution that mass percent concentration is 0.3～1.0% Sodium dodecylbenzene sulfonate, the beaker that above-mentioned solution is housed is placed in to ultrasonic separating apparatus disperses 10～20min that sodium-chlor is dissolved completely by the ultrasonic wave of 30kHz～40kHz, throw out in solution is filtered, by washed with de-ionized water 3～4 times, then use Constant Temp. Oven in 80～90 ℃ of dry 2～4h, make the boron-carbon nanotube after purification.
The preparation method of above-mentioned boron-carbon nanotube, related starting material are all by commercially available, and equipment and process used is all that those skilled in the art are known.
The invention has the beneficial effects as follows:
Compared with prior art, the preparation method of boron-carbon nanotube of the present invention has outstanding substantive distinguishing features and is:
(1) because boron-carbon nanotube length-to-diameter ratio is large, specific surface energy is high, in liquid phase thermal decomposition method building-up process, be subject to strong van der Waals interaction, the boron-carbon nanotube of synthesized is unavoidably reunited and in subsequent processes, is difficult to disperse together in liquid phase; In solid-phase pyrolysis building-up process, though the carrier for dispersed catalyst can play the effect that disperses boron-carbon nanotube indirectly, but be often difficult to remove, the technique of removing carrier by strong acid, highly basic can cause damage to the structure of boron-carbon nanotube itself, and follow-up dispersing technology is complicated, dispersion effect is poor.The inventive method is the carrier as support nickel catalyzator by sodium-chlor, in early stage, in building-up process, can play dissemination to synthetic boron-carbon nanotube, and can realize the removal of carrier and the dispersion of boron-carbon nanotube by synthetic product being put into the method for the aqueous solution that contains dispersion agent, thereby the inventive method propose on sodium-chlor carrier, by technology controlling and process, synthesize the preparation thinking of boron-carbon nanotube, efficiently solve the problem of boron-carbon nanotube reunion and follow-up dispersion, purifying technique complexity and weak effect in existing synthetic method.
(2) to adopt boron source and nitrogenous source to adulterate to carbon nanotube be the common method of preparing boron-carbon nanotube to prior art, but the technique of carbon nanotube being adulterated by boron source and nitrogenous source easily causes that product crystal formation is unstable, the doping efficiency of B and N is low, boron-carbon nanotube purity is low and boron-carbon nanotube productive rate is low; Meanwhile, be subject to the effect of strong Van der Waals force, in starting material, the reunion of carbon nanotube causes subsequent boron carbon-nitrogen nano tube purify and disperse very difficult.The inventive method, by boron source, Carbon and nitrogen sources, makes B, C and N atom in catalyst metal particles, dissolve, spread and separate out in reaction zone, forms pentagonal class graphite linings structure, and then synthetic boron-carbon nanotube, makes it have stable crystal formation; B and N atom directly enter body inside in building-up process, thereby the doping efficiency of B and N, boron-carbon nanotube purity and boron-carbon nanotube synthetic yield all improve, and make boron-carbon nanotube synthetic product have higher chemical stability and thermostability; By water-soluble chlorination sodium, do purification and the dispersion that carrier is more easily realized boron-carbon nanotube.
Compared with prior art, the marked improvement that preparation method has of boron-carbon nanotube of the present invention is:
(1) compare with CN101718732B with prior art CN101718731B, more stable with the prepared boron-carbon nanotube crystal formation of preparation method of boron-carbon nanotube of the present invention, doping efficiency, purity and synthetic yield are higher, and are easy to purify and disperse.
(2) compare with prior art CN100354202C, the inventive method has overcome that the product that above-mentioned prior art makes is difficult to disperse in liquid phase, the poor shortcoming of dispersion effect, has the simple and easy to do feature of dispersing technology, and purification and dispersion effect better.
(3) the inventive method processing method is easy, production cost is low.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the high resolution scanning electron microscope photo of the prepared boron-carbon nanotube-sodium-chlor of the embodiment of the present invention 1 composite powder.
Fig. 2 is the transmission electron microscope photo of the boron-carbon nanotube after the prepared purification of the embodiment of the present invention 1.
Fig. 3 is the high resolution transmission electron microscopy photo of the boron-carbon nanotube after the prepared purification of the embodiment of the present invention 1.
