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CN102398902A - Method for preparing carbon nanomaterials using natural halloysite as template - Google Patents

Method for preparing carbon nanomaterials using natural halloysite as template Download PDF

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CN102398902A
CN102398902A CN2011102054873A CN201110205487A CN102398902A CN 102398902 A CN102398902 A CN 102398902A CN 2011102054873 A CN2011102054873 A CN 2011102054873A CN 201110205487 A CN201110205487 A CN 201110205487A CN 102398902 A CN102398902 A CN 102398902A
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halloysite
hours
natural
carbon
template
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CN102398902B (en
Inventor
刘蓉
严春杰
王洪权
肖国琪
袁六四
夏云山
梁玉军
周春宇
舒国晶
孙露
周森
仇秀梅
许修书
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YUNNAN TIANHONG GAOLING MINING CO Ltd
China University of Geosciences Wuhan
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YUNNAN TIANHONG GAOLING MINING CO Ltd
China University of Geosciences Wuhan
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Abstract

The invention relates to a method for preparing carbon by taking natural halloysite as a templateA method of preparing a nanomaterial. The method for preparing the carbon nano material by taking the natural halloysite as the template is characterized by comprising the following steps: 1) selecting natural halloysite powder and a carbon source according to the mass ratio of the natural halloysite powder to the carbon source of 1: 1-5; 2) firstly, preserving heat of natural halloysite powder for 3 hours at the temperature of 300-900 ℃, then adding acid, stirring, filtering, washing to be neutral, and drying; 3) uniformly mixing activated and modified halloysite and a carbon source, and preserving heat for 6-48 h at the temperature of 130-180 ℃ to obtain a precursor; 4) the precursor is processed at 500-900 ℃ and N2And (3) firing for 3-6 hours in a protective atmosphere, after firing, cooling the product to room temperature along with the furnace, washing with HF to remove the template in the product, washing with deionized water to neutrality, filtering, and drying to obtain the carbon nano material. The prepared carbon nano material not only contains the carbon nano tube, but also contains the carbon nano rod, and the preparation process is simple.

Description

With natural halloysite is the method that template prepares carbon nanomaterial
Technical field
The present invention relates to a kind of is the method that template prepares carbon nanomaterial with natural halloysite.
Background technology
The research of carbon nanomaterial is one of international advanced subject of low in recent years dimension Condensed Matter Physics research, the especially preparation of carbon nanotube, carbon nano rod community of physicists, material educational circles questions of common interest especially.Since Japanese scientist's Iijima in 1991 is found carbon nanotube, carbon nanotube-its structural singularity and show typical One-dimensional Quantum material, it not only has very high intensity, also has extraordinary magnetic resistance, thermal conductivity etc.In addition; Can the various materials of filling such as metal, oxide compound etc. in the inside of carbon nanotube; This not only can prepare the thinnest lead or brand-new one-dimensional material; ME device or nanoelectronics device in future are applied, and can coat in the outside of carbon nanotube, and this is to become the important directions of current research.
Carbon nanotube, nanometer rod are a kind of unidimensional nano material, and be in light weight, has many unusual mechanics, electricity and chemical property.Carbon nanotube has typical stratiform hollow structure characteristic, and carbon nano rod then is solid club shaped structure.The both is a kind of One-dimensional Quantum material with special construction (radial dimension is a nanometer scale, and axial dimension is a micron dimension).Because its particular structure, the research of carbon nanotube and nanometer rod has important in theory meaning and potential using value, as: its particular structure is an ideal one-dimensional model material; Huge length-to-diameter ratio is expected to as tough and tensile thomel it, and its intensity is 100 times of steel, and weight then has only 1/6 of steel; It also is expected to be used as molecular wire, nano semiconductor material, support of the catalyst, molecular absorption agent and near field emissive material etc. simultaneously.Scientists also predict carbon nanotube will become the most promising nano material of 21 century.
In recent years, on various top scholarly journals such as " Science ", " Nature ", " Chem.Lett. ", all there is the compound method of different carbon nanomaterials to release.
