CN102602911A - Method for preparing single-walled carbon nanotube by adopting controllability of low-pressure reactant gas - Google Patents

Method for preparing single-walled carbon nanotube by adopting controllability of low-pressure reactant gas Download PDF

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Publication number
CN102602911A
CN102602911A CN2012100620880A CN201210062088A CN102602911A CN 102602911 A CN102602911 A CN 102602911A CN 2012100620880 A CN2012100620880 A CN 2012100620880A CN 201210062088 A CN201210062088 A CN 201210062088A CN 102602911 A CN102602911 A CN 102602911A
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low pressure
controllability
pressure reaction
reaction property
property gas
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张亚非
苏言杰
张竟
魏浩
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The invention relates to a method for preparing a single-walled carbon nanotube by adopting the controllability of low-pressure reactant gas. The method comprises the steps of: at the buffer atmosphere filled with the low-pressure reactant gas, mixing transition metals such as Ni/ Y, Fe or Ni/ Co/ Fe serving as a catalyst and S serving as a growth promoter with high-purity graphite powder to prepare an anode; carrying out arc discharge between the anode and a pure-graphite cathode; and finally, controlling the discharge current/voltage, the pressure and the type of the low-pressure reactant gas and the like to realize the controllable preparation of the single-walled carbon nanotube. Compared with the prior art, the method disclosed by the invention is simple and flexible in technology, is beneficial to inhibition of generation of amorphous carbon and convenient for large-scale preparation, and the prepared single-walled carbon nanotube has controllable diameter.