Embodiment
Embodiment 1
The first step, prepares nickel oxide-sodium-chlor catalyzer precursor
Be the ratio of nickelous nitrate: sodium-chlor=0.02:1 by weight, take Nickelous nitrate hexahydrate and the sodium-chlor of institute's expense, under induction stirring state, the sodium-chlor taking is dissolved in deionized water by the concentration of 50g/L, then the Nickelous nitrate hexahydrate taking is dissolved in above-mentioned deionized water, continue induction stirring until sodium-chlor and Nickelous nitrate hexahydrate dissolve completely, above-mentioned solution is placed in to Constant Temp. Oven in 60 ℃ of dry 48h, evaporate completely to moisture, then the nickelous nitrate and the sodium-chlor crystalline mixture that after dry, obtain are placed in to ball grinder, adopt planetary ball mill with the speed ball milling 3h of 500r/min, above-mentioned mixture after ball-milling processing is placed in to quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 180ml/min continues to pass into nitrogen and is warming up to 350 ℃ in this tube furnace, insulation 2h, make this tube furnace under the nitrogen atmosphere of 180ml/min flow velocity till cool to room temperature, make nickel oxide-sodium-chlor catalyzer precursor,
Second step, prepares boron-carbon nanotube-sodium-chlor composite powder
Nickel oxide-sodium-chlor catalyzer precursor that the first step is made is placed in quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 180ml/min passes into hydrogen and is warming up to 550 ℃ in this tube furnace, insulation 1.5h, then close hydrogen, by volume ratio, be nitrogen again: the gas mixture of methyl-borate steam: methane=4:0.5:1 continues to pass in this tube furnace with the flow velocity of 330ml/min, at 550 ℃, carry out chemical vapour deposition reaction 0.5h, close afterwards methyl-borate steam and methane and adjust nitrogen flow, make above-mentioned tube furnace under the nitrogen atmosphere of 180ml/min flow velocity till cool to room temperature, make thus boron-carbon nanotube-sodium-chlor composite powder, wherein the quality percentage composition of boron-carbon nanotube is 5.1%,
Fig. 1 is the high resolution scanning electron microscope photo of the prepared boron-carbon nanotube-sodium-chlor of the embodiment of the present invention 1 composite powder.In this figure, by the chemical vapour deposition reaction of mixed gas, synthetic a large amount of finely dispersed boron-carbon nanotubes in composite powder, its length-to-diameter ratio is larger, more than length reaches 1 μ m, be subject to the impact of the atom doped formation pentagon of B and N class graphite linings structure, the curvature of tube wall constantly changes, and causes formed boron-carbon nanotube to be bending and surface irregularity.
The 3rd step, purification boron-carbon nanotube
Boron-carbon nanotube-sodium-chlor composite powder second step being made by the concentration of 2g/L is put into the deionized water solution that mass percent concentration is 0.3% Sodium dodecylbenzene sulfonate, the beaker that above-mentioned solution is housed is placed in to ultrasonic separating apparatus disperses 10min that sodium-chlor is dissolved completely by the ultrasonic wave of 30kHz, throw out in solution is filtered, by washed with de-ionized water 3 times, then use Constant Temp. Oven in 80 ℃ of dry 2h, make the boron-carbon nanotube after purification.
Fig. 2 is the transmission electron microscope photo of the boron-carbon nanotube after the prepared purification of the embodiment of the present invention 1.From this figure, the boron-carbon nanotube after purification is not reunited in transmission electron microscope powdered sample preparation process, can realize the dispersed of single boron-carbon nanotube; The boron-carbon nanotube diameter 30nm of synthesized, body has bamboo knot shaped structure, and outside surface is more coarse, has a large amount of projections and depression.
Fig. 3 is the high resolution transmission electron microscopy photo of the boron-carbon nanotube after the prepared purification of the embodiment of the present invention 1.From this figure, the boron-carbon nanotube tube wall of synthesized is multi-walled pipes shape structure, has good crystallization degree, does not find that decolorizing carbon class impurity substances occurs; Outer surface of tube body is coarse, and external diameter is between 25～35nm, and internal diameter of tube body is between 8～15nm; Between boron-carbon nanotube inwall, having formed many connections, is a kind bamboo joint structure, the about 20nm in interval of every joint.
