CN104803362A - Preparation method of hexagonal boron nitride powder and three-dimensional boron nitride - Google Patents
Preparation method of hexagonal boron nitride powder and three-dimensional boron nitride Download PDFInfo
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- CN104803362A CN104803362A CN201510166440.9A CN201510166440A CN104803362A CN 104803362 A CN104803362 A CN 104803362A CN 201510166440 A CN201510166440 A CN 201510166440A CN 104803362 A CN104803362 A CN 104803362A
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Abstract
The invention belongs to the technical field of inorganic synthesis, and particularly relates to a preparation method of hexagonal boron nitride powder and three-dimensional boron nitride. According to the preparation method, a chemical vapor deposition method is adopted, transition metal elementary substance powder or a compound containing transition metal elements is taken as a catalyst, and a porous metal catalyst skeleton is prepared through high-temperature reduction reaction; hexagonal boron nitride grows with the chemical vapor deposition method so as to obtain the hexagonal boron nitride powder with the catalyst skeleton and the three-dimensional boron nitride. According to the preparation method, the operation is simple and convenient, the requirement for equipment is low, and the yield is high; the hexagonal boron nitride powder and the three-dimensional boron nitride can be rapidly and massively prepared, the obtained three-dimensional boron nitride has the advantages of small space ranging from 100 nanometers to 100 micrometers, high density up to 100 mg/ cm<3> and the like, the three-dimensional boron nitride and the boron nitride powder have the wide application prospect in the aspects of space heat conduction, catalyst carriers, sound absorption, shock resistance and the like.
Description
Technical field
The invention belongs to Inorganic synthese technical field, be specifically related to the preparation method of a kind of hexagonal boron nitride powder and three-dimensional structure.
Background technology
Nano-hexagonal boron nitride is the two-dimensional material of a kind Graphene, and be also the new ceramic material of a kind of excellent performance potentiality and tool grows a lot simultaneously, because it has the good feature of high-temperature oxidation resistance, radiation hardness, high thermal conductivity, high temperature lubricating, dielectric properties and insulating property, have a wide range of applications in fields such as metallurgy, space flight and aviation, electronics and nuclear industry.Hexagonal boron nitride powder material is the tridimensional network be cross-linked to form by space based on the boron nitride nanosheet of two dimension, except having the character of two-dimentional boron nitride nanosheet, three-dimensional boron nitride nanometer material is in space heat conduction, and support of the catalyst and the aspect such as shockproof that absorbs sound have larger advantage.
Hexagonal boron nitride still can keep stable at 2500 degrees Celsius under inert atmosphere, can keep satisfactory stability at 850 degrees Celsius under oxidizing atmosphere.In contrast, three-dimensional grapheme and metal array framework thereof there will be and cave in, decompose or be oxidized in temperature is higher than 600 degree of situations, make three-dimensional grapheme materials application field limited.Due to above excellent properties, hexagonal boron nitride has huge application prospect preparing in high heat-conducting ceramic device, high heat conduction speciality coating, heat conductive insulating polymer composites, high temperature resistant solid lubricant and lubricating oil and grease additive etc.2013, the Guo Wanlin group of Nanjing Aero-Space University adopted foamed metal to be the Three-dimensional boron nitride foam that template obtains the excellent properties such as low density, high thermal stability.But the network hole of foamed metal is up to hundreds of micron, and in the Three-dimensional boron nitride foam as Template preparation, volume density is low, is unfavorable for its preparation in macroscopic quantity.The present invention's transition metal simple substance or the compound containing transition metal are raw material, after high temperature reduction, prepare porous catalyst template thus replace traditional foamed metal template, higher than adopting foamed metal to make the three-dimensional boron nitride porosity that catalysis skeleton obtains; In addition, the high-quality hexagonal boron nitride powder of magnanimity can also be prepared.
Summary of the invention
The object of this invention is to provide one and can prepare hexagonal boron nitride powder and three-dimensional boron nitride preparation method fast, in a large number, the three-dimensional boron nitride space obtained is little, density is large.
