CN100480179C - Method of cutting multi-wall carbon nano tube - Google Patents
Method of cutting multi-wall carbon nano tube Download PDFInfo
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- CN100480179C CN100480179C CNB2007100407520A CN200710040752A CN100480179C CN 100480179 C CN100480179 C CN 100480179C CN B2007100407520 A CNB2007100407520 A CN B2007100407520A CN 200710040752 A CN200710040752 A CN 200710040752A CN 100480179 C CN100480179 C CN 100480179C
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Abstract
The invention relates to a cutting method of MWCNTs, which belongs to the nano-technique field. The method comprises the steps of: (1) dispersing the MWCNTs into ferrous salt solution in ultrasonic wave, strongly stirring the solution in water bath of 80 degree and dipping into H2O2 solution, reacting in constant temperature, filtering the solution, drying the solution and then Fe2O3-attached MWCNTs powder obtained; (2) the obtained product in step (1) being heated to 400-500 degree in inert gases, keeping the temperature till the precursor being converted into Fe2O3, then increasing the temperature to be 800-900 degree for reducing reaction, keeping the temperature for cooling, the obtained powder after cooling being back washed in diluted nitric acid solution for removing the metal Fe and the excessive Fe2O3. The cut CNTs is obtained after filtering, washing and drying. The invention obtains CNTs with two open ends and the length between 200 to 500nm finally.
Description
Technical field
What the present invention relates to is the cutting method of a kind of method of field of nanometer technology, particularly a kind of multi-walled carbon nano-tubes.
Background technology
Carbon nanotube since being found just machinery, physics and the chemical property with its uniqueness cause that people pay close attention to, extensively Ying Yu is with fields such as electronics, the energy, materials.But at present the carbon nanotube of prepared in various methods all is a large amount of the reunion together, and length reaches micron order, has seriously limited the application of carbon nanotube, as the molecular electric applicance field, need length at the carbon nanotube of 10～300nm as junctor; As the strongthener of matrix material, homodisperse short carbon nanometer tube can reduce stress concentration, thereby improves mechanical property.In order to obtain required short carbon nanometer tube, treatment process commonly used relates generally to physical process, chemical process and both combinations.It is the mixture that adopts ball milling or supersound process carbon nanotube and abrasive that physics is sheared, stronger between the two frictional force and shearing force make the carbon-carbon bond fracture, reach the purpose of shearing, be difficult to separate with abrasive yet this method exists the carbon pipe, and introduce the problem of impurity easily.A kind of physics cutting method of up-to-date report is the pulverize at low temperature method, carbon nanotube is distributed in the aqueous isopropanol handled 30 minutes in Lowtemperaturepulverizer, obtains the carbon nanotube of length less than 500nm.This method need be carried out in liquid nitrogen, and needs special equipment, is unfavorable for scale operation.Initial chemical shearing is with the vitriol oil, concentrated nitric acid or both nitration mixture reflow treatment carbon nanotubes, and the carbon atom of carbon nanotube wall fault location is blocked by acid oxidase.In the acid treatment process, can introduce functional groups such as hydroxyl, carboxyl, carbonyl on the carbon tube wall simultaneously, make it in composite matrix, reach better dispersion.
Find through literature search prior art, Z.Gu etc. are in " NANO LETT. " (nanometer communication), " the Cutting Single-Wall Carbon Nanotubes throughFluorination (fluorination shearing Single Walled Carbon Nanotube) " that delivers on 9 (2002) 1009-1013, the method that fluoridation is sheared carbon nanotube is proposed in this article, concrete grammar is: at first carbon nanotube is fluoridized in fluorine-containing atmosphere, heat reason or oxidation in concentrated acid in argon gas atmosphere then makes the carbon-fluorine bond fracture that forms in the fluorination process to reach the purpose of shearing carbon nanotube.Its deficiency is: it all is to have corrosively that these chemical processes are applied to concentrated acid and fluorine gas, and operational hazards and treating processes are consuming time, generally need several hours even tens hours.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of cutting method of multi-walled carbon nano-tubes is provided, make it solve problem in the background technology, resulting short carbon nanometer tube length is at 200～500nm.
The present invention is achieved by the following technical solutions, and the present invention adopts the method for wet-chemical at carbon nano tube surface deposition of iron oxide particle, utilizes the reaction of carbon reduction ferric oxide again, and carbon nanotube is carried out chemical shearing.
The present invention includes following steps:
(1) the ferric oxide presoma is in the deposition of carbon nano tube surface: with the multi-walled carbon nano-tubes ultra-sonic dispersion in the aqueous solution of ferrous salt, violent stirring and drip hydrogen peroxide liquid under 80 ℃ of water bath condition, keep thermotonus after-filtration, drying, obtain the carbon nanotube powder that tube wall adheres to the ferric oxide presoma;
The concentration of aqueous solution of described ferrous salt is 0.5M, and ferrous salt can be selected from iron vitriol or iron protochloride;
The organic millipore filtration of F type polyvinylidene difluoride (PVDF) is adopted in described filtration, and its filter opening diameter is 0.45 μ m;
The ratio of the aqueous solution of described multi-walled carbon nano-tubes and ferrous salt is: 0.01～0.02g/ml;
The ratio of the aqueous solution of described hydrogen peroxide liquid and ferrous salt is: 3～5 (vol/vol);
Described maintenance thermotonus, the reaction times is 4 hours;
Described hydrogen peroxide liquid, its concentration are 30%;
Described drying was meant: 100～120 ℃ of dryings 2～4 hours.