Embodiment 2
The first step, prepares nickel oxide-sodium-chlor catalyzer precursor
Be the ratio of nickelous nitrate: sodium-chlor=0.55:1 by weight, take Nickelous nitrate hexahydrate and the sodium-chlor of institute's expense, under induction stirring state, the sodium-chlor taking is dissolved in deionized water by the concentration of 80g/L, then the Nickelous nitrate hexahydrate taking is dissolved in above-mentioned deionized water, continue induction stirring until sodium-chlor and Nickelous nitrate hexahydrate dissolve completely, above-mentioned solution is placed in to Constant Temp. Oven in 90 ℃ of dry 96h, evaporate completely to moisture, then the nickelous nitrate and the sodium-chlor crystalline mixture that after dry, obtain are placed in to ball grinder, adopt planetary ball mill with the speed ball milling 6h of 1000r/min, above-mentioned mixture after ball-milling processing is placed in to quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 240ml/min continues to pass into nitrogen and is warming up to 600 ℃ in this tube furnace, insulation 4h, make this tube furnace under the nitrogen atmosphere of 240ml/min flow velocity till cool to room temperature, make nickel oxide-sodium-chlor catalyzer precursor,
Second step, prepares boron-carbon nanotube-sodium-chlor composite powder
Nickel oxide-sodium-chlor catalyzer precursor that the first step is made is placed in quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 240ml/min passes into hydrogen and is warming up to 750 ℃ in this tube furnace, insulation 3.5h, then close hydrogen, by volume ratio, be nitrogen again: the gas mixture of methyl-borate steam: methane=8:1:1 continues to pass in this tube furnace with the flow velocity of 600ml/min, at 750 ℃, carry out chemical vapour deposition reaction 1.5h, close afterwards methyl-borate steam and methane and adjust nitrogen flow, make above-mentioned tube furnace under the nitrogen atmosphere of 240ml/min flow velocity till cool to room temperature, make thus boron-carbon nanotube-sodium-chlor composite powder, wherein the quality percentage composition of boron-carbon nanotube is 17.6%,
The 3rd step, purification boron-carbon nanotube
Boron-carbon nanotube-sodium-chlor composite powder second step being made by the concentration of 5g/L is put into the deionized water solution that mass percent concentration is 1.0% Sodium dodecylbenzene sulfonate, the beaker that above-mentioned solution is housed is placed in to ultrasonic separating apparatus disperses 20min that sodium-chlor is dissolved completely by the ultrasonic wave of 40kHz, throw out in solution is filtered, by washed with de-ionized water 4 times, then use Constant Temp. Oven in 90 ℃ of dry 4h, make the boron-carbon nanotube after purification.
Embodiment 3
The first step, prepares nickel oxide-sodium-chlor catalyzer precursor
Be the ratio of nickelous nitrate: sodium-chlor=0.26:1 by weight, take Nickelous nitrate hexahydrate and the sodium-chlor of institute's expense, under induction stirring state, the sodium-chlor taking is dissolved in deionized water by the concentration of 65g/L, then the Nickelous nitrate hexahydrate taking is dissolved in above-mentioned deionized water, continue induction stirring until sodium-chlor and Nickelous nitrate hexahydrate dissolve completely, above-mentioned solution is placed in to Constant Temp. Oven in 75 ℃ of dry 72h, evaporate completely to moisture, then the nickelous nitrate and the sodium-chlor crystalline mixture that after dry, obtain are placed in to ball grinder, adopt planetary ball mill with the speed ball milling 4h of 800r/min, above-mentioned mixture after ball-milling processing is placed in to quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 210ml/min continues to pass into nitrogen and is warming up to 470 ℃ in this tube furnace, insulation 3h, make this tube furnace under the nitrogen atmosphere of 210ml/min flow velocity till cool to room temperature, make nickel oxide-sodium-chlor catalyzer precursor,
Second step, prepares boron-carbon nanotube-sodium-chlor composite powder
Nickel oxide-sodium-chlor catalyzer precursor that the first step is made is placed in quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 210ml/min passes into hydrogen and is warming up to 650 ℃ in this tube furnace, insulation 2.5h, then close hydrogen, by volume ratio, be nitrogen again: the gas mixture of methyl-borate steam: methane=6:0.8:1 continues to pass in this tube furnace with the flow velocity of 470ml/min, at 650 ℃, carry out chemical vapour deposition reaction 1h, close afterwards methyl-borate steam and methane and adjust nitrogen flow, make above-mentioned tube furnace under the nitrogen atmosphere of 210ml/min flow velocity till cool to room temperature, make thus boron-carbon nanotube-sodium-chlor composite powder, wherein the quality percentage composition of boron-carbon nanotube is 8.3%,
The 3rd step, purification boron-carbon nanotube
Boron-carbon nanotube-sodium-chlor composite powder second step being made by the concentration of 4g/L is put into the deionized water solution that mass percent concentration is 0.65% Sodium dodecylbenzene sulfonate, the beaker that above-mentioned solution is housed is placed in to ultrasonic separating apparatus disperses 15min that sodium-chlor is dissolved completely by the ultrasonic wave of 35kHz, throw out in solution is filtered, by washed with de-ionized water 3 times, then use Constant Temp. Oven in 85 ℃ of dry 3h, make the boron-carbon nanotube after purification.
