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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- carbon nanotubes
- purity
- preparation
- spiral carbon
- alpha
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 67
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 230000033228 biological regulation Effects 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 17
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- OHZCFWMJMWFNFP-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;iron(2+) Chemical compound [Fe+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O OHZCFWMJMWFNFP-ZVGUSBNCSA-L 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 13
- 229940057006 ferrous tartrate Drugs 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710119447.4A CN106829926B (en) | 2017-03-02 | 2017-03-02 | A kind of high-purity spiral carbon nanotubes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710119447.4A CN106829926B (en) | 2017-03-02 | 2017-03-02 | A kind of high-purity spiral carbon nanotubes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106829926A true CN106829926A (en) | 2017-06-13 |
| CN106829926B CN106829926B (en) | 2019-03-05 |
Family
ID=59138846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710119447.4A Active CN106829926B (en) | 2017-03-02 | 2017-03-02 | A kind of high-purity spiral carbon nanotubes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106829926B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110244061A (en) * | 2019-07-17 | 2019-09-17 | 福建师范大学 | A kind of zearalenone multi channel signals detection immunoassay method based on spiral carbon nanotubes photo-thermal effect |
| CN112421988A (en) * | 2020-11-12 | 2021-02-26 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663411A (en) * | 2013-12-03 | 2014-03-26 | 贵州大学 | High-yield synthesis method of double-helix carbon nanotube |
| CN104148670A (en) * | 2014-07-16 | 2014-11-19 | 电子科技大学 | Method for preparing porous iron powder on basis of thermal composition process |
| CN104760943A (en) * | 2015-02-10 | 2015-07-08 | 山东玉皇新能源科技有限公司 | Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition |
-
2017
- 2017-03-02 CN CN201710119447.4A patent/CN106829926B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663411A (en) * | 2013-12-03 | 2014-03-26 | 贵州大学 | High-yield synthesis method of double-helix carbon nanotube |
| CN104148670A (en) * | 2014-07-16 | 2014-11-19 | 电子科技大学 | Method for preparing porous iron powder on basis of thermal composition process |
| CN104760943A (en) * | 2015-02-10 | 2015-07-08 | 山东玉皇新能源科技有限公司 | Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition |
Non-Patent Citations (1)
| Title |
|---|
| 张洋 等: "螺旋碳纳米管的制备、表征及性能", 《微纳电子技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110244061A (en) * | 2019-07-17 | 2019-09-17 | 福建师范大学 | A kind of zearalenone multi channel signals detection immunoassay method based on spiral carbon nanotubes photo-thermal effect |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106829926B (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101314483B (en) | Method for synthesizing alpha-Fe2O3 nano-particle with controllable shape size | |
| CN102786097A (en) | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles | |
| CN104495950A (en) | Preparation method of carbon encapsulated magnetic C/Fe3O4 nano composite material and application thereof | |
| CN106829926B (en) | A kind of high-purity spiral carbon nanotubes and preparation method thereof | |
| CN104292236A (en) | Preparation method of three-dimensional porous g-C3N4 material | |
| CN103449403A (en) | Method for manufacturing nitrogen-doped multi-wall carbon nano tube | |
| CN106430327A (en) | Porous sea-urchin-shaped Fe3O4@C composite material and preparation method thereof | |
| CN104117339A (en) | Preparation method and application method of adsorbent for adsorbing dye | |
| CN107572509A (en) | A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof | |
| CN102897805B (en) | Preparation method of one-dimensional porous magnesium oxide nano wire | |
| CN111204818A (en) | Method for preparing magnetic mesoporous silica particles by using pollen as template | |
| CN105499561A (en) | Preparing method of magnetic carbon nano tubes | |
| CN102976344A (en) | Preparation method of zinc silicate nanometer material | |
| CN108405879A (en) | A kind of preparation method of nano zero valence iron@meso pore silicon oxide materials | |
| CN105110381A (en) | Method for preparing nanopore alpha-Fe2O3 | |
| CN103739020B (en) | Method for preparing porous nano ferroferric oxide | |
| CN106215968B (en) | A kind of carbon coating CuO composite material and preparation methods of doping nitrogen | |
| CN108002382A (en) | N doping porous carbon loads Fe2O3The preparation method of composite material | |
| Guo et al. | MoO3-templated synthesis of TiO2@ C-Ni microtubes for efficient catalysis and protein adsorption | |
| WO2021238083A1 (en) | Method for preparing silicate/carbon composite by using attapulgite, and application of material | |
| CN104415773B (en) | Platinum Nanoparticles of high loadingses and preparation method thereof | |
| CN110171811B (en) | Preparation method of thermostable copper phosphate crystal nano material | |
| CN112108137A (en) | Method for uniformly preparing attapulgite-titanium dioxide composite material | |
| Wang et al. | Bio-inspired synthesis of TiO2 hollow nanospheres in agarose gels | |
| CN103771533A (en) | Preparation method of alpha-Fe2O3 microsphere with flower-like hierarchical structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |