CN106829926A - A kind of high-purity spiral carbon nanotubes and preparation method thereof - Google Patents

A kind of high-purity spiral carbon nanotubes and preparation method thereof Download PDF

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CN106829926A
CN106829926A CN201710119447.4A CN201710119447A CN106829926A CN 106829926 A CN106829926 A CN 106829926A CN 201710119447 A CN201710119447 A CN 201710119447A CN 106829926 A CN106829926 A CN 106829926A
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carbon nanotubes
purity
preparation
spiral carbon
alpha
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CN106829926B (en
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周祚万
王颖
孟凡彬
赵蒙蒙
姜曼
何平
周雪松
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Southwest Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/30—Purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Abstract

The present invention relates to a kind of high-purity spiral carbon nanotubes and preparation method thereof.The method is comprised the following steps：(1) alpha-crystal form nano iron oxide catalyst precursor is prepared：Alpha-crystal form nano iron oxide catalyst precursor is prepared using preformed precipitate combination sol-gal process；(2) high-purity spiral carbon nanotubes are prepared：The alpha-crystal form nano iron oxide catalyst precursor is placed in tube furnace, is allowed to be reduced to a nanometer iron catalyst using local reduction way, while introducing carbon source and steam as catalysis regulation auxiliary agent, be incubated 6 10 hours, obtain high-purity spiral carbon nanotubes.The method is simple and safe, environment-friendly, preparation-obtained spiral carbon nanotubes high purity more than 99%, and yield is up to 7,709 8077 (g HCNTs/g catalyst), and the parameter such as product diameter, spiral shell footpath, pitch is uniform, and pattern is complete.

Description

A kind of high-purity spiral carbon nanotubes and preparation method thereof
Technical field
The present invention relates to micro Nano material preparation field, and in particular to a kind of high-purity spiral carbon nanotubes and its preparation side Method.
Background technology
The molecule of helical structure has chirality, so as to make it have the physical properties such as unique optics, electricity and magnetics, and And had broad application prospects at aspects such as chiral separation, opto-electronic device and electro-magnetic wave absorptions；Helical structure is present in certainly Right boundary, meets the development law of nature, it then follows the law of thermodynamics, the CNT (spiral carbon nanotubes with spiral HCNTs it is) also such, it is contemplated that HCNTs can play important work in terms of micro-nano device and polymer-modified composite With；But technology of preparing about HCNTs and immature, it is mainly shown as that the size and homogeneity of catalyst are difficult to ensure that, The spiral purity of HCNTs is difficult to control to, yield is too low and complex technical process etc., it is impossible to meet requirement of the people to applying.
At present, the preparation method of HCNTs is similar to the preparation method of CNT (CNTs), mainly using chemical gaseous phase Prepared by sedimentation, but its product spiral purity is not high, and the preparation of high-purity HCNTs is still highly difficult, and main cause is catalysis Agent particle size, pattern are difficult to control to, and cause product spiral purity low；In the prior art, main solution is typically The second component is added in catalyst or H is introduced during catalytic growth2S, thiophene etc. can be carried significantly as growth auxiliary agent The spiral purity of product high, but so not only make the preparation process of catalyst more complicated, while H2S, thiophene etc. be poisonous and dirt The introducing for contaminating material can also cause environmental problem.Thus need a kind of easy and effective and environment-friendly method for preparing HCNTs badly.
The content of the invention
The above-mentioned problems in the prior art is directed to, is received it is an object of the present invention to provide a kind of high-purity spiral carbon The preparation method of mitron, the method is simple and safe, environment-friendly, high-purity spiral carbon nanotubes high purity 99% of preparation with On.
The technical scheme that present invention solution above-mentioned technical problem is used is as follows：A kind of new high-purity spiral carbon nanotubes are provided Preparation method, including：
(1) alpha-crystal form nano iron oxide catalyst precursor is prepared：α is prepared using preformed precipitate combination sol-gel process Crystal type nano ferric oxide catalyst precursor；
(2) high-purity spiral carbon nanotubes are prepared：The alpha-crystal form nano iron oxide catalyst precursor is placed in tube furnace In, it is allowed to be reduced to a nanometer iron catalyst using local reduction way, while introducing carbon source and steam as catalysis regulation auxiliary agent, protect It is warm 6-10 hours, obtain high-purity spiral carbon nanotubes.
