CN103407982B - A kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof - Google Patents
A kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof Download PDFInfo
- Publication number
- CN103407982B CN103407982B CN201310298295.0A CN201310298295A CN103407982B CN 103407982 B CN103407982 B CN 103407982B CN 201310298295 A CN201310298295 A CN 201310298295A CN 103407982 B CN103407982 B CN 103407982B
- Authority
- CN
- China
- Prior art keywords
- carbon
- graphene
- doping
- pipe array
- nano pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof that belong to carbon material preparing technical field, this hybrid is made up of the carbon nano pipe array of N doping and Graphene, and carbon nano pipe array end is directly connected effectively with graphene sheet layer.Method in the present invention has the material with microcosmic flat surface of high density catalyst particle for catalyzer with load, pass through chemical vapour deposition, grow carbon nano pipe array and the Graphene of N doping at catalyst surface, and both are directly effectively connected to form 3-D solid structure.The present invention has enriched the kind of multifunctional special nano-carbon material; achieve the assembling of nano-carbon material from bottom to top from low-dimensional to three-dimensional material; also moving-bed, fluidized-bed etc. can be adopted to realize engineering amplify and large-scale production simultaneously, contribute to the research of the promotion carbon nano pipe array of N doping and the hybrid of Graphene, supply and practical application.<!--1-->
Description
Technical field
The invention belongs to carbon material preparing technical field, be specifically related to hybrid of a kind of carbon nanotube and Graphene and preparation method thereof, particularly relate to a kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof.
Background technology
The progress and development of human society and the continuous improvement of daily life condition be unable to do without the change that modern science and technology are maked rapid progress, and wherein a most important part is exactly exploitation and the preparation of Multifunction material.Since Iijima in 1991 successfully utilizes high-resolution-ration transmission electric-lens to observe the clear structure (IijimaS.Nature of carbon nanotube first, 1991,354 (6348): 56-58), Geim in 2004 etc. adopt mechanically peel method to obtain single-layer graphene structure (NovoselovKSetal., Science, 2004,306 (5696): 666-669) rise, the nano-carbon material family as representative is just subject to extensive concern and the research of researcher always.Desirable carbon nanotube and graphene-structured by carbon atom through sp
2hydridization is formed, and all shows excellent performance, thus make it be with a wide range of applications in fields such as matrix material, electron device, thermally conductive material, drug conveying, energy storage at numerous areas such as mechanics, optics, electromagnetism, calorifics.But, practical study and industrial application show, the performance anisotropic intrinsic due to low-dimensional materials and the scattering problem of nano material, no matter be carbon nanotube or Graphene, its performance in three-dimensional macro material often all have received great restriction, thus have impact on the industrial application of nano-carbon material.
Low-dimension nano material being assembled into 3-D solid structure is from bottom to top a kind of feasible method overcome the above problems, can either aid dispersion, is expected to again the optimization realizing three-dimensional performance.For the carbon nanotube of one dimension and the Graphene of two dimension, GeorgiosK proposes a kind of structure (GeorgiosKetal. of three-dimensional hybrid theoretically, NanoLett., 2008,8 (10): 3166-3170), carbon nano pipe array statuary column equally connects and supports perpendicular graphene sheet layer, thus form three-dimensional electric transmission and conductive network and three-dimensional pore passage structure, thus greatly facilitate the performance that carbon material applies in the fields such as electrochemistry, molecular adsorption and energy storage and express.Current report prepare similar hybrid method or at graphite oxide surface directly loaded metal active ingredient catalytic growth carbon nanotube (FanZJ, etal., Adv.Mater.2010,22,3723 – 3728), but due to unstable at graphite surface under metal nanoparticle high temperature, in products therefrom carbon nanotube mass and pattern poor, affect performance expression; Or at expanded graphite area load last layer intermediate oxidation film with the dispersion (DuF of cocatalyst particle, etal., Chem.Mater., 2011,23 (21): 4810-4816), although product morphology is better, between carbon nano pipe array and Graphene, there is oxidation film layer hinder electric transmission.
Further, some heteroatoms is introduced in the hybrid of carbon nano pipe array and Graphene and can also give its new performance and application, as the carbon nano pipe array of lithium atom doping and the hybrid hydrogen storage ability at ambient pressure of Graphene reach 41g/L, close to the demand (GeorgiosKetal. of mobile equipment application, NanoLett., 2008,8 (10): 3166-3170).And nitrogen atom doping modifies a kind of very conventional method in field at nano-carbon material, the modulation to material structure and surface property can be realized, make the nano-carbon material of inertia have certain chemically reactive, thus bring the application in the field such as electrochemical reaction and catalysis.
In view of above consideration, the present invention proposes the extraordinary nano-carbon material of a kind of carbon nano pipe array of N doping and the hybrid of Graphene, achieve the assembling from bottom to top of low-dimensional nano-carbon material, practical application for nano-carbon material provides a kind of well solution, and by the introducing of nitrogen-atoms, for this hybrid brings the performance of more novelties, thus widen its Application Areas.In addition, the present invention also developed a kind ofly has high density catalyst particle based on load and the method for the carbon nano pipe array of this kind of N doping and the hybrid of Graphene prepared by the material with microcosmic flat surface, the easy engineering of the method is amplified, universality is strong, can preparation in macroscopic quantity be realized, effectively advance the research of the carbon nano pipe array of this kind of N doping and the hybrid of Graphene, supply and practical application.
Summary of the invention
The object of the invention is to overcome the bottleneck that current nano-carbon material is encountered in practical application in industry, provide a kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof.
Technical scheme of the present invention is as follows:
The carbon nano pipe array of N doping and a hybrid for Graphene, this hybrid is made up of the carbon nano pipe array of N doping and Graphene, and carbon nano pipe array end is directly connected effectively with graphene sheet layer.
In described hybrid, nitrogen atom doping in carbon nano pipe array or graphene-structured or be entrained in the two structure simultaneously.
A preparation method for the carbon nano pipe array of above-mentioned N doping and the hybrid of Graphene, is characterized in that, the method comprises the steps:
1) to be not less than the carrier of material as catalyzer of the microcosmic flat surface of 500 nanometers containing radius-of-curvature, catalytic active component is loaded to the surface of carrier;
2) above-mentioned catalyzer is placed in reactor, under the mixed atmosphere of carbon source, nitrogenous source and carrier gas, pass through chemical vapor deposition processes, simultaneously or the successively carbon nano pipe array of growth N doping and Graphene on the surface of the catalyst, obtains the carbon nano pipe array of N doping and the hybrid of Graphene after then products therefrom purifying being removed catalyzer.
The material being not less than the microcosmic flat surface of 500 nanometers containing radius-of-curvature described in step 1) is vermiculite, laminated dihydroxy composite metal hydroxide, SiO
2, MgO, wollastonite, mica or polynite.
Catalytic active component described in step 1) is one or more in Fe, Co, Ni, Cu, Mo, W, rare earth element, wherein each catalytic active component accounts for 0.1% ~ 50% of catalyst quality respectively, and catalytic active component total mass is no more than 60% of catalyst quality.
Step 2) described in carbon source be one or more in the low-carbon (LC) gas of below eight carbon, carbon monoxide, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene, dimethylbenzene.
Step 2) described in nitrogenous source be one or more in the itrogenous organic substance of ammonia, two carbon to two ten carbon.
Step 2) described in carrier gas be one or more in argon gas, nitrogen, helium, hydrogen.
Step 2) in the carbon nano pipe array of N doping or being grown to of Graphene carry out simultaneously or successively, in process of growth, the mol ratio of carbon atom and nitrogen-atoms is 1:0 ~ 100; And the dividing potential drop of control carbon source is lower than 80%; The growth temperature of the carbon nano pipe array of N doping is 500 ~ 1000
oc, the growth temperature of the Graphene of N doping is 600 ~ 1200
oc.
Step 2) described in the type of reactor that adopts in chemical vapor deposition processes be one or more in fixed bed, moving-bed, fluidized-bed, rotary drum reactor.
The present invention compared with prior art, tool has the following advantages and high-lighting effect: in the present invention, the carbon nano pipe array of N doping is directly connected effectively with Graphene, provide a kind of new special multifunctional nano carbon material, achieve the assembling from bottom to top of nano material, can play on three-dimensional macro and expand the performance of nano-carbon material; Preparation method of the present invention can prepare the carbon nano pipe array of N doping and the hybrid of Graphene in enormous quantities; Catalyzer, source of the gas etc. that the method adopts have ubiquity; and it is cheap and easy to get; technique is relatively simple, and fluidized-bed reactor etc. are convenient to engineering amplification and mass-producing preparation simultaneously, contribute to the research of the propelling carbon nano pipe array of N doping and the hybrid of Graphene, preparation and industrial applied research.
Accompanying drawing explanation
Fig. 1 is the white vermiculite of FeMo/ and with the digital photograph of the hybrid of the carbon nano pipe array of its N doping being catalyst preparing and Graphene.
Fig. 2 is the stereoscan photograph with the white vermiculite of the FeMo/ carbon nano pipe array of N doping that is catalyst preparing and the hybrid of Graphene.
Fig. 3 is the stereoscan photograph with the white vermiculite of the FeMo/ carbon nano pipe array of N doping that is catalyst preparing and the hybrid of Graphene.
Fig. 4 is the transmission electron microscope photo with the white vermiculite of the FeMo/ carbon nano pipe array of N doping that is catalyst preparing and the hybrid of Graphene.
Fig. 5 is with the high power transmission electron microscope photo of the carbon nano pipe array of N doping in the white vermiculite of the FeMo/ carbon nano pipe array of N doping that is catalyst preparing and the hybrid of Graphene.
Fig. 6 is take FeMoMgLDH as the carbon nano pipe array of N doping of catalyst preparing and the high power stereoscan photograph of the hybrid of Graphene.
Fig. 7 is take FeMoMgLDH as the carbon nano pipe array of N doping of catalyst preparing and the transmission electron microscope photo of the hybrid of Graphene.
Fig. 8 is the scanned photograph with the NiMo/ vermiculite carbon nano pipe array of N doping that is catalyst preparing and the hybrid of Graphene.
Fig. 9 is take CuNi/MgO as the carbon nano pipe array of N doping of catalyst preparing and the stereoscan photograph of the hybrid of Graphene.