The main method of preparation carbon nanotube, nanometer rod has arc process, laser burn method, chemical Vapor deposition process (CVD), catalytic pyrolysis method and solid-state permutoid reaction etc.Someone also utilizes the pyrolysis of organo-metallic precursor, TCD thermochemical deposition to obtain Y type carbon nanotube, has obtained spiral carbon nano pipe with the CVD method.Solvent-thermal method more is used for synthesizing the carbon nanomaterial of multiple pattern widely in recent years.The preparation method of the carbon nanomaterial of announcing like patents such as CN200510037474.4, CN200510100053.1, CN200510100771.9 all adopts vapour deposition process (CVD) synthetic.But be that the report that method that template utilizes template to combine with hydrothermal method prepares carbon nanomaterial is found as yet up to the present, with natural halloysite.The present invention utilizes this new raw material and method to come to prepare simultaneously carbon nanotube and the carbon nano rod that is different from traditional material.
In sum, template is a kind of simple method, also is the effective ways of mesoporous rate of control and pore structure, size.It is through selecting for use a kind of material with special construction as template; Import target material or presoma and it is reacted in the hole of this mould material; Utilize the confinement effect of mould material; Reach the purpose that the physics in the preparation process and chemical reaction are regulated and control, finally obtain microcosmic and nacrostructure controlled and on traditional sense diverse carbon nanometer novel material.The characteristics that template is the most outstanding are to have good controllable structure system property, and it provides one can control and improve the effective means that nanoparticle is arranged in structured material.Prepared in this way material has the constitutional features similar with template.
Summary of the invention
The object of the present invention is to provide a kind of is the method that template prepares carbon nanomaterial with natural halloysite, and the carbon nanomaterial of preparing had both included carbon nanotube and also included carbon nano rod, and preparation technology is simple.
For realizing the object of the invention, the technical scheme that the present invention taked is: with natural halloysite is the method that template prepares carbon nanomaterial, it is characterized in that it may further comprise the steps:
1) mass ratio by natural halloysite powder and carbon source is 1: 1～1: 5, chooses natural halloysite powder and carbon source, and is subsequent use;
2) be 5g: 100mL by natural halloysite powder with sour proportioning, choose acid; Be 300 ℃～900 ℃ 3 hours (thermal activation treatment) of insulation down with natural halloysite powder in temperature earlier; Add acid then; 2 hours after-filtration of mechanical stirring, washing were dried by the fire 24～36 hours in 85～100 ℃ of baking ovens to neutral, obtained activation, halloysite that modification is good;
3) activation, halloysite and carbon source that modification is good are mixed, obtain halloysite/charcoal mixture; Halloysite/charcoal mixture is placed (being the tetrafluoroethylene storage tank) in the autoclave, and autoclave places the baking oven case, and insulation is 6h-48h hour under 130 ℃ of-180 ℃ of temperature, obtains presoma;
4) with presoma in 500 ℃～900 ℃, N 2Carried out calcination 3～6 hours under the atmosphere of protection, calcination cools to product with the furnace room temperature after finishing, and removes template in the product in 15～24 hours with the HF washing.
5) extremely neutral with deionized water wash again, filter, dry, obtain carbon nanomaterial.
The preparation of the said natural halloysite powder of step 1), it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension-s that concentration is 10-20wt% (quality) (containing the 10-20g raw ore in the expression 100g suspension-s) at halloysite raw ore and the water of 30-50%;
2) add-on by Sodium hexametaphosphate 99 is the 0.2-0.5% of halloysite ore quality, in suspension-s, adds Sodium hexametaphosphate 99, and mechanical stirring 2-4h obtains slurry;
3) slurry after will stirring is put into the whizzer spinning, rotating speed 1500-2000r/min, and the spinning time is 5-10min; After centrifugal, lower sediment is removed, get upper strata suspension-s, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains centrifugal throw out for the second time;
4) get centrifugal throw out for the second time, 80-100 ℃ of oven dry (baking 5-8h) promptly obtains high-purity halloysite [purity of resulting high-purity halloysite is greater than 85% (quality)].
Described halloysite raw ore is natural halloysite ore deposit, Lincang, Yunnan, and composition is seen table 1.Mineral composition is halloysite, kaolinite, illite, gipsite, quartz and feldspar.