Beneficial effects of the present invention are：The present invention mainly uses specific catalyst precursor technology of preparing and catalysagen Position regulation and control method prepares high-purity spiral carbon nanotubes, specially：Prepared by using preformed precipitate technique combination sol-gel process Even scattered catalyst precursor, and the introducing of the in-situ reducing and carbon-source gas by presoma prepares spiral carbon nanotubes, And in growth course by carbon-source gas by the form of bubbling introduce Trace Water Vapor (<1.0 μ L/min), by it to catalysis The regulation and control of agent crystal prepare the spiral carbon nanotubes of high-purity；The method is simple and safe, environment-friendly, preparation-obtained Spiral carbon nanotubes high purity more than 99%, it is equal that yield is up to the parameters such as 8078g/g catalyst, product diameter, spiral shell footpath, pitch Even, pattern is complete.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, in step (2), using Bubbling method, carbon-source gas bring steam into, and the introduction volume of steam is carbon-source gas The 1 × 10 of volume-5~1.3 × 10-5, continue more uniform introducing Trace Water Vapor.
The present invention regulates and controls the purity of spiral carbon nanotubes using water as auxiliary agent, by a small amount of steam to photocatalyst crystals Original position regulation and control, you can increase substantially spiral carbon nanotubes purity, reduce accessory substance；Compared to other auxiliary agent (thiophene, hydrogen sulfide Deng) to more environment-friendly, the preparation method of spiral carbon nanotubes is simple, gained spiral carbon nanotubes purity few using equipment Height, with potential application value.
Using having the beneficial effect that for above-mentioned further scheme:
Further, the specific method of step (1) is：
(11) Iron dichloride tetrahydrate and Rochelle salt are each configured to concentration identical solution, are taken identical The solution of volume, at room temperature, Iron dichloride tetrahydrate solution is added drop-wise in Rochelle salt solution, is stood, and is ground Mill, obtains ferrous tartrate powder；
(12) ferrous tartrate powder and citric acid are mixed in absolute ethyl alcohol and form suspension, stirred at 60-100 DEG C Mix 3-8 hours and form blackish green gel, after being dried at 90-100 DEG C, be placed in tube furnace, under air atmosphere, in 400- 600 DEG C are calcined 1-3 hours, and grinding obtains alpha-crystal form nano iron oxide catalyst precursor.
Using having the beneficial effect that for above-mentioned further scheme：The alpha-crystal form nano iron oxide catalyst precursor preparation method Simply, low cost, safety non-toxic.
Further, in step (12), ferrous tartrate powder is 1 with the amount ratio of the material of citric acid：1-1：2.
Further, in step (12), ferrous tartrate powder is 1 with the amount ratio of the material of citric acid：1.5.
Using having the beneficial effect that for above-mentioned further scheme：
Further, in step (12), ferrous tartrate powder and citric acid are mixed in absolute ethyl alcohol and form suspension, Blackish green gel is formed in stirring 3-8 hours at 70-90 DEG C.
Further, the specific method of step (2) is：
(21) alpha-crystal form nano iron oxide catalyst precursor is placed in tube furnace, is passed through with the flow of 100ml/min lazy 400-500 DEG C is heated to after property gas and keeps more than 10min, be then shut off carrier gas, be passed through with the flow of 40-100ml/min Hydrogen, the constant in-situ reducing of keeping temperature is reacted -1 hour 30 minutes, obtains Nanoscale Iron；
(22) carbon source is passed through with 60-100ml/min flows again and ensures carbon source concentration, promote the carrying out of reaction, using drum Bubble method, carbon-source gas bring steam into, and keeping temperature is constant, react 6-10 hours, and high-purity spiral carbon nanotubes are obtained.
Using having the beneficial effect that for above-mentioned further technical scheme：
Further, the carbon source is acetylene gas or methane gas or ethylene gas.
It is a further object to provide high-purity spiral shell that above-mentioned high-purity spiral carbon nanotubes preparation method is prepared Rotation CNT, the purity of high-purity spiral carbon nanotubes is more than 99%, and caliber is 80-120nm, and yield is up to 8078g/g and urges Agent (far above the peak 1000-7000g/g catalyst of document report), the parameter such as product diameter, spiral shell footpath, pitch is uniform, Pattern is complete, with huge application value.
