CN102398902A - 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 PDFInfo
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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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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
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.
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
Claims (7)
1. be the method that template prepares carbon nanomaterial with natural halloysite, it is characterized in that it may further comprise the steps:
1) mass ratio by natural halloysite powder and carbon source is 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 ℃ insulations 3 hours 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 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, cool to product with the furnace room temperature after the calcination end, removed template in the product in 15～24 hours with the HF washing, extremely neutral with deionized water wash again, filter, dry, obtain carbon nanomaterial.
2. according to claim 1 is the method that template prepares carbon nanomaterial with natural halloysite, and it is characterized in that: the preparation of said natural halloysite powder, it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension-s that concentration is 10-20wt% 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 promptly obtains the natural halloysite powder of purity greater than 85wt%.
3. according to claim 1 is the method that template prepares carbon nanomaterial with natural halloysite, it is characterized in that the Chemical Composition of said natural halloysite powder 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%; Halloysite purity is greater than 85wt% in the natural halloysite powder, and the median size of natural halloysite powder is 5.226um.
4. according to claim 1 is the method that template prepares carbon nanomaterial with natural halloysite, it is characterized in that the carbon source in the said step 1) is furfuryl alcohol or sucrose or glucose.
5. according to claim 1 is the method that template prepares carbon nanomaterial with natural halloysite, it is characterized in that said step 2) middle sour be HCl, HNO
3, H
2SO
4In any or several kinds by the solution of any mixed in molar ratio; The volumetric molar concentration of acid is 0.5mol/L～10mol/L.
6. according to claim 1 is the method that template prepares carbon nanomaterial with natural halloysite, it is characterized in that the bake out temperature in the step 4) is 80 ℃-100 ℃, and the time is 12～24 hours.
7. according to claim 1 is the method that template prepares carbon nanomaterial with natural halloysite, and the concentration that it is characterized in that the HF in the step 4) is 40wt%.
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| CN104874357A (en) * | 2015-05-04 | 2015-09-02 | 河南师范大学 | Preparation method of modified halloysite oil absorbent |
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