The Chemical Composition and the quality percentage composition of the said natural halloysite powder above-mentioned steps 1) are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%; Purity is greater than 85wt%; Median size is 5.226um; Halloysite, is leaned on hydrogen bond to connect, thereby constitutes stacked in layers according to the layer silicate mineral that 1: 1 form crenel forms by Si-O tetrahedrallayer and Al-O octahedral layer between each unit layer; With kaolinic structural similitude, difference is that its interlayer contains water molecule layer in various degree; (0.514 * 0.893nm) greater than octahedral layer (0.506 * 0.862nm) owing to tetrahedral sheet in its crystalline structure; Growth does not match fully; In order better to mate each other, the halloysite unit layer curls into the multilayer hollow tubular structures, and having formed with the Si-O-Si tetrahedron is outside surface; Internal surface is formed by A-OH is octahedra, all comprises 15～20 crystal layers (the SEM shape appearance figure of halloysite among Fig. 1) in each multilayer tubular structures; Natural halloysite sample ore moderate purity is more than 85%, wherein contains tubulose and a small amount of sheet halloysite, sheet kaolinite and gipsite, so the raw material of wood-charcoal material of preparation has two kinds of forms, and sheet structure, tubular structure and club shaped structure, general designation carbon nanomaterial.
Above-mentioned steps 1) carbon source in is furfuryl alcohol or carbon sources such as sucrose or glucose.
Above-mentioned steps 2) acid is HCl, HNO in 3, H 2SO 4Deng in any or several kinds of solution by any mixed in molar ratio as properties-correcting agent natural halloysite is carried out modification; The volumetric molar concentration of acid is 0.5mol/L～10mol/L.
Above-mentioned steps 4) bake out temperature in is 80 ℃-100 ℃, and the time is 12～24 hours.
Above-mentioned steps 4) concentration of the HF in is 40wt%.
Ultimate principle of the present invention is to adopt hydro-thermal synthetic method organism evenly to be placed the hole of natural halloysite template; Then mixture is carried out high temperature carbonization; Obtain halloysite/charcoal mixture, remove template, the carbon nanomaterial that promptly obtains having the formwork structure characteristic with acid again.The biggest advantage that adopts natural halloysite to make template is that raw material sources are extensive, cheap.
Compared with prior art; The advantage that the present invention has is: it is that template has successfully been synthesized carbon nanomaterial with natural halloysite that the present invention adopts template; This carbon nanomaterial of preparing had both copied the shape characteristic of tubulose halloysite, had made carbon nanotube, also made carbon source enter into the inside, aperture of tubulose halloysite through hydro-thermal reaction; Synthesized carbon nano rod (product had both included carbon nanotube and also included carbon nano rod); And this compound method is very simple, and raw material sources are abundant, and are cheap.
Description of drawings
Fig. 1 is the SEM shape appearance figure of natural halloysite.
Fig. 2 is the XRD figure spectrum of embodiment 1 gained carbon nanomaterial.
Fig. 3 receives the TEM collection of illustrative plates of the tubular structure in the material and the electron diffraction collection of illustrative plates of carbon nanotube for embodiment 1 gained carbon.
Fig. 4 is the TEM collection of illustrative plates and the electron diffraction collection of illustrative plates of embodiment 1 gained carbon nano rod; Fig. 3 a representes the TEM collection of illustrative plates of the club shaped structure in the carbon nanomaterial, and Fig. 3 b representes the electron diffraction collection of illustrative plates of the club shaped structure in the carbon nanomaterial.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with instance, but the present invention not only is confined to following embodiment.
The preparation of natural halloysite powder described in following examples, it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension-s that concentration is 10-20wt% (quality) (containing the 10-20g raw ore in the expression 100g suspension-s) at halloysite raw ore and the water of 30-50%;
2) add-on by Sodium hexametaphosphate 99 is the 0.2-0.5% of halloysite ore quality, in suspension-s, adds Sodium hexametaphosphate 99, and mechanical stirring 2-4h obtains slurry;
3) slurry after will stirring is put into the whizzer spinning, rotating speed 1500-2000r/min, and the spinning time is 5-10min; After centrifugal, lower sediment is removed, get upper strata suspension-s, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains centrifugal throw out for the second time;
4) get centrifugal throw out for the second time, 80-100 ℃ of oven dry (baking 5-8h) promptly obtains high-purity halloysite [purity of resulting high-purity halloysite is greater than 85% (quality)].
Described halloysite raw ore is natural halloysite ore deposit, Lincang, Yunnan, and composition is seen table 1.Mineral composition is halloysite, kaolinite, illite, gipsite, quartz and feldspar.
Embodiment 1:
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) (be called for short halloysite, purity is the halloysite sample more than 85%, wherein contains tubulose and a small amount of sheet halloysite, sheet kaolinite and gipsite to take by weighing natural halloysite powder; Identical in following examples) 5.00g, measure furfuryl alcohol 8.80ml.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 700 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier; The HCl that adds 100ml, 2mol/L then; To neutral (pH is 6～8), baking is 24 hours in 85 ℃ of baking ovens in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing, obtains activation, halloysite that modification is good.