Embodiment
A kind of carbon nano pipe array of N doping provided by the invention and the hybrid of Graphene, be made up of the carbon nano pipe array of N doping and Graphene, carbon nano pipe array end is directly connected effectively with graphene sheet layer.Nitrogen atom doping, in carbon nano pipe array or graphene-structured, also can be entrained in the structure of the two simultaneously.
Below by several specific embodiment, the present invention is further illustrated.
Embodiment 1: with the white vermiculite of FeMo/ for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed.
Vermiculite is a kind of common lamella stacked material, has good divisibility under high temperature, and radius-of-curvature is very large, has microcosmic flat surface.Adopt white vermiculite as support of the catalyst, obtain by dip loading the catalyzer that active ingredient Fe, Mo account for total mass 20%, 2% respectively.Catalyzer is placed in the tubular fixed-bed central authorities that internal diameter is 20mm, under the atmosphere of 200sccm argon gas and 100sccm hydrogen, is warming up to 650
oc, passes into the mixture of carbon source ethene and nitrogenous source ammonia then, and carbon and nitrogen atoms is than being 1:1, carbon source dividing potential drop is 25%, temperature maintains the carbon nano pipe array of 30min by chemical vapor deposition growth N doping, closes carbon source, nitrogenous source and hydrogen afterwards, is warming up to 950 under an argon atmosphere
oc, then pass into carbon source methane, carbon source dividing potential drop is 80%, reaction 1hr growing graphene.After cooling, products therefrom macro morphology is see Fig. 1, because the intercalation growth between vermiculite lamella of array and Graphene causes volumetric expansion.By product 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 12hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 98%, only has carbon nano-pipe array to show nitrogen atom doping.This hybrid pattern is as shown in Fig. 2-3 stereoscan photograph, and carbon nano pipe array end is directly connected effectively with graphene sheet layer, forms 3-D solid structure.Transmission electron microscope photo shown in Fig. 3 further demonstrates effective connection of carbon nano pipe array and Graphene, and in Fig. 4, typical bamboo-like carbon nano tubes also illustrate that the successful doping of nitrogen-atoms simultaneously.
Embodiment 2: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed with FeMoMgLDH.
LDH is laminated dihydroxy composite metal hydroxide, has the laminated structure of houghite, and radius-of-curvature is very large.With active ingredient Fe, Mo content be respectively 30% and 3%, Mg content be the FeMoMgLDH of 30% for catalyzer, being positioned over internal diameter is in the fixed bed of 20mm, under the atmosphere of 200sccm nitrogen and 50sccm hydrogen, be warming up to 700
oc, passes into carbon source propylene then, and carbon source dividing potential drop is 50%, and temperature maintains 30min by chemical vapor deposition growth carbon nano pipe array, closes carbon source and hydrogen afterwards, is warming up to 900 in a nitrogen atmosphere
oc, then the mixture passing into carbon source Benzene and Toluene and nitrogenous source pyridine, carbon and nitrogen atoms is than being 1:5, and carbon source dividing potential drop is 10%, and reaction 5hr grows the Graphene of N doping.After cooling, products therefrom uses the NaOH aqueous solution of 5mol/L 180 successively
othe HCl aqueous solution of 12hr and 1mol/L is processed 80 under C
oprocess 24hr under C and can obtain the carbon nano pipe array of N doping and the hybrid of Graphene, purity reaches 99%, only has Graphene to have nitrogen atom doping.Carbon nano pipe array end is directly connected effectively with graphene sheet layer, and form 3-D solid structure, its pattern is see Fig. 5.High-resolution-ration transmission electric-lens shown in Fig. 6 further illustrates the efficient connection of carbon nanotube and Graphene.
Embodiment 3: with NiMo/ vermiculite for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed.
Be respectively the vermiculite of 1% and 0.1% with Ni, Mo charge capacity for catalyzer, be placed on the tubular fixed-bed central authorities that internal diameter is 50mm, under the atmosphere of 200sccm helium, be warming up to 700
oc, passes into the mixture of carbon source butylene and nitrogenous source pyridine then, and carbon and nitrogen atoms is than being 1:2, carbon source dividing potential drop is 25%, temperature maintains the carbon nano pipe array of 30min by chemical vapor deposition growth N doping, closes Carbon and nitrogen sources afterwards, under helium atmosphere, is warming up to 1000
oc, then the mixture passing into carbon source methane and nitrogenous source quadrol, carbon and nitrogen atoms is than being 1:1, and carbon source dividing potential drop is 30%, and reaction 1hr grows the Graphene of N doping.After cooling, products therefrom is 80
othe carbon nano pipe array of N doping and the hybrid of Graphene can be obtained with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, pattern shown in Fig. 7 illustrates that carbon nano pipe array end is directly connected effectively with graphene sheet layer, form 3-D solid structure, carbon nano pipe array and Graphene all have nitrogen atom doping.
Embodiment 4: with CoMo/SiO
2particle is that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fluidized-bed.
Adopt radius-of-curvature to be 50 microns, there is the spherical SiO of microcosmic flat surface
2particle, as carrier, obtains by dip loading the catalyzer that active ingredient Co, Mo account for total mass 50%, 10% respectively.Being positioned over internal diameter is in the fluidized-bed of 25mm, under the atmosphere of 200sccm nitrogen and 100sccm hydrogen, be warming up to 800
oc, passes into the mixture of carbon source dimethylbenzene and nitrogenous source ammonia then, and carbon and nitrogen atoms is than being 1:100, carbon source dividing potential drop is 0.5%, temperature maintains the carbon nano pipe array of 5hr by chemical vapor deposition growth N doping, closes carbon source, nitrogenous source and hydrogen afterwards, is warming up to 1200 in a nitrogen atmosphere
oc, then pass into carbon source ethanol, carbon source dividing potential drop is 80%, reaction 1hr growing graphene.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, only has carbon nano-pipe array to show nitrogen atom doping.
Embodiment 5: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fluidized-bed with CuNi/MgO.
With Cu, Ni for catalytic active component, load on stratiform MgO, Cu, Ni component accounts for 50%, 10% of catalyst quality respectively, and being positioned over internal diameter is in the fluidized-bed of 50mm, under 500sccm argon atmosphere, be warming up to 900
oc, passes into the mixture of carbon source toluene and nitrogenous source octylame then, and carbon and nitrogen atoms is than being 1:0.1, and carbon source dividing potential drop is 50%, and reaction 2hr grows carbon nano pipe array and the Graphene of N doping simultaneously.After cooling, products therefrom is 80
othe carbon nano pipe array of N doping and the hybrid of Graphene can be obtained with the HCl aqueous solution process 24hr of 1mol/L under C, purity reaches 98.5%, wherein carbon nano pipe array end is directly connected effectively with graphene sheet layer, form 3-D solid structure, carbon nano pipe array and Graphene all have nitrogen atom doping, and pattern as shown in Figure 8.
Embodiment 6: with CuCo/ wollastonite for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed.
Wollastonite belongs to triclinic(crystalline)system, usually in the form of sheets, radial or fibrous agrregate, has good divisibility.Be greater than the fibrous wollastonite of 20 microns with radius-of-curvature for carrier, obtain through Cu, Co load the catalyzer that active ingredient accounts for 10%, 1% respectively.This catalyzer is placed in the tubular fixed-bed central authorities that internal diameter is 25mm, under the atmosphere of 300sccm argon gas and 100sccm hydrogen, is warming up to 1000
oc, then the mixture of carbon source carbon monoxide and nitrogenous source ammonia and quadrol is passed into, carbon and nitrogen atoms is than being 1:2, carbon source dividing potential drop is 20%, temperature maintains the carbon nano pipe array of 30min by chemical vapor deposition growth N doping, close carbon source, nitrogenous source and hydrogen afterwards, be warming up to 1100 under an argon atmosphere
oc, then pass into carbon source methyl alcohol, carbon source dividing potential drop is 60%, reaction 1hr growing graphene.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with each 24hr of HF aqueous solution process of the HCl aqueous solution 1mol/L of 1mol/L successively under C, purity reaches 99%, only has carbon nano-pipe array to show nitrogen atom doping.
Embodiment 7: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by the combination of fluidized-bed and rotary drum reactor with FeMgAlLDH.
With active ingredient Fe content be 50%, Mg, the content of Al is respectively the FeMgAlLDH of 20% and 10% for catalyzer, being positioned over internal diameter is in the fluidized-bed of 20mm, under the atmosphere of 200sccm argon gas and 50sccm hydrogen, be warming up to 500
oc, then the mixture of carbon source hexanaphthene and nitrogenous source ammonia is passed into, carbon and nitrogen atoms is than being 1:10, carbon source dividing potential drop is 5%, temperature maintains the carbon nano pipe array of 5hr by chemical vapor deposition growth N doping, close carbon source, nitrogenous source and hydrogen afterwards, under an argon atmosphere product is blown in rotary drum reactor, and is warming up to 900
oc, then the mixture passing into carbon source benzene and nitrogenous source octylame, carbon and nitrogen atoms is than being 1:1, and carbon source dividing potential drop is 30%, and reaction 5hr grows the Graphene of N doping.After cooling, products therefrom uses the NaOH aqueous solution of 5mol/L 180 successively
othe HCl aqueous solution of 12hr and 1mol/L is processed 80 under C
oprocess 24hr under C and can obtain the carbon nano pipe array of N doping and the hybrid of Graphene, purity reaches 99%, and carbon nano pipe array and Graphene all have nitrogen atom doping,
Embodiment 8: with FeCe/ mica for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by moving-bed.
Adopt radius-of-curvature to be greater than 10 microns of column micas with microcosmic flat surface as carrier, obtain by dip loading the catalyzer that active ingredient Fe, Ce account for total mass 10%, 1% respectively.Being positioned over internal diameter is in the moving-bed of 50mm, under the atmosphere of 1000sccm helium, be warming up to 600
oc, passes into the mixture of carbon source dimethylbenzene and nitrogenous source pyrroles then, and carbon and nitrogen atoms is than being 1:50, and carbon source dividing potential drop is 1%, and temperature maintains 5hr grows N doping simultaneously carbon nano pipe array and Graphene by chemical vapour deposition.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 12hr of HF aqueous solution process of 0.5mol/L successively under C, purity reaches 98%, and carbon nano pipe array and Graphene all have nitrogen atom doping.