Description

A kind of method that adopts low pressure reaction property gas controllability to prepare SWCN
Technical field
The present invention relates to a kind of preparation method of technical field of nano material, especially relate to a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN.
Background technology
Since nineteen ninety-one, carbon nanotube (Carbon nanotubes; CNTs) caused and the extensive concern of numerous areas such as comprising physics, chemistry and Materials science at present carbon nanotube has been applied to numerous areas such as nanometer electronic device, a lift-off technology, biological medicine carrying, hydrogen storage technology because of having remarkable machinery, calorifics, electric property.CNTs is a kind of novel hollow tubular nanostructure that is bent to form by two-dimentional graphene film; By tube wall layer number can with carbon nanotube can be divided into single ancient piece of jade, round, flat and with a hole in its centre carbon nanotube (Single-walled carbon nanotubes, SWNTs) and multi-walled carbon nano-tubes (Multi-walled carbon nanotubes MWNTs).Wherein SWNTs is as good quasi-one-dimensional nanometer material; Be used as and make field-effect transistor (FET), thin film transistor nanometer electronic devices such as (TFT) because of it has higher carrier mobility, be expected to replace silicon materials and the critical material that becomes microelectronic device of future generation.
As everyone knows, the optics of SWNTs, electrical properties depend on that their diameter and chirality distribute, different according to diameter and chirality, and SWNTs can show as metallicity; Also can show as semiconductive, and the band gap of semiconductive SWNTs and its diameter is reciprocal linear.Yet; Present most SWNTs sample is made up of multiple SWNTs with different diameter and chirality; Twine each other between these carbon nanotubes; Be difficult to separate, and then can't guarantee the homogeneity of SWNTs base device performance, this has become a science difficult problem that needs to be resolved hurrily that has hindered SWNTs large-scale application in nanometer electronic device.In recent years, the controllability of SWNTs obtained aspect preparing many progress (M.G.Hahm, et al.J.Phys.Chem.C 2008,112:17143-17147).But these controllability technologies of preparing mainly are to utilize chemical Vapor deposition process (CVD) control catalyst size, carbon source or growth conditions to wait the controllability that realizes SWNTs to prepare.And the prepared SWNTs of CVD method has the not high shortcoming of textural defect, percent crystallinity, is unfavorable for bringing into play the excellent electrical of SWNTs.
Summary of the invention
The object of the invention is exactly to provide a kind of arc discharge method and reactant gas to combine controllability to prepare the method for SWCN for the defective that overcomes above-mentioned prior art existence.
The object of the invention can be realized through following technical scheme:
A kind of method that adopts low pressure reaction property gas controllability to prepare SWCN; With sulphur is growth stimulant; Make anode with transition-metal catalyst, growth stimulant and after the high purity graphite powder mixes; In the buffer gas that is filled with low pressure reaction property gas, carry out arc-over then, through kind of regulating discharging current, voltage, low pressure reaction property gas and the controllability preparation that pressure carries out SWCN with pure graphite cathode.
Described transition-metal catalyst is one or more of iron, cobalt, nickel or yttrium, or in the compound of above-mentioned transition metal one or more.
The mixture of mixture, iron powder or the iron-cobalt-nickel of the preferred nickel-yttrium of described transition-metal catalyst.
The content of the transition-metal catalyst in the described anode is 1～6at%.
The content of the growth stimulant in the described anode is 0.2～2at%.
Described low pressure reaction property gas is carbonic acid gas, oxynitrides or hydrogen sulfide, and described oxynitrides is NO 2Or N 2O, the pressure of low pressure reaction property gas are 0.1～10kPa.
Described buffer gas is one or more in helium, argon gas or the hydrogen, and the air pressure of buffer gas is 20～40kPa.
Electric current 70～the 120A of electrical discharge arc, voltage are 30～70V.
Compared with prior art; The present invention is through introducing low pressure reaction property gas in buffer gas; Both can to regulation and control SWCN growth and realize controllable diameter; Etching prepares the decolorizing carbon in the process and improves product purity to a certain extent again, can also have the low defective characteristics that arc process prepares SWCN concurrently simultaneously.
Description of drawings
Fig. 1 is the Raman spectrogram of the prepared SWCN of Comparative Examples;
Fig. 2 is the Raman spectrogram of the prepared SWCN of embodiment 1;
Fig. 3 is for adding different content CO 2The time prepared SWCN Raman spectrogram;
Fig. 4 is the Raman spectrogram of the prepared SWCN of embodiment 2.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Comparative Examples
With high purity graphite powder, Ni powder, Y 2O 3(C: Ni: Y: S is 93.5: 4.2: 1: process the 6mm graphite anode rod after 0.5) mixing according to mol ratio for powder, sulphur powder.Putting into the arc chamber that is connected with 40kPa helium (He) then is that the pure graphite cathode of 8mm carries out arc-over relatively with carrying out diameter.Discharging current is 80～90A, and voltage is 40～45V.Be 7 minutes discharge time, makes about 0.75g SWCN.Its Raman spectrogram can draw through calculating that the diameter of SWNTs is respectively 1.49nm and 1.35nm in the product shown in 1.
Embodiment 1
With high purity graphite powder, Ni powder, Y 2O 3(C: Ni: Y: S is 94.3: 4.2: 1: process the 6mm graphite anode rod after 0.5) mixing according to mol ratio for powder, sulphur powder.Be connected with 40kPa helium (He) and 4.8kPa carbonic acid gas (CO then 2) arc chamber in to carry out diameter be that the pure graphite cathode of 8mm carries out arc-over relatively.Discharging current is 95～100A, and voltage is 50～55V.Be 6 minutes discharge time, makes about 0.5g SWCN.The Raman spectrogram of SWNTs sample can be found out CO on low frequency Raman spectrum shown in 2 2The SWNTs diameter is respectively 1.70nm and 1.52nm in the back prepared sample of introducing, shows that the content of small dia SWNTs in sample reduces, and major diameter SWNTs tends to grow.Fig. 3 is different content CO 2The Raman spectrum of prepared SWNTs sample under the condition can be known by figure, introduces CO 2The content not diameter Distribution of prepared simultaneously SWNTs also is not quite similar, and also is CO 2Diameter Distribution to SWNTs has produced regulating and controlling effect.
Embodiment 2
With high purity graphite powder, Ni powder, Y 2O 3(C: Ni: Y: S is 93.5: 4.8: 1.2: process the 6mm graphite anode rod after 0.5) mixing according to mol ratio for powder, sulphur powder.Put into then and be connected with 20kPa helium (He) and 0.8kPa nitrogen peroxide (N 2O) arc chamber is interior to be that the pure graphite cathode of 8mm carries out arc-over relatively with carrying out diameter.Discharging current is 80～85A, and voltage is 40～45V.Be 7 minutes discharge time, makes about 0.8g SWCN.The Raman spectrogram of SWNTs sample shown in 4, N 2The SWNTs diameter that O introduces the prepared SWNTs sample in back is respectively 1.71nm, 1.51nm and 1.34nm, on low frequency Raman spectrum, can find out, compares 181cm with Comparative Examples -1The reduction of peak intensity means that the content of sample medium-small diameter SWNTs (1.71nm) in sample reduces.Hence one can see that, through in buffer gas, introducing N 2O can regulate and control the diameter Distribution of SWNTs.
Embodiment 3
Process the 6mm graphite anode rod after high purity graphite powder, Fe powder, sulphur powder mixed according to mol ratio (C: Fe: S is 97.5: 2: 0.5).Put into then and be connected with 30kPa helium/hydrogen (Ar/H 22) and 10kPa carbonic acid gas (CO=3: 2) arc chamber in to carry out diameter be that the pure graphite cathode of 8mm carries out arc-over relatively.Discharging current is 70～75A, and voltage is 30～35V.Be 20 minutes discharge time, makes the controlled SWCN of about 1.2g diameter Distribution.
Embodiment 4
Process the 6mm graphite anode rod after high purity graphite powder, Fe powder, Co powder, Ni powder, sulphur powder mixed according to mol ratio (C: Fe: Co: Ni: S is 96.5: 1: 0.5: 1.5: 0.5).Put into then and be connected with 35kPa argon gas/hydrogen (ratio is 3: 2) and 0.1kPa hydrogen sulfide (H 2S) arc chamber is interior to be that the pure graphite cathode of 8mm carries out arc-over relatively with carrying out diameter.Discharging current is 115～120A, and voltage is 65～70V.Be 12 minutes discharge time, makes the controlled SWCN of about 0.9g diameter Distribution.
Embodiment 5
A kind of method that adopts low pressure reaction property gas controllability to prepare SWCN is a growth stimulant with sulphur, makes anode with metal Fe catalyzer, sulphur powder and after the high purity graphite powder mixes; Wherein, the content of metal Fe catalyzer is 1at%, and the content of sulphur powder is 0.2at%; In being filled with the argon gas/hydrogen of dioxide gas, carry out arc-over then with pure graphite cathode; The pressure of dioxide gas is 0.1kPa, and the pressure of argon gas/hydrogen (ratio is 3: 2) is 20kPa, and the adjusting discharging current is 70A; Voltage is 30V, promptly can carry out the controllability preparation of SWCN.
Embodiment 6
A kind of method that adopts low pressure reaction property gas controllability to prepare SWCN is a growth stimulant with sulphur, makes anode with metal Fe catalyzer, sulphur powder and after the high purity graphite powder mixes; Wherein, The content of metal Fe catalyzer is 6at%, and the content of sulphur powder is 2at%, is being filled with NO then 2Carry out arc-over with pure graphite cathode in the argon gas/hydrogen of gas; The pressure of dioxide gas is 10kPa, and the pressure of argon gas/hydrogen (ratio is 3: 2) is 40kPa, and the adjusting discharging current is 120A; Voltage is 70V, promptly can carry out the controllability preparation of SWCN.

Claims (10)

1. method that adopts low pressure reaction property gas controllability to prepare SWCN; It is characterized in that; This method is growth stimulant with sulphur; Make anode with transition-metal catalyst, growth stimulant and after the high purity graphite powder mixes, in the buffer gas that is filled with low pressure reaction property gas, carry out arc-over then, through kind of regulating discharging current, voltage, low pressure reaction property gas and the controllability preparation that pressure carries out SWCN with pure graphite cathode.
2. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1; It is characterized in that; Described transition-metal catalyst is one or more of iron, cobalt, nickel or yttrium, or in the compound of above-mentioned transition metal one or more.
3. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 2 is characterized in that the mixture of mixture, iron powder or the iron-cobalt-nickel of the preferred nickel-yttrium of described transition-metal catalyst.
4. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that the content of the transition-metal catalyst in the described anode is 1～6at%.
5. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that the content of the growth stimulant in the described anode is 0.2～2at%.
6. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that described low pressure reaction property gas is carbonic acid gas, oxynitrides or hydrogen sulfide, and described oxynitrides is NO 2Or N 2O.
7. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that the pressure of low pressure reaction property gas is 0.1～10kPa.
8. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that described buffer gas is one or more in helium, argon gas or the hydrogen.
9. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that the air pressure of described buffer gas is 20～40kPa.
10. a kind of method that adopts low pressure reaction property gas controllability to prepare SWCN according to claim 1 is characterized in that the electric current 70～120A of electrical discharge arc, voltage are 30～70V.
CN2012100620880A 2012-03-07 2012-03-07 Method for preparing single-walled carbon nanotube by adopting controllability of low-pressure reactant gas Pending CN102602911A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104603051A (en) * 2012-09-18 2015-05-06 埃克森美孚上游研究公司 Reactor system for the production of carbon allotropes

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Publication number Priority date Publication date Assignee Title
CN1749156A (en) * 2005-10-18 2006-03-22 南开大学 Arc method for synthesizing controllable single wall carbon nano tube
CN101671001A (en) * 2009-10-15 2010-03-17 上海交通大学 Preparation method for semiconductor single wall carbon nano tube
CN101905880A (en) * 2010-07-23 2010-12-08 上海交通大学 Method for preparing diameter-controllable single-walled carbon nanotube
WO2010143585A1 (en) * 2009-06-11 2010-12-16 Ｄｏｗａホールディングス株式会社 Carbon nanotubes and process for producing same
CN102351171A (en) * 2011-09-15 2012-02-15 上海交通大学 Method for selectively preparing single-walled carbon nanotube in magnetic field

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1749156A (en) * 2005-10-18 2006-03-22 南开大学 Arc method for synthesizing controllable single wall carbon nano tube
WO2010143585A1 (en) * 2009-06-11 2010-12-16 Ｄｏｗａホールディングス株式会社 Carbon nanotubes and process for producing same
CN101671001A (en) * 2009-10-15 2010-03-17 上海交通大学 Preparation method for semiconductor single wall carbon nano tube
CN101905880A (en) * 2010-07-23 2010-12-08 上海交通大学 Method for preparing diameter-controllable single-walled carbon nanotube
CN102351171A (en) * 2011-09-15 2012-02-15 上海交通大学 Method for selectively preparing single-walled carbon nanotube in magnetic field

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104603051A (en) * 2012-09-18 2015-05-06 埃克森美孚上游研究公司 Reactor system for the production of carbon allotropes
CN104603051B (en) * 2012-09-18 2017-06-09 埃克森美孚上游研究公司 Produce the reactor assembly of carbon allotrope

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Application publication date: 20120725