3) again that activation, modification is good halloysite and 8.80ml furfuryl alcohol mix the back and move in the autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere; After calcination finishes; Treat that sample cools to room temperature with the furnace, take out sample then and removed the mineral template in 15 hours, with deionized water sample is washed to neutral (pH is 6～8), filters at last with the HF washing; Handled 12 hours in 100 ℃ of oven dry, obtain carbon nanomaterial (the finished product).
Fig. 1 is the XRD diffractogram of present embodiment gained carbon nanomaterial, and as can be seen from Figure 1, the carbon nanomaterial that makes is amorphous amorphous charcoal; Fig. 1 shows, a diffraction bag near 23 ° and 44 °, all occurs, respectively correspondence the position of (002) and (101) face diffraction peak of graphite, explain some faint graphite microcrystal orderings in 800 ℃ carbonization process, to have occurred.Fig. 2 and Fig. 3 (a, b) are the transmission electron microscope and the electron diffraction picture of prepared carbon nanomaterial; As can beappreciated from fig. 2 use natural halloysite successfully to prepare the carbon nanotube that keeps the halloysite tubular structure as template; Moreover; Transmission electron microscope photo and electron diffraction collection of illustrative plates through Fig. 3 can be known, also make carbon source enter into the inside, aperture of tubulose halloysite through hydro-thermal reaction, have synthesized carbon nano rod.In this carbon nanomaterial that synthesizes, include a large amount of carbon nanotubes and a spot of carbon nano rod simultaneously, the carbon nano rod diameter of preparing combines electron-diffraction diagram can explain that this rod is entirely the composition of graphite in 10nm in addition.
Embodiment 2
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) takes by weighing halloysite 5.00g, glucose 10.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 600 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier; The HCl that adds 100ml, 2mol/L then; To neutral, baking is 24 hours in 85 ℃ of baking ovens in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing, obtains activation, halloysite that modification is good.
3) again that activation, modification is good halloysite and 10.00g glucose mix the back and move in the autoclave, and autoclave is placed 180 ℃ baking oven insulation 24 hours, make presoma.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere; After calcination finishes; Treat that product (being sample) cools to room temperature with the furnace, take out product (being sample) then and use concentration to remove the mineral template in 15 hours, with deionized water that the sample washing is extremely neutral at last, filtration as the HF washing of 40wt%; Handled 16 hours in 100 ℃ of oven dry, obtain carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis with embodiment 1 identical method, confirm that this product had both included carbon nanotube and also included carbon nano rod, wherein the carbon nano rod diameter Distribution is about 2-20nm.
Embodiment 3
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) takes by weighing halloysite 5.00g, sucrose 10.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 700 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier; The HCl that adds 100ml, 2mol/L then; To neutral, baking is 24 hours in 85 ℃ of baking ovens in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing, obtains activation, halloysite that modification is good.
3) again that activation, modification is good halloysite and 10.00g sucrose mix the back and move in the autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 18 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 4
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure furfuryl alcohol 8.80ml.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 700 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, add the HNO of 100ml, 2mol/L then 3, to neutral baking 24 hours in 85 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and 8.80ml furfuryl alcohol mix in the back immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 20 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis with embodiment 1 identical method, confirm this product for both to include the carbon nanomaterial that carbon nanotube also includes carbon nano rod, wherein the carbon nano rod diameter is about 10nm.
Embodiment 5
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure furfuryl alcohol 8.80ml.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 700 ℃ temperature, to be incubated 3 hours the halloysite that weighs up; The HSO4 that adds 100ml, 2mol/L then; To neutral baking 24 hours in 85 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and 8.80ml furfuryl alcohol mix in the back immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 20 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 6
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure furfuryl alcohol 5.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up, add the HSO of 100ml, 0.5mol/L then 4, to neutral baking 24 hours in 100 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and furfuryl alcohol mix in the back immigration autoclave, and place 130 ℃ baking oven insulation to make presoma in 6 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 500 ℃, N 2Calcination is 3 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 20 hours in 80 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 7
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure sucrose 25.00g.Halloysite is natural halloysite powder, and its Chemical Composition is: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up, add the HSO of 100ml, 10mol/L then 4, to neutral baking 24 hours in 100 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and sucrose mix in the back immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 6 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 900 ℃, N 2Calcination is 6 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 22 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 8
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure glucose 5.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up, add the HSO of 50ml, 2mol/L then 4HNO with 50ml, 2mol/L 3, to neutral baking 24 hours in 85 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and glucose mix, and move in the autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 22 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 9
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure glucose 15.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up, add the HSO of 50ml, 2mol/L then 4, 50ml, 2mol/L HCl, to neutral baking 24 hours in 85 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and glucose mix in the back immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 10
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure sucrose 15.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up, add the HNO of 50ml, 2mol/L then 3With the HCl of 50ml, 2mol/L, to neutral baking 24 hours in 85 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and sucrose mix in the back immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 20 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
Embodiment 11
With natural halloysite is the method that template prepares carbon nanomaterial, and it may further comprise the steps:
1) take by weighing halloysite 5.00g, measure sucrose 15.00g.Halloysite is natural halloysite powder, and its Chemical Composition and quality percentage composition are: SiO 2=45.04%, Al 2O 3=38.31%, TFe 2O 3=0.16%, MgO=0.05%, CaO=0.05%, Na 2O=0.05%, K 2O=0.03%, TiO 2=0.04%, P 2O 5=0.02%, MnO 5=0.002%, H 2O -=2.27%, loss on ignition=17.94%, purity is greater than 85wt%, and median size is 5.226um.
2) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up, add the HNO of 25ml, 2mol/L then 3H with the HCl of 25ml, 2mol/L and 50ml, 2mol/L 2SO 4, to neutral baking 24 hours in 85 ℃ of baking ovens, obtain activation, halloysite that modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and sucrose mix in the back immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing; Take out sample then and removed the mineral template in 24 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 36 hours in 100 ℃ of oven dry, obtained carbon nanomaterial (the finished product).
By product being carried out XRD and TEM analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod with embodiment 1 identical method.
The complete chemical analysis of table 1 halloysite raw ore
Figure BDA0000077545380000091

Claims (7)

