CN104291313A - Preparation method of nano carbon fiber - Google Patents
Preparation method of nano carbon fiber Download PDFInfo
- Publication number
- CN104291313A CN104291313A CN201410498805.3A CN201410498805A CN104291313A CN 104291313 A CN104291313 A CN 104291313A CN 201410498805 A CN201410498805 A CN 201410498805A CN 104291313 A CN104291313 A CN 104291313A
- Authority
- CN
- China
- Prior art keywords
- preparation
- carbon nano
- nano fiber
- tic
- carbon
- 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.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920000049 Carbon (fiber) Polymers 0.000 title abstract description 21
- 239000004917 carbon fiber Substances 0.000 title abstract description 21
- 229910021392 nanocarbon Inorganic materials 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000002134 carbon nanofiber Substances 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 36
- 230000012010 growth Effects 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 26
- 239000002105 nanoparticle Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 13
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002245 particle Substances 0.000 description 22
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- -1 pyrolysis method Chemical compound 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparation method of a nano carbon fiber, particularly a preparation method of a nano carbon fiber by a chemical vapor deposition process by using TiC nanoparticles as a catalyst. The method comprises the following steps: 1. preparing TiC; and 2. catalytically growing the nano carbon fiber by a matrix process, wherein the catalyst is a titanium-containing compound. The preparation process is simple and easy to operate, and simple and accessible in raw materials; and the prepared nano carbon fiber has the characteristic of symmetrically growing by using the catalyst as the center.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano fiber, being specifically related to a kind of TiC of employing nanoparticle is that catalyzer utilizes chemical Vapor deposition process to prepare the preparation method of carbon nano fiber.
Background technology
Carbon nano fiber is except there being the characteristic of other gas-phase growth of carbon fibre, beyond many characteristics such as the specific modulus that such as density is low, specific tenacity is high, electric conductivity is high and higher, also there is many advantages such as considerably less defects count, larger specific surface area, good conductivity, compact structure, be therefore widely used in the aspects such as the high sorbent material of catalyzer and catalyst support material, separating agent, the strongthener of structure, lithium ion electrical double layer capacitor electrodes, the anode material of secondary cell, field emission electron material and adsorption efficiency.
Through constantly exploring, people have grasped many methods obtaining carbon nano fiber, such as pyrolysis method, chemical Vapor deposition process, solid-phase synthesis etc.Wherein chemical vapour deposition (CVD) method is taking hydrocarbon as carbon source, under the active temperature of catalyzer (generally between 300 C-1000 C), make hydrocarbon molecule in the less metallic catalyst surfaces thermolysis of diameter to prepare the method for carbon nano fiber.The existence form different according to catalyzer and Adding Way, can be divided into following several by chemical Vapor deposition process: matrix method, spraying process and gas phase flowing catalysis method.
Wherein matrix method be by nano-catalyst particles uniformly dispersing pottery or graphite matrix on (catalyzer mostly is the transition metal such as Fe, Co, Ni), and pass into hydrocarbon gas at moderate temperatures, make it to decompose under catalyst action and separate out carbon nano fiber on its surface.The carbon fiber purity adopting the catalysis of matrix method to prepare is higher, but it is more difficult to prepare superfine catalyst particle early stage, if catalyst particle size is comparatively large, then the carbon nano fiber of the thin diameter of difficult preparation, carbon fiber is difficult to growth even.In addition, carbon nano fiber only grows on the part of matrix sprayed or be coated with granules of catalyst, and thus the output of carbon fiber is lower, generally can only single growth, is difficult to realize suitability for industrialized production.
Spraying process refers to and utilizes liquid phase organism to disperse or dissolve catalyzer, then sprays in pyroreaction room by the mixed solution being dispersed with catalyzer, grows carbon nanofiber by the catalyst disperseed in liquid phase particulate.Owing to can realize spraying into catalyzer continuously in reaction system, therefore the continuous volume production of industrialization is likely realized, its shortcoming is, catalyzer disperses often uneven in dispersion medium, the two ratio is wayward, and sprays because liquid-phase particle skewness causes granules of catalyst skewness in process, and catalyzer is difficult to reach nanometer scale, therefore the carbon fiber that the method obtains is not often nanometer scale, and normal association has carbon black.
Gas phase flowing catalysis method is by heatable catalyst presoma, the precursor of gaseous state is made jointly to enter reaction chamber with hydrocarbon gas, the decomposition of catalyst precursor and the decomposition of hydrocarbon gas is completed respectively in differing temps district, after catalyst precursor decomposes, atoms metal is wherein assembled gradually, become nanoscale metal particles, the carbon atom that metallic particles pyrolysis hydro carbons produces is piled into carbon fiber at catalyst surface.Because catalyst precursor is with gaseous state and hydro carbons Homogeneous phase mixing, and the amount of catalyzer accurately can control by controlling the amount of precursor, and therefore, the catalyzer obtained and carbon fiber are all at nanoscale and reaction is very fast, and output is high, and easily realizes continuous seepage.
Chinese invention patent CN 102502591 B just adopts gas phase flowing catalysis method improve the productive rate of carbon fiber and reduce cost, the preparation method of its carbon nano fiber provided, comprises the following steps: one, by being heated in the tubulose confined reaction chamber of vertically setting up>=700 to≤1200 DEG C; Two, simultaneously from top insufflation gas 1 and the catalyzer of body of heater, pass into gas 2 from the below of body of heater, the time is 1-120min, obtains carbon nano fiber; Catalyst flow is solid 1-100g/s m
3, or liquid or gas 1-100g/min m
3for Compound I, Compound II per and compound III, Compound I is more than one in the compound of the compound of Fe, the compound of Co and Ni, Compound II per is the compound containing more than one metallic elements in the periodic table of chemical element IA, IIA, IIIA, IVA, and compound III is the compound of more than one elements except Fe, Co and Ni in the periodic table of chemical element IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII; The atomic molar of the element of the element of Compound I and Compound II per and compound III is than being 0.9-5:1; Gas 1 is the mixed gas of carbon-source gas and carrier gas, and the volume ratio of carbon-source gas and carrier is>=2 to≤3:1, and flow is 1-100mL/s m
3, carbon-source gas is more than one of methane, ethane, propane, butylene, toluene, iso-butylene, divinyl, dimethylbenzene, hexanaphthene, formaldehyde, acetaldehyde, acetone and benzene, Sweet natural gas, liquefied petroleum gas (LPG), volatile oil or kerosene, and carrier gas is nitrogen or argon gas; Gas 2 is nitrogen or hydrogen, and flow is 1-100mL/s m
3.
But there is following defect in above-mentioned patented technology: the catalyzer 1, adopted is for being Compound I, Compound II per and compound III, Compound I, and catalyst type is various, some catalyzer such as compound containing VIII element is difficult to obtain, and cost is higher; 2, the flowing catalysis method that above-mentioned patented technology adopts needs top insufflation gas 1 from body of heater and catalyzer, gas 2 is passed into from the below of body of heater, and each gas or catalyzer are made up of many kinds of substance, flow for catalyzer and gas also will be controlled, complicated operation, add the difficulty of preparation, be unfavorable for improving preparation efficiency; Although 3, above-mentioned patented technology improves productive rate, but just because of adding various catalyzer in the process preparing carbon nano fiber, passing into multiple gases, increase the risk containing impurity in obtained carbon nano fiber, be unfavorable for the carbon nano fiber generating form rule simultaneously.
Yet there are no in prior art and adopt TiC to be the report of catalyzer by chemical Vapor deposition process catalytic growth carbon nano fiber separately.
Summary of the invention
for solving the problem, the object of the present invention is to provide a kind of preparation method of carbon nano fiber, its adopt TiC be catalyzer by chemical Vapor deposition process catalytic growth carbon nano fiber, have that preparation process is simple to operation, raw material is simple and easy to get, a feature of carbon nano fiber symmetric growth centered by catalyzer of preparation.
Technical scheme of the present invention is: a kind of preparation method of carbon nano fiber, and its catalyzer adopted is the compound containing titanium elements.
Optimize, its catalyzer adopted is TiC.
Optimize, the vapour deposition temperature that it adopts is 430-470 DEG C.
Optimize, the vapour deposition temperature that it adopts is 450 DEG C.
Optimize, it comprises the steps: step one, preparation TiC; Step 2, employing matrix method catalytic growth carbon nano fiber.
Optimizing, adopt that titanium plate is anode, graphite rod is negative electrode when step one prepares TiC, is argon gas and methane by the gas passed into after airtight for reaction chamber vacuumizing.
Optimize, the ratio of the dividing potential drop of argon gas and methane is 1:1.
Optimizing, during step 2 catalytic growth carbon nano fiber, take acetylene as carbon source.
Beneficial effect of the present invention is:
1, the catalyzer that the present invention adopts is the compound containing titanium elements, and catalyst type is single, and raw material is easy to get, and the carbon nano fiber of obtained symmetric growth centered by catalyzer.
2, the present invention adopts matrix method, only needs the catalyzer of solid to be dispersed in uniformly on matrix, need not be converted into the moving phase such as gas phase or liquid phase and add, need not control flow, add simple to operate, reduce the difficulty of preparation, is conducive to improving preparation efficiency.
3, just because of adding single catalyzer in the process preparing carbon nano fiber, passing into a kind of gas of acetylene, improve the purity of obtained carbon nano fiber, be conducive to the carbon nano fiber generating form rule simultaneously.
4, the present invention is by the consistent TiC nanocatalyst of preparation high purity, regular shape, diameter, has obtained uniform diameter, carbon nano fiber that fiber growth is good further.
5, the present invention urges the key elements such as vapour deposition temperature and carbon source by adjustment, and obtained carbon nano fiber diameter is suitable with catalyst particle size, thus can be controlled the diameter of carbon nano fiber by the diameter controlling catalyzer.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of TiC prepared by embodiment 1;
Fig. 2 is the XRD spectra of TiC prepared by comparative example 1;
Fig. 3 is the XRD spectra of TiC prepared by comparative example 2;
Fig. 4 is the stereoscan photograph of TiC nanoparticle prepared by embodiment 1;
Fig. 5 is the perspective electromicroscopic photograph of the position same with Fig. 4 of TiC nanoparticle prepared by embodiment 1;
Fig. 6 is the high-resolution electron microscopy photo of TiC nanoparticle prepared by embodiment 1;
Fig. 7 is the enlarged view of the high-resolution electron microscopy photo of TiC nanoparticle prepared by embodiment 1;
Fig. 8 is the stereoscan photograph of carbon nano fiber prepared by embodiment 2;
Fig. 9 is the stereoscan photograph of carbon nano fiber prepared by comparative example 3;
Figure 10 is the stereoscan photograph of carbon nano fiber prepared by comparative example 4;
Figure 11 is the high-resolution-ration transmission electric-lens photo of carbon nano fiber prepared by embodiment 2;
Figure 12 is the enlarged view of the high resolution perspective electromicroscopic photograph of carbon nano fiber prepared by embodiment 2.
Embodiment
The present invention is illustrated below in conjunction with drawings and embodiments.
Embodiment 1
The present embodiment TiC used is prepared by arc plasma process.Specifically with titanium plate be anode, graphite rod for negative electrode, both adjustments spacing to about 2 mm, is fixed in device of arc, rotates knob and drives negative electrode away from anode, to avoid power initiation instantaneous short circuit; Enclosed reaction chamber, vacuumizes 30 min with mechanical pump, reaches below 1Pa to pressure, and close mechanical pump, in reaction chamber, pass into argon gas and methane, the ratio of the dividing potential drop of the two is 1:1, and after keeping ventilation, pressure is less than 5 Pa, closed reaction chamber; Open the cooling water switch of reaction chamber, regulate electrical control cubicles voltage to be 45 V, open electrical control cubicles, rotate knob and drive movable cathode, make to draw electric arc between anode and cathode, and keep arc stability by rotating negative electrode; React powered-down after 2 min, continue logical water coolant and cool completely to equipment; Collect the powder of reaction chamber wall with hairbrush, cross 400 mesh sieves, after removing the metallic particles wherein mixed, obtain product TiC.