Embodiment 9: with FeMoCo/ polynite for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed.
Polynite is the silicate crystal of stratiform, surface curvature radius is larger, with Fe, Mo, Co for active constituent loading and content is respectively the polynite of 5%, 0.5%, 3% for catalyzer, be placed on the tubular fixed-bed central authorities that internal diameter is 25mm, under the atmosphere of 300sccm argon gas and 100sccm hydrogen, be warming up to 650
oc, passes into the mixture of carbon source carbon monoxide and ethene then, carbon source dividing potential drop 70%, and temperature maintains 15min by chemical vapor deposition growth carbon nano pipe array, closes carbon source and hydrogen afterwards, is warming up to 1000 under an argon atmosphere
oc, then the mixture passing into carbon source methane and nitrogenous source ammonia, carbon and nitrogen atoms is than being 1:10, and carbon source dividing potential drop is 3%, and reaction 5hr grows the Graphene of N doping.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, only has Graphene to have nitrogen atom doping.
Embodiment 10: with FeW/ mica for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fluidized-bed.
Be respectively the mica of 5% and 1% with Fe, W charge capacity for catalyzer, being positioned over internal diameter is in the fluidized-bed of 50mm, under the atmosphere of 700sccm argon gas, be warming up to 1000
oc, passes into the mixture of carbon source ethene and nitrogenous source octylame then, and carbon and nitrogen atoms is than being 1:1, and carbon source dividing potential drop is 30%, and reaction 5hr grows carbon nano pipe array and the Graphene of N doping simultaneously.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 12hr of HF aqueous solution process of 0.5mol/L successively under C, purity reaches 98%, and carbon nano pipe array and Graphene all have nitrogen atom doping.
Embodiment 11: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fluidized-bed with FeMoMgAlLDH.
With Fe, Mo charge capacity be respectively 5% and 0.5%, Mg, Al content be respectively the FeMoMgAlLDH of 40%, 20% for catalyzer, being positioned over internal diameter is in the fluidized-bed of 20mm, under the atmosphere of 200sccm nitrogen, be warming up to 500
oc, passes into the mixture of carbon source ethene and nitrogenous source quadrol then, and carbon and nitrogen atoms is than being 1:0.5, carbon source dividing potential drop is 40%, temperature maintains the carbon nano pipe array of 2hr by chemical vapor deposition growth N doping, closes Carbon and nitrogen sources afterwards, is warming up to 1200 in a nitrogen atmosphere
oc, then pass into carbon source methane, carbon source dividing potential drop is 50%, reaction 1hr growing graphene.After cooling, products therefrom uses the NaOH aqueous solution of 5mol/L 180 successively
othe HCl aqueous solution of 12hr and 1mol/L is processed 80 under C
oprocess 24hr under C and can obtain the carbon nano pipe array of N doping and the hybrid of Graphene, purity reaches 99%, only has carbon nano-pipe array to show nitrogen atom doping.
Embodiment 12: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fluidized-bed with NiCo/MgO.
With Ni, Co for catalytic active component, load on stratiform MgO, Ni, Co component accounts for 10%, 5% of catalyst quality respectively, and being positioned over internal diameter is in the fluidized-bed of 25mm, under the atmosphere of 200sccm helium and 100sccm hydrogen, be warming up to 700
oc, passes into the mixture of carbon source toluene and positive 20 amine of nitrogenous source then, and carbon and nitrogen atoms is than being 1:2, and carbon source dividing potential drop is 20%, and reaction 30min grows the carbon nano pipe array of N doping.Close carbon source, nitrogenous source and hydrogen afterwards, under helium atmosphere, be warming up to 1000
oc, then pass into carbon source carbon monoxide, carbon source dividing potential drop is 50%, reaction 1hr growing graphene.After cooling, products therefrom is 80
othe carbon nano pipe array of N doping and the hybrid of Graphene can be obtained with the HCl aqueous solution process 24hr of 1mol/L under C, purity reaches 98.5%, wherein carbon nano pipe array end is directly connected effectively with graphene sheet layer, form 3-D solid structure, only have carbon nano-pipe array to show nitrogen atom doping.
Embodiment 13: with FeCoCe/SiO
2particle is that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by the combination of fluidized-bed and rotary drum reactor.
Adopt radius-of-curvature to be not less than 500 nanometers, there is the spherical SiO of microcosmic flat surface
2particle, as carrier, obtains by dip loading the catalyzer that active ingredient Fe, Co, Ce account for total mass 30%, 25%, 5% respectively.Being positioned over internal diameter is in the fluidized-bed of 25mm, under the atmosphere of 200sccm nitrogen, be warming up to 1000
oc, then the mixture of carbon source octane and nitrogenous source n-hexadecane amine is passed into, carbon and nitrogen atoms is than being 1:10, carbon source dividing potential drop is 5%, temperature maintains the carbon nano pipe array of 2hr by chemical vapor deposition growth N doping, close Carbon and nitrogen sources afterwards, in a nitrogen atmosphere product is blown in rotary drum reactor, and is warming up to 1200
oc, then the mixture passing into carbon source normal butane and dimethylbenzene, carbon source dividing potential drop is 50%, reaction 1hr growing graphene.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, only has carbon nano-pipe array to show nitrogen atom doping.
Embodiment 14: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed with CoMoMgAlLDH.
With active ingredient Co, Mo content be respectively 20% and 2%, Mg, Al content be respectively the CoMoMgAlLDH of 20%, 30% for catalyzer, being positioned over internal diameter is in the fixed bed of 20mm, under the atmosphere of 100sccm nitrogen and 50sccm hydrogen, be warming up to 500
oc, passes into the mixture of carbon source hexanaphthene and nitrogenous source octylame then, and carbon and nitrogen atoms is than being 1:2, carbon source dividing potential drop is 10%, temperature maintains the carbon nano pipe array of 30min by chemical vapor deposition growth N doping, closes carbon source, nitrogenous source and hydrogen afterwards, is warming up to 600 in a nitrogen atmosphere
oc, then the mixture passing into carbon source ethane and nitrogenous source pyridine, carbon and nitrogen atoms is than being 1:4, and carbon source dividing potential drop is 10%, and reaction 5hr grows the Graphene of N doping.After cooling, products therefrom uses the NaOH aqueous solution of 5mol/L 180 successively
othe HCl aqueous solution of 12hr and 1mol/L is processed 80 under C
oprocess 24hr under C and can obtain the carbon nano pipe array of N doping and the hybrid of Graphene, purity reaches 99%, and carbon nano pipe array and Graphene all have nitrogen atom doping.
Embodiment 15: with CuCoMo/ mica for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed.
Be respectively the mica of 10%, 5%, 1% with Cu, Co, Mo charge capacity for catalyzer, being positioned over internal diameter is in the fixed bed of 50mm, under the atmosphere of 500scc nitrogen, be warming up to 800
oc, passes into the mixture of carbon source acetylene and nitrogenous source butylamine then, and carbon and nitrogen atoms is than being 1:2, and carbon source dividing potential drop is 20%, and reaction 1hr grows carbon nano pipe array and the Graphene of N doping simultaneously.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 12hr of HF aqueous solution process of 0.5mol/L successively under C, purity reaches 98%, and carbon nano pipe array and Graphene all have nitrogen atom doping.
Embodiment 16: be that catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed with NiW/MgO.
Be respectively the stratiform MgO of 10%, 5% with Ni, W charge capacity for catalyzer, be positioned over the fixed bed central authorities that internal diameter is 25mm, under the atmosphere of 100sccm argon gas and 50sccm hydrogen, be warming up to 600
oc, passes into the mixture of carbon source ethanol and nitrogenous source n-amylamine then, and carbon and nitrogen atoms is than being 1:1, and carbon source dividing potential drop is 20%, and reaction 30min grows the carbon nano pipe array of N doping.Close carbon source, nitrogenous source and hydrogen afterwards, be warming up to 800 under an argon atmosphere
oc, then the mixture passing into carbon source methyl alcohol and methane, carbon source dividing potential drop is 50%, reaction 1hr growing graphene.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution process 24hr of 1mol/L under C, purity reaches 98.5%, only has carbon nano-pipe array to show nitrogen atom doping.
Embodiment 17: with CoMo/ vermiculite for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fixed bed.
Be respectively the vermiculite of 50% and 5% with Co, Mo charge capacity for catalyzer, be placed on the tubular fixed-bed central authorities that internal diameter is 25mm, under the atmosphere of 100sccm argon gas, be warming up to 900
oc, passes into the mixture of carbon source carbon monoxide and nitrogenous source pyridine then, and carbon and nitrogen atoms is than being 1:2, and carbon source dividing potential drop is 25%, and temperature maintains 5hr grows N doping simultaneously carbon nano pipe array and Graphene by chemical vapour deposition.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, and carbon nano pipe array and Graphene all have nitrogen atom doping.
Embodiment 18: with FeW/ wollastonite for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by the combination of fluidized-bed and rotary drum reactor.
Be greater than the wollastonite of 1 micron with radius-of-curvature for carrier, obtain through Fe, W load the catalyzer that active ingredient accounts for 30%, 3% respectively, being positioned over internal diameter is in the fluidized-bed of 25mm, under the atmosphere of 200sccm nitrogen and 100sccm hydrogen, be warming up to 700
oc, then carbon source benzene and nitrogenous source 1 is passed into, the mixture of 7-heptamethylene diamine, carbon and nitrogen atoms is than being 1:4, carbon source dividing potential drop is 5%, and temperature maintains the carbon nano pipe array of 1hr by chemical vapor deposition growth N doping, closes carbon source, nitrogenous source and hydrogen afterwards, in a nitrogen atmosphere product is blown in rotary drum reactor, and is warming up to 900
oc, then pass into carbon source methane, carbon source dividing potential drop is 50%, reaction 1hr growing graphene.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, only has carbon nano-pipe array to show nitrogen atom doping.
Embodiment 19: with CuCe/ polynite for catalyzer prepares the carbon nano pipe array of N doping and the hybrid of Graphene by fluidized-bed.
With Cu, Ce for active constituent loading and content is respectively the polynite of 5%, 0.5% for catalyzer, being placed on internal diameter is in the fluidized-bed of 25mm, under the atmosphere of 150sccm nitrogen and 50sccm hydrogen, be warming up to 750
oc, passes into the mixture of carbon source ethene and propylene and nitrogenous source ammonia then, and carbon and nitrogen atoms is than being 1:10, carbon source dividing potential drop is 3%, temperature maintains the carbon nano pipe array of 30min by chemical vapor deposition growth N doping, closes carbon source, nitrogenous source and hydrogen afterwards, is warming up to 1000 in a nitrogen atmosphere
oc, then pass into carbon source methane, carbon source dividing potential drop is 30%, reaction 1hr growing graphene.After cooling, products therefrom is 80
ocan obtain the carbon nano pipe array of N doping and the hybrid of Graphene with the HCl aqueous solution of 1mol/L and each 24hr of HF aqueous solution process of 1mol/L successively under C, purity reaches 99%, only has carbon nano-pipe array to show nitrogen atom doping.
Claims (8)
1. a preparation method for the carbon nano pipe array of N doping and the hybrid of Graphene, is characterized in that, comprises the steps:
1) to be not less than the carrier of material as catalyzer of the microcosmic flat surface of 500 nanometers containing radius-of-curvature, catalytic active component is loaded to the surface of carrier;
2) above-mentioned catalyzer is placed in reactor, under the mixed atmosphere of carbon source, nitrogenous source and carrier gas, pass through chemical vapor deposition processes, simultaneously or the successively carbon nano pipe array of growth N doping and Graphene on the surface of the catalyst, obtains the carbon nano pipe array of N doping and the hybrid of Graphene after then products therefrom purifying being removed catalyzer.
2. preparation method as claimed in claim 1, is characterized in that, step 1) described in be not less than the microcosmic flat surface of 500 nanometers containing radius-of-curvature material be vermiculite, laminated dihydroxy composite metal hydroxide, SiO
2, MgO, wollastonite, mica or polynite.
3. preparation method as claimed in claim 1, it is characterized in that, step 1) described in catalytic active component be one or more in Fe, Co, Ni, Cu, Mo, W, rare earth element, wherein each catalytic active component accounts for 0.1% ~ 50% of catalyst quality respectively, and catalytic active component total mass is no more than 60% of catalyst quality.
4. preparation method as claimed in claim 1, is characterized in that: step 2) described in carbon source be one or more in the low-carbon (LC) gas of below eight carbon.
5. preparation method as claimed in claim 1, is characterized in that: step 2) described in nitrogenous source be one or more in the itrogenous organic substance of ammonia, two carbon to two ten carbon.
6. preparation method as claimed in claim 1, is characterized in that: step 2) described in carrier gas be one or more in argon gas, nitrogen, helium, hydrogen.
7. preparation method as claimed in claim 1, is characterized in that: step 2) in the carbon nano pipe array of N doping or being grown to of Graphene carry out simultaneously or successively, in process of growth, the mol ratio of carbon atom and nitrogen-atoms is 1:0 ~ 100; And the dividing potential drop of control carbon source is lower than 80%; The growth temperature of the carbon nano pipe array of N doping is 500 ~ 1000 DEG C, and the growth temperature of the Graphene of N doping is 600 ~ 1200 DEG C.
8., as according to preparation method according to claim 1, it is characterized in that: step 2) described in the type of reactor that adopts in chemical vapor deposition processes be one or more in fixed bed, moving-bed, fluidized-bed, rotary drum reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298295.0A CN103407982B (en) | 2013-07-16 | 2013-07-16 | A kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298295.0A CN103407982B (en) | 2013-07-16 | 2013-07-16 | A kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103407982A CN103407982A (en) | 2013-11-27 |
| CN103407982B true CN103407982B (en) | 2016-02-10 |
Family
ID=49601044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310298295.0A Active CN103407982B (en) | 2013-07-16 | 2013-07-16 | A kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103407982B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706388B (en) * | 2013-12-30 | 2016-01-06 | 中国科学院化学研究所 | Composite of N doping porous carbon enveloped carbon nanometer tube and its preparation method and application |
| CN103910349B (en) * | 2014-03-13 | 2015-11-11 | 吉林大学 | A kind of method preparing the directed bamboo-like carbon nano tubes/Graphene complex metal oxides of nitrating |
| CA2949913A1 (en) * | 2014-05-23 | 2015-11-26 | Canatu Oy | Method and apparatus for producing nanomaterial |
| CN105000542B (en) * | 2015-04-27 | 2017-07-07 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method of graphene carbon nanotube three-dimensional structure composite |
| CN105118682B (en) * | 2015-09-14 | 2018-04-10 | 清华大学 | Activated carbon and the composite particles of graphene hybrid composition, preparation method and application |
