CN102398902B - Method for preparing carbon nano material by using natural endellite as formwork - Google Patents

Method for preparing carbon nano material by using natural endellite as formwork Download PDF

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CN102398902B
CN102398902B CN 201110205487 CN201110205487A CN102398902B CN 102398902 B CN102398902 B CN 102398902B CN 201110205487 CN201110205487 CN 201110205487 CN 201110205487 A CN201110205487 A CN 201110205487A CN 102398902 B CN102398902 B CN 102398902B
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halloysite
hours
natural
carbon
template
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CN102398902A (en
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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 KAOLIN MINING Co Ltd
China University of Geosciences
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YUNNAN TIANHONG KAOLIN MINING Co Ltd
China University of Geosciences
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Abstract

The invention relates to a method for preparing carbon nano material by using a natural endellite as a template. The method comprises the following steps: 1) selecting the natural endellite powder and a carbon source according with the mass ratio 1:1-5 of the natural endellite powder to the carbon source; 2) keeping the natural endellite powder at 300 DEG.C-900 DEG.C for three hours, then adding acid, stirring, filtering, washing to neutral, drying; 3) mixing the activated and modified endellite with the carbon source evenly, then keeping the mixed endellite and carbon source at 130 DEG.C-180 DEG.C for 6h-48h, and obtaining a precursor; 4) firing the precursor with 500 DEG.C-900 DEG.C for 3-6 hours in the protective atmosphere of N2, cooling to room temperature after firing, removing the formwork by HF washing, then washing the precursor to neutral by using deionized water, filtering, drying, and obtaining the carbon nano materials. The prepared carbon nano materials not only comprise carbon nano tubes, but also comprise carbon nano rods, which have a simple preparation technology.

Description

The method for preparing carbon nanomaterial take natural halloysite as template
Technical field
The present invention relates to a kind of method for preparing carbon nanomaterial take natural halloysite as template.
Background technology
The research of carbon nanomaterial is preparation community of physicists, the material educational circles questions of common interest especially of one of international advanced subject of low-dimensional Condensed Matter Physics research in recent years, especially carbon nanotube, carbon nano rod.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 wire or brand-new one-dimensional material, molectronics device or nanoelectronics device in future are applied, and can coat in the outside of carbon nanotube, this is to become the important directions of current research.
Carbon nanotube, nanometer rod are a kind of nano material of one dimension, and be lightweight, has many abnormal mechanics, electricity and chemical property.Carbon nanotube has typical stratiform hollow structure feature, and carbon nano rod is solid club shaped structure.A kind of One-dimensional Quantum materials with special construction (radial dimension is nanometer scale, and axial dimension is micron dimension) both.Due to its unique structure, the research of carbon nanotube and nanometer rod has great theory significance and potential using value, as: its unique structure is desirable one-dimensional model material; Huge length-to-diameter ratio is expected to as tough and tensile carbon fiber it, and its intensity is 100 times of steel, and weight only has 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, all there is the synthetic method of different carbon nanomaterials to release on the various top scholarly journals such as " Science ", " Nature ", " Chem.Lett. ".
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 widely used for the carbon nanomaterial of synthetic different morphologies in recent years.The preparation method of the carbon nanomaterial of announcing as patents such as CN200510037474.4, CN200510100053.1, CN200510100771.9 all adopts vapour deposition process (CVD) synthetic.But the method for up to the present, utilizing template to combine with hydrothermal method take natural halloysite as template prepares the report of carbon nanomaterial not yet to be found.The present invention utilizes this new raw material and method 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, is also the effective ways of the mesoporous rate of control and pore structure, size.It a kind ofly has the material of special construction as template by selecting, 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 physical and chemical reaction in preparation process is regulated and controled, finally obtain microcosmic and macrostructure controlled and on traditional sense diverse carbon nanometer novel material.The characteristics that template is the most outstanding are to have good structure controllability, and it provides one can control and improve the effective means that nanoparticle is arranged in structured material.Prepared material has the constitutional features similar to template in this way.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing carbon nanomaterial take natural halloysite as template, the carbon nanomaterial of preparing had both included carbon nanotube and had also included carbon nano rod, and preparation technology is simple.
For realizing the object of the invention, the technical solution used in the present invention is: prepare the method for carbon nanomaterial take natural halloysite as template, it is characterized in that it comprises the following 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 standby;
2) proportioning by natural halloysite powder and acid is 5g: 100mL, chooses acid; Be first 3 hours (thermal activation treatment) of insulation under 300 ℃～900 ℃ with natural halloysite powder in temperature, then add acid, mechanical stirring is filtered after 2 hours, is washed to neutral, dries by the fire 24～36 hours the halloysite that activated, modification is good in 85～100 ℃ of baking ovens;
3) halloysite and the carbon source that will activate, modification are good mix, and obtain halloysite/Carbon composites; Halloysite/Carbon composites is placed in (being the tetrafluoroethylene storage tank) in autoclave, and autoclave is placed in the baking oven case, and insulation is 6h-48h hour at 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 product in 15～24 hours with the HF washing.
5) extremely neutral with deionized water wash again, filter, dry, obtain carbon nanomaterial.
Step 1) preparation of described natural halloysite powder, it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension that concentration is 10-20wt% (quality) (containing the 10-20g raw ore in expression 100g suspension) 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, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 2-4h obtains slurry;
3) slurry after stirring is put into the whizzer centrifugation, rotating speed 1500-2000r/min, and the centrifugation time is 5-10min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains centrifugal for the second time throw out;
4) get centrifugal for the second time throw out, 80-100 ℃ of oven dry (baking 5-8h) namely obtains high-purity halloysite [purity of resulting high-purity halloysite is greater than 85% (quality)].
Described halloysite raw ore is the natural halloysite of Lincang ore deposit, and composition sees Table 1.Mineral composition is halloysite, kaolinite, illite, gibbsite, quartz and feldspar.
Chemical Composition and the quality percentage composition of the described 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, the layer silicate mineral that halloysite is formed according to the form crenel of 1: 1 by Si-O tetrahedrallayer and Al-O octahedral layer, connect by hydrogen bond between each unit layer, thereby formation stacked in layers, 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) due to tetrahedral sheet in its crystalline structure, growth is not mated fully, in order better mutually to mate, the halloysite unit layer curls into the multilayer hollow tubular structures, formed take the Si-O-Si tetrahedron as outside surface, internal surface is comprised of the A-OH octahedron, comprises 15～20 crystal layers (the SEM shape appearance figure of halloysite in 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 gibbsite, so the Carbon Materials 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 the carbon sources such as sucrose or glucose.
Above-mentioned steps 2) in, acid is HCl, HNO 3, H 2SO 4Deng in any or several 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 the method for Hydrothermal Synthesis organism evenly to be placed in the hole of natural halloysite template, then mixture is carried out high temperature carbonization, obtain halloysite/Carbon composites, then remove template, the carbon nanomaterial that namely obtains having the formwork structure feature with acid.The advantage that adopts natural halloysite to make the maximum of template is that raw material sources are extensive, cheap.
Compared with prior art, the advantage that the present invention has is: the present invention adopts template successfully to synthesize carbon nanomaterial take natural halloysite as template, this carbon nanomaterial of preparing had both copied the shape characteristic of tubulose halloysite, made carbon nanotube, also make carbon source enter into the inside, aperture of tubulose halloysite by hydro-thermal reaction, synthesized carbon nano rod (product had both included carbon nanotube and also included carbon nano rod), and this synthetic method is very simple, 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 is that embodiment 1 gained carbon is received the TEM collection of illustrative plates of the tubular structure in material and the electron diffraction collection of illustrative plates of carbon nanotube.
Fig. 4 is TEM collection of illustrative plates and the electron diffraction collection of illustrative plates of embodiment 1 gained carbon nano rod; Fig. 3 a represents the TEM collection of illustrative plates of the club shaped structure in carbon nanomaterial, and Fig. 3 b represents the electron diffraction collection of illustrative plates of the club shaped structure in carbon nanomaterial.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with example, but the present invention not only is confined to the following examples.
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 that concentration is 10-20wt% (quality) (containing the 10-20g raw ore in expression 100g suspension) 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, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 2-4h obtains slurry;
3) slurry after stirring is put into the whizzer centrifugation, rotating speed 1500-2000r/min, and the centrifugation time is 5-10min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains centrifugal for the second time throw out;
4) get centrifugal for the second time throw out, 80-100 ℃ of oven dry (baking 5-8h) namely obtains high-purity halloysite [purity of resulting high-purity halloysite is greater than 85% (quality)].
Described halloysite raw ore is the natural halloysite of Lincang ore deposit, and composition sees Table 1.Mineral composition is halloysite, kaolinite, illite, gibbsite, quartz and feldspar.
Embodiment 1:
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following 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 gibbsite to take 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) first the halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 700 ℃, then the HCl that adds 100ml, 2mol/L, filter after 2 hours, wash to neutral (pH is 6～8) in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite that will activate again, modification is good and 8.80ml furfuryl alcohol mix in rear immigration autoclave, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, after calcination finishes, treat that sample cools to room temperature with the furnace, then take out sample and removed the mineral template in 15 hours with the HF washing, with deionized water, sample is washed to neutral (pH is 6～8), filters at last, in 100 ℃ of drying and processings 12 hours, obtain carbon nanomaterial (the finished product).
Fig. 1 is the XRD diffractogram of the 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, all occurs a diffraction bag near 23 ° and 44 °, respectively correspondence the position of (002) and (101) face diffraction peak of graphite, illustrate some faint graphite microcrystal orderings to have occurred in the carbonization process of 800 ℃.Fig. 2 and Fig. 3 (a, b) are transmission electron microscope and the electron diffraction picture of prepared carbon nanomaterial, be that template has successfully been prepared the carbon nanotube that keeps the halloysite tubular structure with natural halloysite as can be seen from Figure 2, moreover, transmission electron microscope photo by Fig. 3 and electron diffraction collection of illustrative plates are as can be known, also make carbon source enter into the inside, aperture of tubulose halloysite by hydro-thermal reaction, synthesized carbon nano rod.In this carbon nanomaterial that synthesizes, include simultaneously a large amount of carbon nanotubes and a small amount of carbon nano rod, the carbon nano rod diameter of preparing can illustrate that in conjunction with electron-diffraction diagram this rod is entirely the composition of graphite in addition in 10nm.
Embodiment 2
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) first the halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 600 ℃, then the HCl that adds 100ml, 2mol/L, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite that will activate again, modification is good and 10.00g glucose mix in rear immigration autoclave, and autoclave is placed in the baking oven insulation 24 hours of 180 ℃, make presoma.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, after calcination finishes, treat that product (being sample) cools to room temperature with the furnace, then the mineral template was removed in the HF washing that to take out product (being sample) be 40wt% with concentration in 15 hours, the sample washing is extremely neutral with deionized water, filtration at last, in 100 ℃ of drying and processings 16 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product had both included carbon nanotube and also included carbon nano rod, wherein the carbon nano rod diameter Distribution is in the 2-20nm left and right.
Embodiment 3
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) first the halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 700 ℃, then the HCl that adds 100ml, 2mol/L, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite that will activate again, modification is good and 10.00g sucrose mix in rear immigration autoclave, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 18 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 4
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) first the halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 700 ℃, then add the HNO of 100ml, 2mol/L 3, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and 8.80ml furfuryl alcohol that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 20 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, 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
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 700 ℃, then add the HSO of 100ml, 2mol/L 4, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and 8.80ml furfuryl alcohol that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 20 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 6
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 300 ℃, then add the HSO of 100ml, 0.5mol/L 4, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 100 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and furfuryl alcohol that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 130 ℃ makes presoma in 6 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 500 ℃, N 2In atmosphere, calcination is 3 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 80 ℃ of drying and processings 20 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 7
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 900 ℃, then add the HSO of 100ml, 10mol/L 4, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 100 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and sucrose that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 6 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 900 ℃, N 2In atmosphere, calcination is 6 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 22 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 8
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 900 ℃, then add the HSO of 50ml, 2mol/L 4HNO with 50ml, 2mol/L 3, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and glucose that modification is good mixes again, moves in autoclave, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 22 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 9
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 900 ℃, then add the HSO of 50ml, 2mol/L 4, 50ml, 2mol/L HCl, filter after 2 hours, wash to neutral baking 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and glucose that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 10
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 900 ℃, then add the HNO of 50ml, 2mol/L 3With the HCl of 50ml, 2mol/L, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and sucrose that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 20 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
Embodiment 11
Prepare the method for carbon nanomaterial take natural halloysite as template, it comprises the following steps:
1) take 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) halloysite that weighs up is placed in crucible and is incubated 3 hours at the temperature of 900 ℃, then add the HNO of 25ml, 2mol/L 3With the HCl of 25ml, 2mol/L and the H of 50ml, 2mol/L 2SO 4, filter after 2 hours, wash to neutral and dried by the fire 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 60 ℃ of lower mechanical stirring.
3) halloysite and sucrose that modification is good mixes in rear immigration autoclave again, and autoclave is placed in the baking oven insulation of 180 ℃ makes presoma in 24 hours.
4) presoma is placed in porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N 2In atmosphere, calcination is 4 hours, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 24 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 36 hours, obtain carbon nanomaterial (the finished product).
By the method identical with embodiment 1, product is carried out XRD and TEM (transmission electron microscope) analysis, confirm that this product is for both including the carbon nanomaterial that carbon nanotube also includes carbon nano rod.
The complete chemical analysis of table 1 halloysite raw ore
Figure GDA0000120989550000091