Comparative example 1
With the difference of embodiment 1, this comparative example is that by the gas passed into after airtight for reaction chamber vacuumizing be hydrogen.
Comparative example 2
With the difference of embodiment 1, this comparative example is that by the gas passed into after airtight for reaction chamber vacuumizing be hydrogen and argon gas, the ratio of the dividing potential drop of the two is 1:1.
Embodiment 2
The TiC that the present embodiment utilizes embodiment 1 to prepare, adopt matrix method catalytic growth carbon nano fiber, concrete steps are as follows:
Get appropriate TiC nanoparticle, be sprinkled upon in porcelain boat with standard sieve paving, TiC nanoparticle is spread bottom porcelain boat as far as possible uniformly and spills one deck, porcelain boat is placed in tube furnace silica tube, makes porcelain boat be positioned at silica tube mid-way, closed quartz tube, vacuumize 10 min, pass into acetylene to 50 kPa, again vacuumize, with the foreign gas in clean pipe; With the ramp to 450 DEG C of 10 DEG C/min, pass into acetylene and equal normal atmosphere to overpressure, again vacuumize in pipe after isothermal reaction 30 min, system to room temperature, takes out sample at vacuum Temperature fall.
Comparative example 3
With the difference of embodiment 2, this comparative example is that the vapour deposition temperature that it adopts is 400 DEG C.
Comparative example 4
With the difference of embodiment 2, this comparative example is that the vapour deposition temperature that it adopts is 500 DEG C.
The TiC nanoparticle that present embodiment adopts X-ray diffraction spectrogram (XRD), scanning electronic microscope (band power spectrum) (SEM-EDS), high resolution transmission electron microscopy (HR-TEM) comparative study embodiment 1 and comparative example 1-2 to prepare; Adopt carbon nano fiber prepared by scanning electronic microscope (band power spectrum) (SEM-EDS) and high resolution transmission electron microscopy (HR-TEM) comparative study embodiment 2 and comparative example 3-4.
Table 1
| ? | embodiment 1 | comparative example 1 | comparative example 2 |
| atmosphere | argon gas and methane | hydrogen | hydrogen and argon gas |
| xRD spectra (accompanying drawing 1-3) | tiC well-crystallized, purity are higher | tiC well-crystallized, but be mixed with more Ti impurity | be mixed with a large amount of titanium simple substance and unformed impurity |
| sEM-EDS(accompanying drawing 4-5) | tiC particle shape rule, size distribution is comparatively even | --- | --- |
| hR-TEM(accompanying drawing 6-7) | crystal face complete display, atomic arrangement is neat, and well-crystallized is face-centred cubic TiC. | —— | —— |
First can be learnt by the contrast of accompanying drawing 1-3: in Fig. 1, can see that embodiment 1 spectrogram baseline is comparatively steady, several stronger diffraction peak is all clear and sharp keen, corresponding with titanium carbide (111) in PDF 65-0971, (200), (220) face respectively the diffraction peaks of 31 °, 42 °, 60 °, illustrate that product is the face-centered cubic TiC of well-crystallized, and near 41 °, only have very faint Ti (101) face diffraction peak, illustrate that the titanium foreign matter content being mixed into product is very low, purity is higher.Can find out in Fig. 2 that comparative example 1 is at H
2the X-ray diffraction spectrogram of the TiC nanoparticle that arc plasma is obtained by reacting is carried out under atmosphere, spectrogram has very by force and very sharp keen diffraction peak near 35 °, 38 °, 41 °, these diffraction peaks are corresponding with (100), (002) of hexagonal system Ti simple substance in standard diffraction collection of illustrative plates PDF 65-3362, (101) face respectively, and the diffraction peak of TiC is also clear and obvious, this illustrates obtained TiC nanoparticle well-crystallized, but is wherein mixed with more Ti impurity.Fig. 3 is with H
2be atmosphere with Ar mixed gas, by the XRD spectra of the standby TiC of arc plasma legal system, analysis of spectra can be seen, the diffraction peak in obvious titanium (101) face is had near 41 °, and spectrogram baseline is very not steady between 10 ° to 30 °, illustrate in product and be mixed with more amorphous substance, can think that the TiC nanoparticle purity obtained is not high in conjunction with XRD spectra, be mixed with a large amount of titanium simple substance and unformed impurity.
Therefore, as seen from the above comparison, adopt that titanium plate is anode, graphite rod is negative electrode during preparation TiC, the gas passed into after airtight for reaction chamber vacuumizing is adopted argon gas and methane, the TiC nanoparticle well-crystallized of preparation, purity are higher, due to other atmospheres.
Further by the scanning transmission electron microscope photo of the TiC nanoparticle of accompanying drawing 4-5 embodiment 1 preparation, can see, because particle diameter is less in stereoscan photograph, adsorb each other between particle, the agglomeration of product is more serious, mostly be gathered into the cluster of diameter at about 200 nm, be difficult to see single TiC nanoparticle; And as can be seen from the projection electromicroscopic photograph of same position, the TiC nanoparticle obtained projection mostly is rhombus or hexagon, particle diameter is between 10 ~ 40 nm, and size distribution is comparatively even; In order to better see the pattern of single particle, HRTEM analysis being done to nano TiC and has seen accompanying drawing 6-7.
The projection of TiC nanoparticle mostly is square or hexagon as can be seen from Figure 6, and particle diameter is between 10 ~ 40 nm, and the endocorpuscular size distribution in the visual field is very even, most particle adhesion together, rarer single particle, this shows that particle is more easily reunited; And can be seen by the Fig. 7 amplified particle, the plane projection of product TiC nanoparticle is similar to regular hexagon, crystal face complete display, atomic arrangement is neat, through measuring, in figure, the spacing of nano silicon carbide titanium particle is 0.25 nm, and this is corresponding with TiC (111) interplanar distance 0.24999 nm, this illustrates product well-crystallized, is face-centred cubic TiC.
In sum, embodiment provided by the invention has prepared the consistent TiC nanocatalyst of high purity, regular shape, diameter, and for having obtained uniform diameter further, carbon nano fiber that fiber growth is good gets ready.
Table 2
| ? | Embodiment 3 | Comparative example 3 | Comparative example 4 |
| Vapour deposition temperature is | 450℃ | 400℃ | 500℃ |
| SEM spectrogram (accompanying drawing 8-10) | There is carbon fibre growth, and uniform diameter, grow along catalyzer symmetric helix | Obvious fibrous carbon is not had to grow | Have carbon fiber to generate, but different diameters is greatly different, profile is uneven, |
| HR-TEM(accompanying drawing 11-12) | That confirmed katalysis is TiC | —— | —— |
Can be seen by the stereoscan photograph of accompanying drawing 8-10, the temperature of reaction that comparative example 3 adopts is when being 400 DEG C, and catalyst surface does not have obvious fibrous carbon grow, just has the shorter and carbon filament that growth conditions is not good appearance on individual catalyst surface; And the temperature of reaction that comparative example 4 adopts is when being 500 DEG C, although can see that reaction has carbon fiber to generate, the different diameters great disparity of carbon fiber, profile inequality, product comprises the fiber of linear pattern, spiral type and sheet, and carbon fiber is very mixed and disorderly; And the temperature of reaction that embodiment 2 adopts is 450 DEG C, the uniform diameter of carbon fiber can be seen and fiber growth is good, the carbon fiber diameter obtained is 10 ~ 40 nm, and can know and see that catalyst particle is positioned at the center of the helical fiber of two symmetric growths, the diameter of catalyzer both sides fiber, screw diameter, pitch are all identical, and the hand of spiral is contrary, and carbon fiber diameter is suitable with catalyst particle size, the plane projection of catalyst particle is rhombus, with Hrtem Observation arrive identical.
High resolution perspective electromicroscopic photograph further by carbon nano fiber in accompanying drawing 11-12 is known, be that the carbon fiber diameter of catalyst growth is between 10 ~ 40 nm with TiC, roughly the same with catalyst particle, from amplifying the crystal face clearly can seeing catalyst particle, through measuring, its spacing is that (200) interplanar distance 0.2165nm of 0.217 nm and TiC coincide, the XRD spectra of combined catalyst particle, and can face is that TiC is playing katalysis.
In sum, the present invention adopts the compound containing titanium elements to be single catalyst, and raw material is easy to get, and obtains uniform diameter and fiber growth carbon nano fiber that is good, symmetric growth centered by catalyzer.By contrast, preferred vapour deposition temperature is 430-470 DEG C.
Present embodiment adopts JSM-6700F type scanning electronic microscope (band power spectrum), and because SiC is excellent semi-conductor, and carbon fiber guiding is electrically good, therefore test does not need metal spraying, directly by (the ultrasonic 30 min) observation in ethanol of sample ultrasonic disperse; Adopt JSM-1200EX type transmission electron microscope, sample needs fully ultrasonic, is dispersed in dehydrated alcohol, traps sample with copper mesh, is placed in sample table and observes; The high resolution transmission electron microscopy (HR-TEM) adopted is that NEC produces JEOL JSM-2100, and sample ultrasonic disperse in ethanol in advance, makes ethanol volatilize after copper mesh trapping, be placed in Electronic Speculum and observe; Adopt D/max-2500 type X-ray diffraction spectrometer, test condition is room temperature, Cu target, λ=0.154 nm, and step-length is 0.02 °.
Claims (8)
1. a preparation method for carbon nano fiber, is characterized in that: its catalyzer adopted is the compound containing titanium elements.
2. the preparation method of carbon nano fiber according to claim 1, is characterized in that: its catalyzer adopted is TiC.
3. the preparation method of carbon nano fiber according to claim 2, is characterized in that: the vapour deposition temperature that it adopts is 430-470 DEG C.
4. the preparation method of carbon nano fiber according to claim 3, is characterized in that: the vapour deposition temperature that it adopts is 450 DEG C.
5. the preparation method of carbon nano fiber according to claim 4, is characterized in that: it comprises the steps: step one, preparation TiC; Step 2, employing matrix method catalytic growth carbon nano fiber.
6. the preparation method of carbon nano fiber according to claim 5, is characterized in that: adopt when step one prepares TiC that titanium plate is anode, graphite rod is negative electrode, is argon gas and methane by the gas passed into after airtight for reaction chamber vacuumizing.
7. the preparation method of carbon nano fiber according to claim 6, is characterized in that: the ratio of the dividing potential drop of argon gas and methane is 1:1.
8. the preparation method of carbon nano fiber according to claim 7, is characterized in that: during step 2 catalytic growth carbon nano fiber, take acetylene as carbon source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410498805.3A CN104291313A (en) | 2014-09-26 | 2014-09-26 | Preparation method of nano carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410498805.3A CN104291313A (en) | 2014-09-26 | 2014-09-26 | Preparation method of nano carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104291313A true CN104291313A (en) | 2015-01-21 |
Family
ID=52311307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410498805.3A Pending CN104291313A (en) | 2014-09-26 | 2014-09-26 | Preparation method of nano carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104291313A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327093A (en) * | 2000-06-07 | 2001-12-19 | 华侨大学 | High elastic screw carbon fibre and its preparing method |
| CN1429767A (en) * | 2001-10-04 | 2003-07-16 | 佳能株式会社 | Method for preparing nanometer carbon material |
| US20030148097A1 (en) * | 2002-01-08 | 2003-08-07 | Futaba Corporation | Method for preparing nano-carbon fiber and nano-carbon fiber |
| CN1660692A (en) * | 2005-02-01 | 2005-08-31 | 上海纳晶科技有限公司 | Method for preparing film made from compound Nano carbon fiber |
| CN102203006A (en) * | 2008-06-18 | 2011-09-28 | 昭和电工株式会社 | Carbon nanofiber, producing method and use of the same |
| CN102616780A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Method for preparing titanium carbide nanometer particles and composite materials thereof by direct current arc method |
| CN103088648A (en) * | 2013-01-25 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
-
2014
- 2014-09-26 CN CN201410498805.3A patent/CN104291313A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327093A (en) * | 2000-06-07 | 2001-12-19 | 华侨大学 | High elastic screw carbon fibre and its preparing method |
| CN1429767A (en) * | 2001-10-04 | 2003-07-16 | 佳能株式会社 | Method for preparing nanometer carbon material |
| US20030148097A1 (en) * | 2002-01-08 | 2003-08-07 | Futaba Corporation | Method for preparing nano-carbon fiber and nano-carbon fiber |
| CN1660692A (en) * | 2005-02-01 | 2005-08-31 | 上海纳晶科技有限公司 | Method for preparing film made from compound Nano carbon fiber |
| CN102203006A (en) * | 2008-06-18 | 2011-09-28 | 昭和电工株式会社 | Carbon nanofiber, producing method and use of the same |
| CN102616780A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Method for preparing titanium carbide nanometer particles and composite materials thereof by direct current arc method |
| CN103088648A (en) * | 2013-01-25 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Novel Ni catalysts for methane decomposition to hydrogen and carbon nanofibers | |
| Qian et al. | Non-catalytic CVD preparation of carbon spheres with a specific size | |
| Zhai et al. | Porous graphitic carbons prepared by combining chemical activation with catalytic graphitization | |
| Awadallah et al. | Various nickel doping in commercial Ni–Mo/Al2O3 as catalysts for natural gas decomposition to COx-free hydrogen production | |
| Zhu et al. | The design and construction of 3D rose-petal-shaped MoS 2 hierarchical nanostructures with structure-sensitive properties | |
| Kumar et al. | Scalable synthesis of aligned carbon nanotubes bundles using green natural precursor: neem oil | |
| Liang et al. | Carbon nanotube growth on Ni-particles prepared in situ by reduction of La2NiO4 | |
| Ghosh et al. | Micro-structural, electron-spectroscopic and field-emission studies of carbon nitride nanotubes grown from cage-like and linear carbon sources | |
| Hsieh et al. | Parameter setting on growth of carbon nanotubes over transition metal/alumina catalysts in a fluidized bed reactor | |
| WO2010137592A1 (en) | Carbon material and method for producing the same | |
| JP2016501813A (en) | Carbon nanotube having high specific surface area and method for producing the same | |
| JP2008529957A (en) | Single-walled carbon nanotube catalyst | |
| Pudukudy et al. | Production of COx free hydrogen and nanocarbon via methane decomposition over unsupported porous nickel and iron catalysts | |
| Liu et al. | Synthesis of structure controlled carbon nanomaterials by AC arc plasma process | |
| KR100801192B1 (en) | Carbonnitride nanotubes with nano-sized pores on their stems, their preparation method and control method of size and quantity of pore thereof | |
| Hintsho et al. | The effect of CO 2 on the CVD synthesis of carbon nanomaterials using fly ash as a catalyst | |
| Xin et al. | Cu cluster embedded porous nanofibers for high-performance CO2 electroreduction | |
| Ding et al. | Large-scale synthesis of neodymium hexaboride nanowires by self-catalyst | |
| Aissou et al. | Synthesis and growth of onion-like polyhedral graphitic nanocapsules by thermal plasma | |
| Cui et al. | Synthesis of mesoporous tungsten carbide by an impregnation–compaction route, and its NH 3 decomposition catalytic activity | |
| Mansoor et al. | Optimization of ethanol flow rate for improved catalytic activity of Ni particles to synthesize MWCNTs using a CVD reactor | |
| CN103241725B (en) | Method for preparing carbon nano tube by taking coke as raw material and prepared carbon nano tube | |
| CN104291313A (en) | Preparation method of nano carbon fiber | |
| KR20120092344A (en) | Fabrication method of carbon nanotube or carbon nanofiber using metal-organic frameworks, and the carbon nanotube or carbon nanofiber thereby | |
| Liu et al. | Single-source precursor route to carbon nanotubes at mild temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150121 |