The spiral carbon nanotubes that the present invention is prepared have potential application value, except with the low of common straight fiber Outside the excellent properties such as density, high specific strength, heat resistance, electric heating conductibility, chemical stability, its special spiral makes material Good combination with typical chirality, excellent super-elasticity and with matrix, is expected to be used for high-performance enhancing composite wood The micromechanical component field such as material, the storage of electromagnet wave absorbent, gas, biosynthesis catalyst, miniature inductance, Microspring； The functionalized application that helical structure material is brought by its spiral characteristic, will be space material, new energy materialses, sensor etc. There is great application prospect in field.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope photo of high-purity spiral carbon nanotubes prepared by the embodiment of the present invention 1.
Fig. 2 is the field emission scanning electron microscope photo of high-purity spiral carbon nanotubes prepared by the embodiment of the present invention 2.
Fig. 3 is the field emission scanning electron microscope photo of high-purity spiral carbon nanotubes prepared by the embodiment of the present invention 3.
Fig. 4 is the field emission scanning electron microscope photo of high-purity spiral carbon nanotubes prepared by the embodiment of the present invention 4.
Fig. 5 is the field emission scanning electron microscope photo of high-purity spiral carbon nanotubes prepared by the embodiment of the present invention 5.
Fig. 6 is the field emission scanning electron microscope photo of spiral carbon nanotubes prepared by comparative example of the present invention 1.
Specific embodiment
Principle of the invention and feature are described below, example is served only for explaining the present invention, is not intended to limit Determine the scope of the present invention.
Embodiment 1：
Prepare alpha-crystal form nano iron oxide catalyst precursor：By Iron dichloride tetrahydrate and Rochelle salt point The solution that concentration is 0.2mol/L is not configured to, two kinds of solution of same volume are taken, and is hydrated chlorine by four while stirring at room temperature Change ferrous iron solution to be slowly dropped in Rochelle salt solution, then obtained after standing, filtering, washing, dry, grinding Ferrous tartrate powder, then with citric acid with the amount ratio of material be 1:1 is mixed in 100mL absolute ethyl alcohols and forms suspension, in Stirring forms blackish green gel in 6 hours under the conditions of 80 DEG C, after drying at 100 DEG C, is placed in tube furnace, under air atmosphere in 400 DEG C are calcined 2 hours, can be fully oxidized, and alpha-crystal form nano iron oxide catalyst precursor powder is obtained after grinding.
Prepare high-purity spiral carbon nanotubes：Take appropriate alpha-crystal form nano iron oxide catalyst precursor powder and be placed in quartz boat Middle part, is placed horizontally in tube furnace, with argon gas as carrier gas, its flow velocity is set for 100ml/min, using the intensification of 10 DEG C/min Speed makes tube furnace be warming up to 500 DEG C, and stabilization more than 10min；After closing carrier gas, with H2To go back Primordial Qi, setting its flow velocity is 60ml/min, the constant reduction 30min of keeping temperature, to guarantee for alpha-crystal form nano-sized iron oxide to be reduced to Nanoscale Iron；Close H2 Afterwards, with C2H2It is carbon source, flow velocity is 80ml/min, is passed to device (device and calcium chloride jar structure class equipped with water Like), reacting furnace into is brought steam by Bubbling method, the introduction volume of steam accounts for the 1 × 10 of carbon source gas volumetric-5, in keeping temperature Reacted 6 hours in the case of constant, high-purity spiral carbon nanotubes are obtained, the purity of the spiral carbon nanotubes is 99.1%, caliber It is 80nm, its scanning electron microscope (SEM) photograph is as shown in Figure 1.
Embodiment 2：
Prepare alpha-crystal form nano iron oxide catalyst precursor：By Iron dichloride tetrahydrate and Rochelle salt point The solution that concentration is 0.1mol/L is not configured to, two kinds of solution of same volume are taken, and is hydrated chlorine by four while stirring at room temperature Change ferrous iron solution to be slowly dropped in Rochelle salt solution, then obtained after standing, filtering, washing, dry, grinding Ferrous tartrate powder, then with citric acid with the amount ratio of material be 1:1.5 are mixed in 100mL absolute ethyl alcohols and form suspension, Stirring forms blackish green gel in 8 hours under the conditions of 60 DEG C, after drying at 90 DEG C, is placed in tube furnace, under air atmosphere in 600 DEG C are calcined 1 hour, can be fully oxidized, and alpha-crystal form nano iron oxide catalyst precursor powder is obtained after grinding.
Prepare high-purity spiral carbon nanotubes：Take appropriate alpha-crystal form nano iron oxide catalyst precursor powder and be placed in quartz boat Middle part, is placed horizontally in tube furnace, with argon gas as carrier gas, its flow velocity is set for 100ml/min, using the intensification of 8 DEG C/min Speed makes tube furnace be warming up to 400 DEG C, and stabilization more than 10min；After closing carrier gas, with H2To go back Primordial Qi, setting its flow velocity is 40ml/min, the constant reduction of keeping temperature 1 hour, to guarantee for alpha-crystal form nano-sized iron oxide to be reduced to Nanoscale Iron；Close H2 Afterwards, with methane gas as carbon source, flow velocity is 100ml/min, is passed to device (device and calcium chloride jar knot equipped with water Structure is similar to), reacting furnace into is brought steam by Bubbling method, the introduction volume of steam accounts for the 1.3 × 10 of carbon source gas volumetric-5, protecting Hold it is temperature-resistant in the case of react 8 hours, high-purity spiral carbon nanotubes are obtained, the purity of the spiral carbon nanotubes is 99.7%, caliber is 100nm, and its scanning electron microscope (SEM) photograph is as shown in Figure 2.
Embodiment 3：
Prepare alpha-crystal form nano iron oxide catalyst precursor：By Iron dichloride tetrahydrate and Rochelle salt point The solution that concentration is 0.3mol/L is not configured to, two kinds of solution of same volume are taken, and is hydrated chlorine by four while stirring at room temperature Change ferrous iron solution to be slowly dropped in Rochelle salt solution, then obtained after standing, filtering, washing, dry, grinding Ferrous tartrate powder, then with citric acid with the amount ratio of material be 1:2 are mixed in 100mL absolute ethyl alcohols and form suspension, in Stirring forms blackish green gel in 3 hours under the conditions of 100 DEG C, after drying at 95 DEG C, is placed in tube furnace, under air atmosphere in 500 DEG C are calcined 3 hours, can be fully oxidized, and alpha-crystal form nano iron oxide catalyst precursor powder is obtained after grinding.
Prepare high-purity spiral carbon nanotubes：Take appropriate alpha-crystal form nano iron oxide catalyst precursor powder and be placed in quartz boat Middle part, is placed horizontally in tube furnace, with argon gas as carrier gas, its flow velocity is set for 100ml/min, using the intensification of 10 DEG C/min Speed makes tube furnace be warming up to 450 DEG C, and stabilization more than 10min；After closing carrier gas, with H2To go back Primordial Qi, setting its flow velocity is 100ml/min, the constant reduction of keeping temperature 40 minutes, to guarantee for alpha-crystal form nano-sized iron oxide to be reduced to Nanoscale Iron；Close H2 Afterwards, with methane gas as carbon source, flow velocity is 60ml/min, is passed to device (device and calcium chloride jar knot equipped with water Structure is similar to), reacting furnace into is brought steam by Bubbling method, the introduction volume of steam accounts for the 1.2 × 10 of carbon source gas volumetric-5, protecting Hold it is temperature-resistant in the case of react 10 hours, high-purity spiral carbon nanotubes are obtained, the purity of the spiral carbon nanotubes is 99.4%, caliber is 100nm, and its scanning electron microscope (SEM) photograph is as shown in Figure 3.
Embodiment 4：
Prepare alpha-crystal form nano iron oxide catalyst precursor：By Iron dichloride tetrahydrate and Rochelle salt point The solution that concentration is 0.2mol/L is not configured to, two kinds of solution of same volume is taken, at room temperature while stirring by frerrous chloride Solution is slowly dropped in potassium sodium tartrate solution, then obtains ferrous tartrate powder after standing, filtering, washing, dry, grinding End, then with citric acid with the amount ratio of material be 1:1.5 are mixed in 100mL absolute ethyl alcohols and form suspension, under the conditions of 78 DEG C Stirring 8h forms blackish green gel, after being dried at 100 DEG C, is placed in tube furnace, the lower 500 DEG C of roastings 2h of air atmosphere, makes it Can be fully oxidized, alpha-crystal form nano iron oxide catalyst precursor powder is obtained after grinding.
Prepare high-purity spiral carbon nanotubes：Appropriate alpha-crystal form nano iron oxide catalyst precursor powder is taken in quartz boat Portion, is placed horizontally in tube furnace, with Ar as carrier gas, its flow velocity is set for 120mL/min, using the heating rate of 8 DEG C/min Tube furnace is set to be warming up to 475 DEG C, and stabilization more than 10min；After closing carrier gas, with H2To go back Primordial Qi, its flow velocity is set for 80mL/ Min, the constant reduction 60min of keeping temperature, to guarantee for alpha-crystal form nano-sized iron oxide powder to be reduced to nanometer Fe；Close H2Afterwards, With C2H2It is carbon source, flow velocity is 100mL/min, the container (device is similar with calcium chloride jar) equipped with water is passed to, by drum Bubble method brings steam into reacting furnace, and the introduction volume of steam accounts for the 1.2 × 10 of carbon source gas volumetric-5, in the feelings that keeping temperature is constant Reacted 6 hours under condition, prepare high-purity spiral carbon nanotubes, the purity of the spiral carbon nanotubes is 99%, and caliber is 90nm, Its scanning electron microscope (SEM) photograph is as shown in Figure 4.
Embodiment 5：
Prepare alpha-crystal form nano iron oxide catalyst precursor：By Iron dichloride tetrahydrate and Rochelle salt point The solution that concentration is 0.2mol/L is not configured to, two kinds of solution of same volume is taken, at room temperature while stirring by frerrous chloride Solution is slowly dropped in potassium sodium tartrate solution, then obtains ferrous tartrate powder after standing, filtering, washing, dry, grinding End, then with citric acid with the amount ratio of material be 1:2 are mixed in 100ml absolute ethyl alcohols and form suspension, are stirred under the conditions of 90 DEG C Mix 4 hours and form blackish green gel, after being dried at 100 DEG C, be placed in tube furnace, the lower 500 DEG C of roastings 2h of air atmosphere makes it Can be fully oxidized, alpha-crystal form nano iron oxide catalyst precursor powder is obtained after grinding.
Appropriate alpha-crystal form nano iron oxide catalyst precursor powder is taken in quartz boat middle part, is placed horizontally in tube furnace, With Ar as carrier gas, its flow velocity is set for 100mL/min, tube furnace is warming up to 450 DEG C using the heating rate of 10 DEG C/min, and Stabilization more than 10min；After closing carrier gas, with H2To go back Primordial Qi, its flow velocity is set for 100mL/min, the constant reduction of keeping temperature 40min, to guarantee for alpha-crystal form nano-sized iron oxide to be reduced to Nanoscale Iron；Close H2Afterwards, with C2H2It is carbon source, flow velocity is 80mL/ Min, is passed to the container (device is similar with calcium chloride jar) equipped with water, and steam is brought into reacting furnace, water by Bubbling method The introduction volume of vapour accounts for the 1.0 × 10 of carbon source gas volumetric-5, reacted 6 hours in the case where keeping temperature is constant, high-purity spiral shell is obtained Rotation CNT, the purity of the spiral carbon nanotubes is 99.1%, and caliber is 95nm, and its scanning electron microscope (SEM) photograph is as shown in Figure 5.
Comparative example：
Iron dichloride tetrahydrate and Rochelle salt are each configured to the solution that concentration is 0.1mol/L, phase is taken , be slowly dropped to solution of ferrous chloride in potassium sodium tartrate solution while stirring at room temperature by two kinds of solution of same volume, and Stand afterwards, filtering, washing, dry, obtain ferrous tartrate powder after grinding, then with citric acid with the amount ratio of material be 1:1 mixes Together in suspension is formed in 100mL absolute ethyl alcohols, 3h is stirred under the conditions of 100 DEG C and forms blackish green gel, dried at 90 DEG C Afterwards, it is placed in tube furnace, air atmosphere lower 400 DEG C of roastings 1h obtains brick-red nano-sized iron oxide powder after grinding.
Appropriate brick-red nano-sized iron oxide powder is taken in quartz boat middle part, is placed horizontally in tube furnace, be load with argon gas Gas, sets its flow velocity for 100mL/min, tube furnace is warming up to 400 using the heating rate of 8 DEG C/min brick-red nano oxidized Iron powder, and stabilization more than 10min；After closing carrier gas, with H2To go back Primordial Qi, its flow velocity is set for 40mL/min, keeping temperature Constant reduction 30min；Close H2Afterwards, with C2H2It is carbon source, flow velocity is 60mL/min, and 5 are reacted in the case where keeping temperature is constant Hour, spiral carbon nanotubes are prepared, its scanning electron microscope (SEM) photograph is as shown in Figure 6.
High-purity spiral carbon nanotubes that the embodiment 1- embodiments 5 prepared using the inventive method are prepared with The structure of the spiral carbon nanotubes prepared using the method for comparative example is contrasted, it can be seen that use the inventive method system The standby spiral carbon nanotubes for obtaining have different, specific data with the spiral carbon nanotubes prepared using comparative example method Table 1 below.
Table 1
As can be seen from the above table, the purity and yield of the spiral carbon nanotubes for being prepared using the inventive method are all remote Much larger than what is prepared using the method for comparative example, therefore, with huge application prospect.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method of high-purity spiral carbon nanotubes, it is characterized in that, including：
(1) alpha-crystal form nano iron oxide catalyst precursor is prepared：Alpha-crystal form is prepared using preformed precipitate combination sol-gel process Nano iron oxide catalyst precursor；
(2) high-purity spiral carbon nanotubes are prepared：The alpha-crystal form nano iron oxide catalyst precursor is placed in tube furnace, is adopted It is allowed to be reduced to a nanometer iron catalyst with local reduction way, while introducing carbon source and steam as catalysis regulation auxiliary agent, is incubated 6- 10 hours, obtain high-purity spiral carbon nanotubes.
2. the preparation method of high-purity spiral carbon nanotubes according to claim 1, it is characterized in that, in step (2), using drum Bubble method, carbon-source gas bring steam into, and the introduction volume of steam is the 1 × 10 of carbon source gas volumetric-5~1.3 × 10-5。
3. the preparation method of high-purity spiral carbon nanotubes according to claim 1 and 2, it is characterized in that, step (1) it is specific Method is：
(11) Iron dichloride tetrahydrate and Rochelle salt are each configured to concentration identical solution, take same volume Solution, at room temperature, Iron dichloride tetrahydrate solution is added drop-wise in Rochelle salt solution, stand, grinding, obtain To ferrous tartrate powder；
(12) ferrous tartrate powder and citric acid are mixed in absolute ethyl alcohol and form suspension, in stirring 3- at 60-100 DEG C Form blackish green gel within 8 hours, after being dried at 90-100 DEG C, be placed in tube furnace, under air atmosphere, in 400-600 DEG C Roasting 1-3 hours, grinding, obtains alpha-crystal form nano iron oxide catalyst precursor.
4. the preparation method of high-purity spiral carbon nanotubes according to claim 3, it is characterized in that, in step (11), four water The concentration for closing frerrous chloride and Rochelle salt is 0.1-0.3mol/l.
5. the preparation method of high-purity spiral carbon nanotubes according to claim 3, it is characterized in that, in step (12), winestone Sour ferrous iron powder is 1 with the amount ratio of the material of citric acid：1-1：2.
6. the preparation method of high-purity spiral carbon nanotubes according to claim 5, it is characterized in that, in step (12), winestone Sour ferrous iron powder is 1 with the amount ratio of the material of citric acid：1.5.
7. the preparation method of high-purity spiral carbon nanotubes according to claim 3, it is characterized in that, in step (12), by wine Stone acid ferrous iron powder and citric acid form suspension in being mixed in absolute ethyl alcohol, form within 3-8 hours blackish green in being stirred at 70-90 DEG C Color gel.
8. the preparation method of high-purity spiral carbon nanotubes according to claim 1 and 2, it is characterized in that, step (2) it is specific Method is：
(21) alpha-crystal form nano iron oxide catalyst precursor is placed in tube furnace, is passed through with the flow of 100-120ml/min lazy 400-500 DEG C is heated to after property gas and keeps more than 10min, be then shut off carrier gas, be passed through with the flow of 40-100ml/min Hydrogen, the constant in-situ reducing of keeping temperature is reacted -1 hour 30 minutes, obtains Nanoscale Iron；
(22) carbon source is passed through with the flow of 60-100ml/min again, using Bubbling method, carbon-source gas bring steam into, keeping temperature It is constant, react 6-10 hours, high-purity spiral carbon nanotubes are obtained.
9. the preparation method of high-purity spiral carbon nanotubes according to claim 6, it is characterized in that, the carbon source is acetylene gas Body or methane gas or ethylene gas.
10. the high-purity spiral shell for being prepared using the preparation method of the high-purity spiral carbon nanotubes described in claim any one of 1-9 Rotation CNT, its purity is more than 99%, and caliber is 80-120nm.
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CN112421988A (en) * 2020-11-12 2021-02-26 福州大学 Spiral magnetic micron motor and preparation method thereof
CN112421988B (en) * 2020-11-12 2022-04-12 福州大学 Spiral magnetic micron motor and preparation method thereof
CN113233443A (en) * 2021-04-22 2021-08-10 电子科技大学 Preparation method of fluorinated spiral carbon nanotube and application of fluorinated spiral carbon nanotube in lithium primary battery

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