The preparation method of hexagonal boron nitride powder provided by the invention and three-dimensional boron nitride, be with transition metal elemental powders or containing the compound of transition metal for catalyzer, through high temperature reduction reaction, prepare porous metal catalyst skeleton; Recycling chemical Vapor deposition process growth hexagonal boron nitride, obtains the hexagonal boron nitride powder with catalyst backbone and three-dimensional boron nitride; Wherein, hexagonal boron nitride powder refers to the three-dimensional netted powder that two-dimentional boron nitride nanosheet overlaps mutually, and nanometer length of a film is 10 nanometer-100 microns, and thickness is 1 nanometer-10 microns; Three-dimensional boron nitride to refer to before with solution etches catalyzer the hexagonal boron nitride obtained after by polymer protection; there is the three-dimensional full UNICOM network structure of high porosity; be by the interconnective network of boron nitride nanometer band, density is 0.2 milligram every cubic centimetre-100 milligrams every cubic centimetre.
The concrete steps of the method are as follows;
The first step, catalyst pre-treatment: described catalyzer is transition metal elemental powders and/or the compound containing transition metal, is positioned in reaction vessel by catalyzer, or by packed catalyst in macrocellular foam metal form, then be placed in reaction vessel; Reaction vessel vacuumizes or passes into inert atmosphere protection, and with the container area residing for 1-100 degree per minute ramp to 500-1500 degrees Centigrade catalyzer, pass into the reducing atmospheres such as hydrogen, anneal 1 minute-10 hours, obtain porous metal catalyst skeleton;
Second step, growing boron nitride: will the catalyzer temperature-elevating of reaction vessel be placed in temperature of reaction (400-1200 degree Celsius), reaction source (i.e. boron, nitrogenous source) is passed into catalyst area (by solid-state boron, nitrogenous source in reacting by heating container simultaneously, or pass into vapor reaction source, also the atmosphere of carrying reaction source can be passed into), growth time is 30 seconds-10 hours, and growth pressure is 1 millitorr-1 normal atmosphere; Then room temperature is cooled to the speed of 1-100 degree per minute; Obtain the hexagonal boron nitride powder with catalyst backbone;
3rd step, aftertreatment: the hexagonal boron nitride powder with catalyst backbone grown is taken out, puts in solution and etch catalyzer, obtain hexagonal boron nitride powder; Or, the boron nitride sample grown is taken out, adopts high molecular polymer protection, then put in solution and etch catalyzer, then remove high molecular polymer, then obtain three-dimensional boron nitride.
In the present invention, described reaction vessel be silica tube, alundum tube or other can the container of input and output gas.
In the present invention, described inert atmosphere is one or more mixed gass in the rare gas element such as nitrogen, argon gas; Reducing atmosphere is the mixed gas of hydrogen or hydrogen and above-mentioned rare gas element.
In the present invention, described transition metal can be selected from but be not limited to nickel, copper, cobalt, platinum, iron or rubidium.Described transition metal elemental powders particle diameter is 0.1 micron-100 microns.The described compound containing transition metal can be selected from but be not limited to transition metal oxide, transition metal salt or its hydrate.
Wherein, for transition metal salt hydrate, it can be dried or the microwave heating water that decrystallizes obtains Anhydrous transition metal-salt or directly carry out high temperature reduction at 50-300 degree Celsius.
In the present invention, described reaction source can be solid phase boron, nitrogenous source, or gas phase boron, nitrogenous source, or liquid phase boron, nitrogenous source, and described solid phase boron, nitrogenous source can be selected from but be not limited to: the boracics such as ammonia borane, nitrogen compound; Gas phase boron, nitrogenous source comprise the boracics such as diborane, boron chloride, nitrogen, ammonia, nitrogen gas one or more mixing; Boron, nitrogen source can also be brought reaction vessel with the liquid of boracic, nitrogen (as inorganic benzene) into by rare gas element and provide boron, nitrogenous source.
In the present invention, described porous catalyst skeleton has three-dimensional cross-linked structure, and its aperture is 100 nanometer-100 micron.
In the present invention, in the hexagonal boron nitride of described band catalyst backbone, the aperture of contained hole is 100 nanometer-100 microns.
In the present invention, described in be used for etching metal catalyst skeleton solution can with containing concentration be 0.05-6 mole often liter sulfuric acid, hydrochloric acid, nitric acid, iron(ic) chloride, iron nitrate, any one or two or more mixtures in ammonium persulphate and Marble reagent solution.
In the present invention, in aforementioned etch processes, also adopt high molecular polymer to protect three-dimensional boron nitride, described high molecular polymer comprises one or several mixing of polymethylmethacrylate, polyethylene, polystyrene or polypropylene.Remove polymer and can adopt high-temperature calcination (100-1000 degree Celsius), or adopt organic solvent (ketone, hydrochloric ether, aromatic hydrocarbon, halohydrocarbon reagent one or more) to dissolve.
As one of scheme that can implement, the program also can comprise: by transition metal simple substance and/or be filled in macrocellular foam metal form containing the compound of transition metal, after high temperature reduction, obtains three-dimensional porous metal catalyst template.
The aperture of aforementioned macrocellular foam metal catalyst contained hole is 500 nanometer-500 microns.Macrocellular foam metal mainly contains nickel foam, foamed iron, foam copper or foam cobalt etc.
As one of comparatively preferred embodiment, in step (1), described high temperature reduction reaction, be carry out in the reducing atmosphere of 100-1200 degree Celsius in temperature, described reducing atmosphere is 1-500 than the argon gas of 10-1000 and hydrogen composition primarily of throughput ratio, and carrier gas overall flow rate is 1-2000 milliliter per minute.
As one of comparatively preferred embodiment, in step (2), described growth temperature is 1000 degrees Celsius, and growth time is 40 minutes, and growth pressure is 1 normal atmosphere.
Compared with prior art, the present invention at least has following advantages: easy and simple to handle, equipment requirements is low, productive rate is high; The present invention can realize the high-quality preparation of boron nitride powder magnanimity; This method can realize three-dimensional boron nitride and prepares fast, in a large number simultaneously, and the three-dimensional boron nitride that obtains has space little (100 nanometer-100 microns), and density (can reach greatly
100 milligram every cubic centimetre) etc. advantage, this three-dimensional boron nitride and boron nitride powder are in space heat conduction, and support of the catalyst and the aspect such as shockproof that absorbs sound have wide practical use.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of hexagonal boron nitride powder.
Fig. 2 is the scanning electron microscope (SEM) photograph of hexagonal boron nitride powder.
Fig. 3 is with polymethylmethacrylate protection, etches away the three-dimensional boron nitride scanning electron microscope (SEM) photograph of nickel catalyzator.
Fig. 4 is the Raman spectrogram of copper powder catalytic growth hexagonal boron nitride.
Fig. 5 is the scanning electron microscope (SEM) photograph after nickel foam adds nickel powder.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail:
(namely the present invention adopts transition metal elemental powders, salt or its hydrate, oxide compound, presoma) obtain the 3-dimensional metal skeleton with catalytic property through high temperature reduction, utilize chemical vapour deposition technique, under suitable atmosphere, catalytic growth boron nitride, finally etches metallic framework and obtains boron nitride powder or three-dimensional boron nitride.Wherein, transition metal salt hydrate, before high temperature reduction, first obtains Anhydrous transition metal-salt after heating, drying or microwave heating decrystallize water treatment.
One, the preparation of hexagonal boron nitride powder
Embodiment 1, first, the preparation work before reaction: 0.5 gram of ammonia borane complex compound (boron, nitrogenous source), 0.5 gram of nickel powder (catalyzer) are loaded in same silica tube, wherein, silica tube front end residing for ammonia borane, and wrap up with heating jacket, residing for nickel powder, silica tube portion is positioned in tube furnace.Open vacuum pump and silica tube air pressure inside is evacuated to 5 × 10
-3below holder, pass into flow velocity be the argon gas of 400 milliliters of per minutes by air pressure refunds to normal pressure, continue to pass into argon gas to drain air (this terminates up to reaction, air outlet valve is opened to maintain atmospheric pressure environment), with the speed of 50 degree of per minutes, tube furnace is warming up to 1000 degrees Celsius, close argon gas afterwards, change the hydrogen reducing annealing nickel powder 30 minutes passing into 200 milliliters of per minutes, obtain nickel porous skeleton.
Secondly, step of reaction: after catalyzer is reduced 30 minutes at 1000 degrees Celsius, holding temperature is constant, simultaneously heating jacket is warming up to 100 degrees Celsius and (bringing to nickel powder place through air-flow) after ammonia borane complex compound (reaction source) heating is started to grow hexagonal boron nitride, now atmosphere is adjusted to argon gas and hydrogen ratio is 40 than 10(milliliter per minute), growth time is 60 minutes.Pluck heating jacket after end, open tube furnace, allow silica tube cool to room temperature with the furnace, obtain the hexagonal boron nitride powder with nickel skeleton.
Again, sample aftertreatment: the sample grown taking-up put in the hydrochloric acid soln of 3 moles often liter and etch, suction filtration obtains boron nitride powder (as Fig. 1,2).
Embodiment 2, preparation method is substantially with embodiment 1, and difference is: adopt copper powder as catalyzer, and the later stage solution of etching catalyzer adopts the iron trichloride of 1 mole often liter and the hydrochloric acid mixed solution of 0.1 mole often liter, can obtain hexagonal boron nitride powder.
Two, the preparation of three-dimensional boron nitride
Embodiment 3, preparation method, substantially with embodiment 1, also adopts nickel powder to make catalyzer.Difference sample processing part after being grown: before with 3 moles often liter salt acid etch nickel skeleton, the methyl-phenoxide solution first sample being dipped into polymethylmethacrylate (massfraction is 4 percent) takes out after 10 minutes and dries.After etching catalyzer, with the three-dimensional boron nitride (as Fig. 3) of polymer protection layer, more three-dimensional boron nitride can be obtained with acetone solution removing polymethylmethacrylate.
Embodiment 4, preparation method is substantially with embodiment 1, and difference is: adopt copper powder as catalyzer, and later stage etching catalyst solution adopts the iron trichloride of 1 mole often liter and the hydrochloric acid mixed solution of 0.1 mole often liter.Before etching, the methyl-phenoxide solution first sample being dipped into polymethylmethacrylate (massfraction is 4 percent) takes out after 10 minutes and dries.After etching, with the three-dimensional boron nitride of polymer protection layer, more three-dimensional boron nitride can be obtained with acetone solution removing polymethylmethacrylate.(as Fig. 4)
Embodiment 5, preparation method is substantially with embodiment 1, difference makes catalyzer for adding nickel powder (as Fig. 5) in nickel foam, and the sample processing part after growth also has difference: before with 3 moles often liter salt acid etch nickel skeleton, the methyl-phenoxide solution first sample being dipped into polymethylmethacrylate (massfraction is 4 percent) takes out after 10 minutes and dries.After etching catalyzer, with the three-dimensional boron nitride of polymer protection layer, more three-dimensional boron nitride can be obtained with acetone solution removing polymethylmethacrylate.
Claims (8)
1. the preparation method of hexagonal boron nitride powder and three-dimensional boron nitride, is characterized in that concrete steps are as follows:
The first step, catalyst pre-treatment: described catalyzer is transition metal elemental powders and/or the compound containing transition metal, is positioned in reaction vessel by catalyzer, or by packed catalyst in macrocellular foam metal form, then be placed in reaction vessel; Reaction vessel vacuumizes or passes into inert atmosphere protection, and with the container area residing for 1-100 degree per minute ramp to 500-1500 degrees Centigrade catalyzer, pass into the reducing atmospheres such as hydrogen, anneal 1 minute-10 hours, obtain porous metal catalyst skeleton;
Second step, growing boron nitride: will the catalyzer temperature-elevating of reaction vessel be placed in temperature of reaction 400-1200 degree Celsius, reaction source and boron, nitrogenous source are passed into catalyst area, growth time is 30 seconds-10 hours, and growth pressure is 1 millitorr-1 normal atmosphere simultaneously; Then room temperature is cooled to the speed of 1-100 degree per minute; Obtain the hexagonal boron nitride powder with catalyst backbone;
3rd step, aftertreatment: the hexagonal boron nitride powder with catalyst backbone grown is taken out, puts in solution and etch catalyzer, obtain hexagonal boron nitride powder; Or, the boron nitride sample grown is taken out, adopts high molecular polymer protection, then put in solution and etch catalyzer, then remove high molecular polymer, then obtain three-dimensional boron nitride.
2. the preparation method of hexagonal boron nitride powder according to claim 1 and three-dimensional boron nitride, is characterized in that, described transition metal is selected from nickel, copper, cobalt, platinum, iron, gold and silver, rubidium; Described transition metal elemental powders particle diameter is 0.1 micron-100 microns; The described compound containing transition metal comprises transition metal oxide, transition metal salt or its hydrate.
3. the preparation method of hexagonal boron nitride powder according to claim 1 and 2 and three-dimensional boron nitride, is characterized in that, described reaction source is boron, the nitrogenous source of solid phase, liquid phase or gas phase, and described solid phase boron, nitrogenous source are selected from boracic, nitrogen compound; Gas phase boron, nitrogenous source comprise diborane, boron chloride, nitrogen, these boracics of ammonia, nitrogen gas one or more mixing; Liquid phase boron, nitrogenous source are ring boron nitrogen six alkane; Described boron, nitrogenous source can also be bring reaction vessel with the liquid of boracic, nitrogen into by rare gas element to provide boron, nitrogenous source.
4. the preparation method of hexagonal boron nitride powder according to claim 3 and three-dimensional boron nitride, it is characterized in that, the aperture of described macrocellular foam metal contained hole is 200 nanometer-500 microns, and macrocellular foam metallic substance is nickel foam, foamed iron, foam copper or foam cobalt.
5. the preparation method of the hexagonal boron nitride powder according to claim 1 or 4 and three-dimensional boron nitride, is characterized in that, described reaction vessel be silica tube, alundum tube, vacuum chamber or other can the container of input and output gas.
6. the preparation method of the hexagonal boron nitride powder according to claim 1 or 4 and three-dimensional boron nitride, is characterized in that, described inert atmosphere is one or more mixed gass in nitrogen, argon gas; Reducing atmosphere is the mixed gas of hydrogen or hydrogen and above-mentioned rare gas element.
7. the preparation method of hexagonal boron nitride powder according to claim 6 and three-dimensional boron nitride, it is characterized in that, described to be used for etching metal catalyst skeleton solution used be sulfuric acid, hydrochloric acid, nitric acid, iron(ic) chloride, iron nitrate, any one in ammonium persulphate and Marble reagent of 0.05-6 mole often liter containing concentration, or the solution of two or more mixtures.
8. the hexagonal boron nitride powder according to claim 1,4 or 7 and the preparation method of three-dimensional boron nitride, it is characterized in that, in described etch processes, the high molecular polymer for the protection of three-dimensional boron nitride is one or several mixing of polymethylmethacrylate, polyethylene, polystyrene or polypropylene; Described removal high molecular polymer adopts the high-temperature calcination of 100-1000 degree Celsius, or adopts one or more dissolvings of organic solvent ketone, hydrochloric ether, aromatic hydrocarbon, halohydrocarbon reagent.
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| CN105253874A (en) * | 2015-09-18 | 2016-01-20 | 复旦大学 | Method for preparing three-dimensional microporous graphene totally without participation of solution |
| CN105854919A (en) * | 2016-04-11 | 2016-08-17 | 广东工业大学 | Alpha-beta-unsaturated aldehyde low temperature hydrogenation catalyst, and preparation method and application thereof |
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| CN105253874A (en) * | 2015-09-18 | 2016-01-20 | 复旦大学 | Method for preparing three-dimensional microporous graphene totally without participation of solution |
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| CN109650356A (en) * | 2019-02-27 | 2019-04-19 | 哈尔滨工业大学 | A method of boron nitride nanometer band is prepared using base metal catalysts |
| CN111483983A (en) * | 2020-05-06 | 2020-08-04 | 河北工业大学 | Preparation method of hexagonal boron nitride nanosphere with layered cavitation structure |
| CN111483983B (en) * | 2020-05-06 | 2021-08-03 | 河北工业大学 | Preparation method of hexagonal boron nitride nanosphere with layered cavitation structure |
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