Claims (5)

1. prepare the method for carbon nanomaterial take natural halloysite as template, it is characterized in that it comprises the following steps:
1) mass ratio by natural halloysite powder and carbon source is 1:1～5, chooses natural halloysite powder and carbon source, and is standby;
The preparation of described natural halloysite powder, it comprises the steps:
(1) the quality percentage composition with halloysite is made at halloysite raw ore and the water of 30-50 % the suspension that concentration is 10-20 wt%;
(2) add-on by Sodium hexametaphosphate 99 is the 0.2-0.5 % of halloysite ore quality, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 2-4 h obtains slurry;
(3) slurry after stirring is put into the whizzer centrifugation, rotating speed 1500-2000 r/min, and the centrifugation time is 5-10 min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3000-3800 r/min, the time is 5-10 min, obtains centrifugal for the second time throw out;
(4) get centrifugal for the second time throw out, 80-100 ℃ of oven dry namely obtains purity greater than the natural halloysite powder of 85wt%;
2) proportioning by natural halloysite powder and acid is 5g:100mL, chooses acid; Be first to be incubated 3 hours under 300 ℃～900 ℃ with natural halloysite powder in temperature, then add acid, mechanical stirring is filtered after 2 hours, is washed to neutral, dries by the fire 24～36 hours the halloysite that activated, modification is good in 85～100 ℃ of baking ovens;
3) halloysite and the carbon source that will activate, modification are good mix, and obtain halloysite/Carbon composites; Halloysite/Carbon composites is placed in autoclave, and autoclave is placed in the baking oven case, and insulation is 6h-48h hour at 130 ℃ of-180 ℃ of temperature, obtains presoma;
4) with presoma in 500 ℃～900 ℃, N 2Carry out calcination 3～6 hours under the atmosphere of protection, cool to product with the furnace room temperature after the calcination end, removed template in product in 15～24 hours with the HF washing, more extremely neutral with deionized water wash, filter, dry, obtain carbon nanomaterial.
2. the method for preparing carbon nanomaterial take natural halloysite as template according to claim 1, is characterized in that the carbon source in described step 1) is furfuryl alcohol or sucrose or glucose.
3. the method for preparing carbon nanomaterial take natural halloysite as template according to claim 1, is characterized in that described step 2) middle sour be HCl, HNO 3, H 2SO 4In any or several solution by any mixed in molar ratio; The volumetric molar concentration of acid is 0.5mol/L～10mol/L.
4. the method for preparing carbon nanomaterial take natural halloysite as template according to claim 1, is characterized in that step 4) in bake out temperature be 80 ℃-100 ℃, the time is 12～24 hours.
5. the method for preparing carbon nanomaterial take natural halloysite as template according to claim 1, is characterized in that step 4) in the concentration of HF be 40wt%.
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