Starting material related in above-mentioned all embodiment are all by commercially available, and equipment and process used is all that those skilled in the art are known.
Claims (1)
1. the preparation method of boron-carbon nanotube, is characterized in that: be a kind of preparation method who synthesizes boron-carbon nanotube by chemical Vapor deposition process, concrete steps are as follows:
The first step, prepares nickel oxide-sodium-chlor catalyzer precursor
Be the ratio of nickelous nitrate: sodium-chlor=0.02～0.55:1 by weight, take Nickelous nitrate hexahydrate and the sodium-chlor of institute's expense, under induction stirring state, the sodium-chlor taking is dissolved in deionized water by the concentration of 50～80g/L, then the Nickelous nitrate hexahydrate taking is dissolved in above-mentioned deionized water, continue induction stirring until sodium-chlor and Nickelous nitrate hexahydrate dissolve completely, above-mentioned solution is placed in to Constant Temp. Oven in 60～90 ℃ of dry 48～96h, evaporate completely to moisture, then the nickelous nitrate and the sodium-chlor crystalline mixture that after dry, obtain are placed in to ball grinder, adopt planetary ball mill with speed ball milling 3～6h of 500～1000r/min, above-mentioned mixture after ball-milling processing is placed in to quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 180～240ml/min continues to pass into nitrogen and is warming up to 350～600 ℃ in this tube furnace, insulation 2～4h, make this tube furnace under the nitrogen atmosphere of 180～240ml/min flow velocity till cool to room temperature, make nickel oxide-sodium-chlor catalyzer precursor,
Second step, prepares boron-carbon nanotube-sodium-chlor composite powder
Nickel oxide-sodium-chlor catalyzer precursor that the first step is made is placed in quartzy Noah's ark, this quartz Noah's ark is placed in to horizontal pipe furnace flat-temperature zone, flow velocity with 180～240ml/min passes into hydrogen and is warming up to 550～750 ℃ in this tube furnace, insulation 1.5～3.5h, then close hydrogen, by volume ratio, be nitrogen again: the gas mixture of methyl-borate steam: methane=4～8:0.5～1:1 continues to pass in this tube furnace with the flow velocity of 330～600ml/min, at 550～750 ℃, carry out chemical vapour deposition reaction 0.5～1.5h, close afterwards methyl-borate steam and methane and adjust nitrogen flow, make above-mentioned tube furnace under the nitrogen atmosphere of 180～240ml/min flow velocity till cool to room temperature, make thus boron-carbon nanotube-sodium-chlor composite powder, wherein the quality percentage composition of boron-carbon nanotube is 5.1～17.6%,
The 3rd step, purification boron-carbon nanotube
Boron-carbon nanotube-sodium-chlor composite powder second step being made by the concentration of 2～5g/L is put into the deionized water solution that mass percent concentration is 0.3～1.0% Sodium dodecylbenzene sulfonate, the beaker that above-mentioned solution is housed is placed in to ultrasonic separating apparatus disperses 10～20min that sodium-chlor is dissolved completely by the ultrasonic wave of 30kHz～40kHz, throw out in solution is filtered, by washed with de-ionized water 3～4 times, then use Constant Temp. Oven in 80～90 ℃ of dry 2～4h, make the boron-carbon nanotube after purification.
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| CN103496689B (en) * | 2013-09-23 | 2015-04-15 | 同济大学 | Preparation method of boron-doped p type carbon nanotube with high seebeck coefficient |
| EP3582951B1 (en) | 2017-04-21 | 2022-06-22 | Hewlett-Packard Development Company, L.P. | Additive manufacturing machine heat flux |
| CN111517356B (en) * | 2020-04-30 | 2022-03-29 | 浙江理工大学 | Cu2O nanotube and method for producing the same |
| CN115124007A (en) * | 2022-06-20 | 2022-09-30 | 北京化工大学 | Preparation method of multi-stage regulation and control hydrophilic-hydrophobic boron carbon nitrogen nano material |
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| CN100354202C (en) * | 2006-03-17 | 2007-12-12 | 燕山大学 | Method of preparing boron carbon nitrogen nanometer pipe under low temperature |
| CN101718731B (en) * | 2009-12-09 | 2012-08-29 | 黑龙江大学 | Boron-carbon nanotube/semiconductor oxide composite and preparation method and application thereof |
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