1.以天然埃洛石为模板制备碳纳米材料的方法，其特征在于它包括以下步骤：1. take natural halloysite as template to prepare the method for carbon nanomaterial, it is characterized in that it comprises the following steps: 1)按天然埃洛石粉体与碳源的质量比为1∶1～5，选取天然埃洛石粉体和碳源，备用；1) according to the mass ratio of natural halloysite powder and carbon source is 1: 1～5, select natural halloysite powder and carbon source, standby; 2)按天然埃洛石粉体与酸的配比为5g∶100mL，选取酸；先将天然埃洛石粉体在温度为300℃～900℃下保温3小时，然后加入酸，机械搅拌2小时后过滤、洗涤至中性，于85～100℃烘箱中烘24～36小时，得到活化、改性好的埃洛石；2) According to the proportion of natural halloysite powder and acid as 5g: 100mL, select the acid; first, the natural halloysite powder is kept at a temperature of 300°C to 900°C for 3 hours, then the acid is added, and mechanically stirred for 2 After 1 hour, filter and wash until neutral, and bake in an oven at 85-100°C for 24-36 hours to obtain activated and modified halloysite; 3)将活化、改性好的埃洛石和碳源混合均匀，得到埃洛石/炭复合物；将埃洛石/炭复合物置于高压反应釜内，高压反应釜置于烘箱箱中，于130℃-180℃温度下保温6h-48h小时，得到前驱体；3) Mix the activated and modified halloysite and the carbon source evenly to obtain a halloysite/carbon composite; place the halloysite/carbon composite in a high-pressure reactor, and the high-pressure reactor is placed in an oven. Precursor is obtained by incubating at 130°C-180°C for 6h-48h; 4)将前驱体于500℃～900℃，N2保护的氛围下进行灼烧3～6小时，灼烧结束后将产物随炉冷却至室温，用HF洗涤15～24小时除去产物中模板，再用去离子水洗涤至中性，过滤、烘干，得到碳纳米材料。4) Burn the precursor at 500°C-900°C under N2 protection atmosphere for 3-6 hours, after the burnt end, cool the product to room temperature with the furnace, wash with HF for 15-24 hours to remove the template in the product, Then wash with deionized water until neutral, filter and dry to obtain carbon nanomaterials. 2.根据权利要求1所述的以天然埃洛石为模板制备碳纳米材料的方法，其特征在于：所述天然埃洛石粉体的制备，它包括如下步骤：2. take natural halloysite as template to prepare the method for carbon nanomaterial according to claim 1, it is characterized in that: the preparation of described natural halloysite powder, it comprises the steps: 1)将埃洛石的质量百分含量在30-50％的埃洛石原矿和水配成浓度为10-20wt％的悬浮液；1) the halloysite mass percentage content is made into the suspension that concentration is 10-20wt% in the halloysite raw ore of 30-50% and water; 2)按六偏磷酸钠的加入量为埃洛石原矿质量的0.2-0.5％，向悬浮液中加入六偏磷酸钠，机械搅拌2-4h，得到浆体；2) Adding sodium hexametaphosphate in an amount of 0.2-0.5% of the mass of the halloysite raw ore, adding sodium hexametaphosphate to the suspension, and mechanically stirring for 2-4 hours to obtain a slurry; 3)将搅拌后的浆体放入离心机中离心分离，转速1500-2000r/min，离心分离时间为5-10min；离心后，将下层沉淀除去，取上层悬浮液，再次离心，转速3000-3800r/min，时间为5-10min，得到第二次离心的沉淀物；3) Put the stirred slurry into a centrifuge for centrifugation at a speed of 1500-2000r/min, and the centrifugation time is 5-10min; after centrifugation, remove the lower sediment, take the upper suspension, and centrifuge again at a speed of 3000- 3800r/min, time is 5-10min, obtain the sediment of the second centrifugation; 4)取第二次离心的沉淀物，80-100℃烘干，即得到纯度大于85wt％的天然埃洛石粉体。4) Take the second centrifuged precipitate and dry it at 80-100°C to obtain natural halloysite powder with a purity greater than 85wt%. 3.根据权利要求1所述的以天然埃洛石为模板制备碳纳米材料的方法，其特征在于所述天然埃洛石粉体的化学成份及质量百分含量为：SiO2＝45.04％，Al2O3＝38.31％，TFe2O3＝0.16％，MgO＝0.05％，CaO＝0.05％，Na2O＝0.05％，K2O＝0.03％，TiO2＝0.04％，P2O5＝0.02％，MnO5＝0.002％，H2O-＝2.27％，烧失量＝17.94％；天然埃洛石粉体中埃洛石纯度大于85wt％，天然埃洛石粉体的平均粒径为5.226um。3. the method for preparing carbon nanomaterials with natural halloysite as template according to claim 1, characterized in that the chemical composition and mass percentage of said natural halloysite powder are: SiO 2 =45.04%, Al 2 O 3 = 38.31%, TFe 2 O 3 = 0.16%, MgO = 0.05%, CaO = 0.05%, Na 2 O = 0.05%, K 2 O = 0.03%, TiO 2 = 0.04%, P 2 O 5 = 0.02%, MnO 5 = 0.002%, H 2 O - = 2.27%, loss on ignition = 17.94%; the purity of halloysite in natural halloysite powder is greater than 85wt%, and the average particle size of natural halloysite powder is It is 5.226um. 4.根据权利要求1所述的以天然埃洛石为模板制备碳纳米材料的方法，其特征在于所述步骤1)中的碳源为糠醇或蔗糖或葡萄糖。4. the method for template preparation of carbon nanomaterials with natural halloysite according to claim 1, characterized in that the carbon source in the step 1) is furfuryl alcohol or sucrose or glucose. 5.根据权利要求1所述的以天然埃洛石为模板制备碳纳米材料的方法，其特征在于所述步骤2)中酸为HCl、HNO3、H2SO4中的任一种或几种按任意摩尔比混合的溶液；酸的摩尔浓度为0.5mol/L～10mol/L。5. The method for preparing carbon nanomaterials using natural halloysite as a template according to claim 1, characterized in that the acid in the step 2) is any one or more of HCl, HNO 3 , H 2 SO 4 A solution mixed in any molar ratio; the molar concentration of the acid is 0.5mol/L to 10mol/L. 6.根据权利要求1所述的以天然埃洛石为模板制备碳纳米材料的方法，其特征在于步骤4)中的烘干温度为80℃-100℃，时间为12～24小时。6. The method for preparing carbon nanomaterials using natural halloysite as a template according to claim 1, characterized in that the drying temperature in step 4) is 80°C-100°C, and the time is 12-24 hours. 7.根据权利要求1所述的以天然埃洛石为模板制备碳纳米材料的方法，其特征在于步骤4)中的HF的浓度为40wt％。7. The method for preparing carbon nanomaterials with natural halloysite as template according to claim 1, characterized in that the concentration of HF in step 4) is 40wt%.
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