| CN105645376B (en) * | 2015-12-17 | 2018-04-24 | 天津工业大学 | A kind of method of the direct growth porous carbon nanotube-graphene alkene hybrid on nano porous copper |
| CN106229506B (en) * | 2016-08-17 | 2018-09-18 | 天津大学 | A method of fluorocarbons discharge voltage is regulated and controled by graphene planes curvature |
| CN106602012B (en) * | 2016-12-13 | 2020-05-26 | 上海交通大学 | Flexible thin film electrode and preparation method and application thereof |
| CN106783217B (en) * | 2017-01-16 | 2018-07-13 | 天津大学 | Method for efficiently preparing nitrogen-doped graphene carbon nanotube film |
| CN108395822A (en) * | 2018-05-31 | 2018-08-14 | 哈尔滨金纳科技有限公司 | A kind of preparation method of spiral carbon nanotubes-graphene hybrid anticorrosive paint |
| CN109181637B (en) * | 2018-08-24 | 2021-02-09 | 东南大学 | Laminated Mo2CTxNitrogen-doped carbon micro-nano hybrid composite wave-absorbing material and preparation method thereof |
| CN110228805B (en) * | 2019-07-24 | 2021-04-16 | 西南交通大学 | Reduced graphene oxide/carbon nanotube composite material and preparation method thereof |
| CN110371956B (en) * | 2019-08-13 | 2022-07-05 | 中国科学院上海高等研究院 | Nitrogen-doped carbon nanotube/graphene composite film and preparation method thereof |
| CN112593203B (en) * | 2020-11-26 | 2022-09-27 | 中国科学院福建物质结构研究所 | Preparation method and application of sulfur and/or nitrogen doped graphene nanosheet |
| CN112779553B (en) * | 2020-12-25 | 2023-09-08 | 中国科学院福建物质结构研究所 | Composite material, preparation method and application thereof |
| CN113912043A (en) * | 2021-11-30 | 2022-01-11 | 南昌大学 | Preparation method of graphene/carbon nanotube composite array material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| CN101665249A (en) * | 2009-09-11 | 2010-03-10 | 清华大学 | Method for preparing minor-diameter carbon nanotube array on surface of flaky material |
| CN102515140A (en) * | 2011-11-29 | 2012-06-27 | 清华大学 | Method for large-scale preparation for nitrogen-doped carbon nanotube aligned array |
-
2013
- 2013-07-16 CN CN201310298295.0A patent/CN103407982B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| CN101665249A (en) * | 2009-09-11 | 2010-03-10 | 清华大学 | Method for preparing minor-diameter carbon nanotube array on surface of flaky material |
| CN102515140A (en) * | 2011-11-29 | 2012-06-27 | 清华大学 | Method for large-scale preparation for nitrogen-doped carbon nanotube aligned array |
Non-Patent Citations (1)
| Title |
|---|
| Three-Dimensional Nitrogen-Doped Carbon Nanotubes/Graphene;Yanwen Ma;《The Hournal of Physical Chemistry》;20111104;第115卷;24592-24597 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103407982A (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103407982B (en) | A kind of carbon nano pipe array of N doping and the hybrid of Graphene and preparation method thereof | |
| Xu et al. | 3D hierarchical carbon-rich micro-/nanomaterials for energy storage and catalysis | |
| Wang et al. | Synthesis of carbon nanotubes by catalytic chemical vapor deposition | |
| Guo et al. | Two‐dimensional materials of group‐IVA boosting the development of energy storage and conversion | |
| Kairi et al. | Recent trends in graphene materials synthesized by CVD with various carbon precursors | |
| Duan et al. | Atomically thin transition‐metal dichalcogenides for electrocatalysis and energy storage | |
| Chen et al. | Emerging two-dimensional nanomaterials for electrochemical hydrogen evolution | |
| CN102674316B (en) | Method for preparing composition of carbon nano tube and graphene by using sheet material | |
| Agudosi et al. | A review of the graphene synthesis routes and its applications in electrochemical energy storage | |
| CN103407985A (en) | Heteratom doped carbon nano-tube-graphene complex and preparation method thereof | |
| CN1302986C (en) | Method for preparing Nano carbon tubes | |
| CN102765713B (en) | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals | |
| Wang et al. | Controllable tailoring graphene nanoribbons with tunable surface functionalities: an effective strategy toward high-performance lithium-ion batteries | |
| Rümmeli et al. | Carbon nanotubes and related structures: production and formation | |
| CN111170309A (en) | Preparation method of ultra-long few-wall carbon nanotube array | |
| Gutiérrez-García et al. | Synthesis of carbon spheres by atmospheric pressure chemical vapor deposition from a serial of aromatic hydrocarbon precursors | |
| Mujib et al. | Design, characterization, and application of elemental 2D materials for electrochemical energy storage, sensing, and catalysis | |
| Afolabi et al. | Synthesis and purification of bimetallic catalysed carbon nanotubes in a horizontal CVD reactor | |
| Takai et al. | Graphene: preparations, properties, applications, and prospects | |
| Liu et al. | Substrate-free synthesis of large area, continuous multi-layer graphene film | |
| Saner Okan et al. | Effect of reaction temperature and catalyst type on the formation of boron nitride nanotubes by chemical vapor deposition and measurement of their hydrogen storage capacity | |
| Lv et al. | Formation of carbon nanofibers/nanotubes by chemical vapor deposition using Al2O3/KOH | |
| Das et al. | Graphene synthesis | |
| Zhu et al. | Advances in precise structure control and assembly toward the carbon nanotube industry | |
| Chen et al. | 2D molybdenum compounds for electrocatalytic energy conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |