CN102530918B - Method for preparing single/double walled carbon nano tube structure with small size of tube bundle - Google Patents
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- 239000002079 double walled nanotube Substances 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002109 single walled nanotube Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000005684 electric field Effects 0.000 claims abstract description 41
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 9
- 238000010891 electric arc Methods 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 210000005239 tubule Anatomy 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005411 Van der Waals force Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 239000007952 growth promoter Substances 0.000 abstract 2
- 239000002071 nanotube Substances 0.000 abstract 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000005611 electricity Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001241 arc-discharge method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004720 dielectrophoresis Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
The invention relates to a technology for preparing a monodisperse single/double walled carbon nano tube, in particular to a method for preparing a single/double walled carbon nano tube structure with a small size of a tube bundle. A nano tube is prepared by adopting a mode of in-situ electric field application-cathode, anode direct current arc discharge; the anode is a consumptive anode formed by pressing graphite, a catalyst and a growth promoter, and an electric field is applied to an arc area through an external lead wire on a stainless steel plate. The method comprises the following steps of: firstly, applying the electric field; then, striking arc and discharging electricity; and finally, co-evaporating the graphite, the catalyst and the growth promoter to generate a single/double walled carbon nano tube. Under the action of the electric field, the surface of each single/double walled carbon nano tube carries electric charge, electrostatic repulsive force between tubes is greatly increased, the nano tube is prevented from being aggregated into a large tube bundle through van der Waals force, so that the single/double walled carbon nano tube which exists in a single or small tube bundle mode and has high quality is obtained. A single/double walled carbon nano tube sample with the small size of the tube bundle retards the change of the intrinsic electric structure of the carbon nano tube by carbon tube aggregation and bundling.
Description
Technical field
The present invention relates to the technology of preparing of monodisperse and single/double-walled carbon nano-tube, be specially a kind of electric field and assist the synthetic preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of arc discharge method.
Background technology
Carbon nanotube has just obtained huge concern because of its particular structure and performance since being found, Theoretical Calculation prediction Single Walled Carbon Nanotube presents metallicity or semiconductive according to the different of diameter and chirality, and two-layer Single Walled Carbon Nanotube has kept original electroconductibility substantially in the double-walled carbon nano-tube.These predictions that the STM observations is verified.But usually synthetic list/double-walled carbon pipe is that form with big tube bank exists.This is because each carbon atom has a unsaturation π key on list/double-walled carbon nano-tube tube wall surface, the effect of these keys is again owing to the characteristics of tubular structure surface negative curvature are strengthened, therefore very strong Van der Waals force effect (the contacting bonding force between two pipes and be of every micron length～500eV) arranged between list/double-walled carbon nano-tube tube wall and the tube wall, under the Van der Waals force effect, list/double-walled carbon nano-tube trends towards combining with pencil.Assemble the electronic structure that bunchy has not only changed the Single Walled Carbon Nanotube intrinsic between the list/double-walled carbon nano-tube, return the follow-up sepn process that obtains single size/conductive properties Single Walled Carbon Nanotube and carry out and caused difficulty.In addition, studies show that tube bank size (but not carbon nanotube diameter or chirality) has played conclusive effect to field emission performance, the tube bank size is more little, and threshold field is more low, and the field emission performance of sample with minimum tube bank size is the most excellent.
Magnanimity obtains single and tubule Shu Dan/double-walled carbon nano-tube and is not only important topic in the carbon nanotube research, also is to realize its key in application in each field.At present, a plurality of research groups explore and use chemical method to come selectivity to obtain monodisperse and single/double-walled carbon nano-tube; After selective chemical is functionalized, utilize various technology, as methods such as dielectrophoresis, chromatograms, list/double-walled carbon nano-tube is separated [document 1 from tube bank, Doorn SK, Fields RE, Hu H, Hamon MA, Haddon RC, Selegue JP, Majidi V, J Am Chem Soc.124,3169-3174 (2002); Document 2, Farkas E, Anderson ME, Chen ZH, Rinzler AG, Chem Phys Lett.363,111-116 (2002)].But these chemistry routes based on liquid phase not only will be used polymkeric substance or tensio-active agent, also relate to multistep chemistry and physical process, and these chemical processes also may and change its performance to list/double-walled carbon nano-tube doping simultaneously; In addition, single list/double-walled carbon nano-tube that chemical method obtains is very short (tens of to hundreds of nanometers) and be easy in liquid phase to assemble again usually, and all drawbacks of these chemistry routes have limited list/double-walled carbon nano-tube preparation of devices and performance study.In addition, people such as Sun explore and use the enclosed pasture explosion method to obtain tube bank than minor diameter, but efficient lower [document 3, Liu GT, Zhao YC, Zheng KH, Liu Z, Ma WJ, Ren Y, Xie SS, Sun LF, Nano Lett.9,239-244 (2009)].Therefore, for further promoting research and the application of list/double-walled carbon nano-tube, present subject matter is: how magnanimity obtains high quality, single and tubule Shu Dan/double-walled carbon nano-tube sample.
Summary of the invention
The purpose of this invention is to provide a kind of the have Single Walled Carbon Nanotube of tubule bundle size or the preparation method of double-walled carbon nano-tube structure, can magnanimity obtain high quality, single and tubule Shu Dan/double-walled carbon nano-tube sample.
The present invention is achieved through the following technical solutions:
A kind of preparation method with list/double-walled carbon nano-tube structure of tubule bundle size adopts original position to apply electric field and assists the arc discharge method preparation, comprises the steps:
(1) adopt original position to apply the mode of electric field-direct current arc discharge: it is graphite rod or other conductive carbon material that negative electrode adopts diameter, the sacrificial anode of anode for being formed by graphite, catalyzer, growth stimulant compacting; Become 20～90 ° angle between negative electrode and anode, the shortest distance between negative electrode and anode is 0.5～2mm.
(2) in the anode material, one or more mixing of catalyzer chosen from Fe, cobalt, nickel transition element, add-on is that 1.0～10.0atm.% (is preferably 2.0～6.0atm.%), growth stimulant is Iron sulfuret, add-on is that (be preferably 0.5～2.0atm.%), surplus is graphite to 0.1～4.0atm.%; Buffer gas is hydrogen or helium, and buffer gas pressure is 20～100KPa; Electric arc is direct-current discharge, and galvanic current 10～300A (is preferably 90～150A).
(3) pair of parallel stainless steel plate symmetry is positioned over the both sides of anode tablet, by the pair of parallel stainless steel plate arc region is applied electric field, and the strength of electric field that original position applies electric field is that 50～300V/cm (is preferably 100～250V/cm); At first apply electric field, then play arc discharge; The graphite of anode, catalyzer, growth stimulant coevaporation generate Single Walled Carbon Nanotube or double-walled carbon nano-tube; Under the electric field action, every Single Walled Carbon Nanotube or double-walled carbon nano-tube surface all have electric charge, electrostatic repulsion forces between the tube and tube increases greatly, stoped carbon nanotube by Robert Van de Walle now power be gathered into big tube bank, thereby obtain many with Single Walled Carbon Nanotube or double-walled carbon nano-tube single or that tubule bundle form exists.
(4) key condition of the controlled preparation of Single Walled Carbon Nanotube is: need to use transition metal nickel to account for the composite catalyst (molar content of nickel is more than 60%) of main component, optimal catalyst mol ratio: Fe: Co: Ni=1: 1: 5.
(5) key condition of the controlled preparation of double-walled carbon nano-tube is: need to use the transition metal cobalt to account for the composite catalyst (molar content of nickel is more than 50%) of main component, optimal catalyst mol ratio: Fe: Co: Ni=1: 2: 0.4.
(6) high-quality controlled preparation is based on the hot conditions (3000～4000K), and electric field is to the influence of arc temperature field of arc process; And the original position corrasion of hydrogen infers it is that nitrogen atmosphere product oxidation resistance temperature is higher than the reason of helium-atmosphere product oxidation resistance temperature and the original position corrasion of hydrogen.
Among the present invention, the oxidation resistance temperature of Single Walled Carbon Nanotube is 720 ℃, and the oxidation resistance temperature of double-walled carbon nano-tube is 750 ℃; Wherein, the oxidation resistance temperature of carbon nanotube is defined as the fastest oxidizing temperature under air atmosphere.
Advantage of the present invention is:
1, the inventive method can directly prepare have tubule bundle size, high-quality list/double-walled carbon nano-tube sample, sample degree of crystallinity height can obtain the magnanimity sample.Provide the prerequisite basis for qualitative with intrinsic performance and the separating of different attribute Single Walled Carbon Nanotube of quantitative examination list/double-walled carbon nano-tube.
2, the present invention has tubule bundle size, high-quality list/double-walled carbon nano-tube structure, the tube bank size of prepared list/double-walled carbon nano-tube sample mostly (more than at least 75%) in 10nm.
Description of drawings
Transmission electron microscope photo (right side) and the tube bank distribution of sizes statistics histogram (left side) of Fig. 1 for synthesizing the Single Walled Carbon Nanotube structure with tubule bundle size among the embodiment 1.
Embodiment
The mode that the present invention adopts original position to apply electric field-cathode and anode direct current arc discharge prepares, and the sacrificial anode of anode for being formed by graphite, catalyzer, growth stimulant compacting applies electric field by the lead-in wire that adds on the stainless steel plate to arc region.At first apply electric field, then play arc discharge, graphite, catalyzer, growth stimulant coevaporation generate list/double-walled carbon nano-tube; Under the electric field action, every list/double-walled carbon nano-tube surface all has electric charge, electrostatic repulsion forces between the tube and tube increases greatly, stoped carbon nanotube by Robert Van de Walle now power be gathered into big tube bank, thereby obtain many with single or tubule bundle form exist, high-quality list/double-walled carbon nano-tube.The list of this less tube bank size/double-walled carbon nano-tube sample has slowed down the carbon pipe and has assembled bunchy to the change of the electronic structure of its intrinsic, obtain the sepn process that single size/conductive properties list/double-walled carbon nano-tube carries out and provide convenience for follow-up, this tubule bundle size, high-quality list/double-walled carbon nano-tube sample also will be beneficial to the performance of its performance simultaneously.
Embodiment 1
The powder mix of the iron sulphide growth stimulant of graphite, 2.0atm.% catalyzer (mol ratio: Fe: Co: Ni=1: 1: 5) and 0.5atm.% is put into anode graphite disk hole and compacting, negative electrode is a graphite rod that diameter is 10mm, charge into 32KPa hydrogen in the reactor, striking current is the 120A direct current, the shortest distance of two interpolar maintenance～2mm and～30 ° of angles, to apply the strength of electric field of electric field be 250V/cm to original position between two-plate.Do not have/have the contrast experiment who applies under the electric field, the transmission electron microscope photo of each position Single Walled Carbon Nanotube sample of gained cavity and tube bank distribution of sizes statistics histogram are as shown in Figure 1.The distribution of sizes of the Single Walled Carbon Nanotube tube bank when not applying electric field in the cavity has 47% between 0～10nm, being distributed in has 42% between 10～20nm approximately, is distributed between 20～40nm on a small quantity in addition.After applying electric field, in the sample between pole plate, the size of 86.4% tube bank concentrates in the 10nm; Be arranged in the outer sample of pole plate, the size of 85.8% tube bank concentrates on below the 10nm; Be arranged in the sample of pole plate lower rim, the size of 98.4% tube bank concentrates on below the 10nm.The oxidation resistance temperature that do not apply electric field, applies the Single Walled Carbon Nanotube for preparing under the electric field is respectively: 653 ℃ and 720 ℃.
Difference from Example 1 is:
The powder mix of the iron sulphide growth stimulant of graphite, 4.0atm.% catalyzer (mol ratio: Fe: Co: Ni=1: 1: 5) and 4.0atm.% is put into anode graphite disk hole and compacting, negative electrode is a graphite rod that diameter is 10mm, charge into the 67KPa helium in the reactor, striking current is the 200A direct current, the shortest distance of two interpolar maintenance～2mm and～40 ° of angles, to apply the strength of electric field of electric field be 125V/cm to original position between two-plate.Do not have/have the contrast experiment who applies under the electric field, each position Single Walled Carbon Nanotube sample of gained cavity is carried out transmission electron microscope characterize and restrain the distribution of sizes statistics.The distribution of sizes that statistics shows the Single Walled Carbon Nanotube tube bank in the cavity when not applying electric field has 42.2% between 0～10nm, being distributed in has 47.0% between 10～20nm approximately, is distributed between 20～40nm on a small quantity in addition.After applying electric field, in the sample between pole plate, the size of 75.7% tube bank concentrates in the 10nm; Be arranged in the outer sample of pole plate, the size of 84.2% tube bank concentrates on below the 10nm; Be arranged in the sample of pole plate lower rim, the size of 87.3% tube bank concentrates on below the 10nm.The oxidation resistance temperature that do not apply electric field, applies the Single Walled Carbon Nanotube for preparing under the electric field is respectively: 608 ℃ and 675 ℃.
Embodiment 3
Difference from Example 1 is:
The powder mix of the iron sulphide growth stimulant of graphite, 4.0atm.% catalyzer (mol ratio: Fe: Co: Ni=1: 2: 0.4) and 0.8atm.% is put into anode graphite disk hole and compacting, negative electrode is a graphite rod that diameter is 10mm, charge into the 32KPa helium in the reactor, striking current is the 150A direct current, the shortest distance of two interpolar maintenance～2mm and～40 ° of angles, to apply the strength of electric field of electric field be 200V/cm to original position between two-plate.Do not have/have the contrast experiment who applies under the electric field, each position double-walled carbon nano-tube sample of gained cavity is carried out transmission electron microscope characterize and restrain the distribution of sizes statistics.Statistics shows, the distribution of sizes of the double-walled carbon nano-tube tube bank when not applying electric field in the cavity has 48.4% between 0～10nm, and being distributed in has 32.3% between 10～20nm approximately, is distributed between 20～40nm on a small quantity in addition.After applying electric field, in the sample between pole plate, the size of 91.6% tube bank concentrates in the 10nm.The oxidation resistance temperature that do not apply electric field, applies the double-walled carbon nano-tube for preparing under the electric field is respectively 680 ℃ and 750 ℃.
Claims (8)
1. the preparation method with list/double-walled carbon nano-tube structure of tubule bundle size is characterized in that, comprises the steps:
(1) adopt original position to apply the mode of electric field-direct current arc discharge: negative electrode adopts graphite rod or other conductive carbon material, the sacrificial anode of anode for being formed by graphite, catalyzer, growth stimulant compacting; In the anode material, one or more mixing of catalyzer chosen from Fe, cobalt, nickel transition element, add-on is 1.0-10.0 atm.%, and growth stimulant is Iron sulfuret, and add-on is 0.1-4.0 atm.%, and surplus is graphite;
(2) pair of parallel stainless steel plate symmetry is positioned over the both sides of anode tablet, by the pair of parallel stainless steel plate arc region is applied electric field, and the strength of electric field that original position applies electric field is 50-300V/cm; At first apply electric field, then play arc discharge; The graphite of anode, catalyzer, growth stimulant coevaporation generate Single Walled Carbon Nanotube or double-walled carbon nano-tube; Under the electric field action, every Single Walled Carbon Nanotube or double-walled carbon nano-tube surface all have electric charge, electrostatic repulsion forces between the tube and tube increases greatly, stoped carbon nanotube by Robert Van de Walle now power be gathered into big tube bank, thereby obtain many with Single Walled Carbon Nanotube or double-walled carbon nano-tube single or that tubule bundle form exists;
The size of list/double-walled carbon nano-tube tube bank more than 75% in 10 nm.
2. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: the oxidation resistance temperature of Single Walled Carbon Nanotube is 720 ° of C, and the oxidation resistance temperature of double-walled carbon nano-tube is 750 ° of C; Wherein, the oxidation resistance temperature of carbon nanotube is defined as the fastest oxidizing temperature under air atmosphere.
3. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: the buffer gas of preparation list/double-walled carbon nano-tube structure is hydrogen or helium, and buffer gas pressure is 20-100 kPa.
4. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: electric arc is direct-current discharge, and galvanic current is 10-300 A.
5. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: become 20-90 ° angle between negative electrode and anode, the shortest distance between negative electrode and anode is 0.5-2 mm.
6. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: the condition of growth tubule bundle size Single Walled Carbon Nanotube is: needs use transition metal nickel to account for the composite catalyst of main component, and catalyst molar ratio is Fe:Co:Ni=1:1:5.
7. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: the condition of growth tubule bundle size double-walled carbon nano-tube is: needs use the transition metal cobalt to account for the composite catalyst of main component, and catalyst molar ratio is Fe:Co:Ni=1:2:0.4.
8. according to the described preparation method with list/double-walled carbon nano-tube structure of tubule bundle size of claim 1, it is characterized in that: the hot conditions of arc process is 3000-4000 K.
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| CN104538268B (en) * | 2014-12-20 | 2016-08-17 | 电子科技大学 | A kind of wet spinning preparation method of carbon nano-tube fibre array cold cathode |
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