(2) shearing of multi-walled carbon nano-tubes: the carbon nanotube that adheres to the ferric oxide presoma that step (1) is obtained heat temperature raising to 400～500 ℃ under the protection of inert gas in silica tube; insulation makes presoma be converted into ferric oxide under this temperature; be warming up to 800～900 ℃ afterwards once more reduction reaction takes place; and under this temperature, be incubated; cooling back gained powder reflow treatment in dilute nitric acid solution; to remove metallic iron and residue ferric oxide; when treating that temperature is reduced to room temperature; with deionized water dilution, after filtration, the carbon nanotube after obtaining shearing after the washing, drying.
Described heat temperature raising to 400～500 ℃, its temperature rise rate is 5～10 ℃/minute, soaking time is 2～3 hours under this temperature;
Describedly be warming up to 800～900 ℃, its temperature rise rate is 5～10 ℃/minute, and soaking time is 2～3 hours under this temperature;
Described cooling is meant: be cooled to room temperature under inert atmosphere, rare gas element is argon gas or nitrogen.
Described in dilute nitric acid solution reflow treatment, be meant: ultra-sonic dispersion in dilute nitric acid solution, and under 100～120 ℃ temperature back flow reaction 2～3 hours;
Described ferric oxide is meant to obtain that its quality percentage composition that accounts for total mixture is: 50～80% after 400～500 ℃ of thermal treatment;
Described dilute nitric acid solution is meant that the ratio of 68% concentrated nitric acid solution and deionized water is: 3～1 (vol/vol);
Described with the deionized water dilution, be meant that being diluted to the pH value is 6～7;
Described gained powder reflow treatment in dilute nitric acid solution, the ratio of carbon nanotube powder and dilute nitric acid solution is: 0.01～0.02g/ml.
The organic millipore filtration of F type polyvinylidene difluoride (PVDF) is adopted in described filtration, and its filter opening diameter is 0.45 μ m;
Described drying was meant: 80～100 ℃ of dryings 2～6 hours.
Ultimate principle of the present invention is such: Fe
2+-H
2O
2System has dual-use function, the strong oxidation of hydroxyl radical free radical and ferric coagulation.Under the hydrogen peroxide and iron ion condition of high density, ferrous ion is oxidized to ferric ion rapidly and is discharged the very strong hydroxyl radical free radical of oxidation capacity, carries out the partical oxidizing modifying of carbon nano tube surface; Ferric ion of Sheng Chenging and water have very strong hydrolysis-polymerization-precipitation trend simultaneously, form the ferric oxide presoma on the carbon nanotube tube wall.This presoma is transformed into ferric oxide particles when low-temperature heat treatment, in ensuing high-temperature heat treatment process, the carbon atom that is attached with the ferric oxide particles place on the carbon nanotube wall reacts with it, thereby carbon is consumed carbon nanotube is blocked, the iron particle that reduction generates is removed through the diluted acid reaction.
The characteristics of the cutting method of multi-walled carbon nano-tubes provided by the invention are: utilized the carbon reaction truncating carbon nano-tubes of reducing iron oxides at high temperature, the loss amount of whole process carbon nanotube is little, the carbon nanotube both ends open and the homodisperse that obtain, length is between 200～500nm.The carbon nanotube of this yardstick has crucial scientific meaning, because it has high dispersive, and small scale, tube chamber available advantage will be used widely in electron device, an emission scan device and prepare composite.
Description of drawings
Fig. 1 is the transmission electron microscope photo of multi-walled carbon nano-tubes (length 1～5 μ m).
Fig. 2 (a), (b) the short carbon nanometer tube (transmission electron microscope photo of length 200～500nm) for shearing through the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
With the carbon nanotube 2 gram ultra-sonic dispersion of as shown in Figure 1 length 1～5 μ m in the copperas solution 100mL of 0.5M, reflow treatment in 80 ℃ of water-baths then, in reactor, drip 30% hydrogen peroxide 300mL simultaneously, react end in 4 hours, to be cooled during to room temperature, with the organic type filtering with microporous membrane and use deionized water wash,, obtain being attached with the carbon nanotube of ferric oxide presoma in 100 ℃ of dryings 4 hours.
With tile quartz boat and place silica tube to heat-treat of the above-mentioned even carbon nanotube that obtains, feed nitrogen protection, be warming up to 450 ℃ with 10 ℃/minute speed, under this temperature, kept 2 hours, the quality percentage composition of the ferric oxide that obtains is 50%.Be warming up to 850 ℃ with same speed again, and be incubated 2 hours.
Carbon nanotube redispersion after the thermal treatment is at HNO
3: H
2O is in the dilute nitric acid solution of 1:1 (vol/vol), 120 ℃ of reflow treatment were removed metallic iron and remaining ferric oxide in 3 hours, it is 6 that cooling back is diluted to pH value with deionized water, filters, washs and in 100 ℃ of dryings 6 hours, the short carbon nanometer tube of finally being sheared.As shown in Figure 2, the transmission electron microscope photo of the carbon nanotube that finally obtains for present embodiment, carbon nanotube is dispersed, and length is at 200～500nm, and both ends open.
Embodiment 2
Carbon nanotube 0.4 is restrained ultra-sonic dispersion in the solution of ferrous chloride 33mL of 0.5M, reflow treatment in 80 ℃ of water-baths drips 30% hydrogen peroxide 132mL simultaneously in reactor then, reacts end in 4 hours, cooling back with embodiment 1 filter, washing, in 120 ℃ of dryings 3 hours.With tile quartz boat and place silica tube thermal treatment of the above-mentioned even carbon nanotube that obtains, feed argon shield, be warming up to 400 ℃ with 10 ℃/minute speed, under this temperature, kept 3 hours, the quality percentage composition of the ferric oxide that obtains is 70%.Be warming up to 800 ℃ with same speed again, and be incubated 3 hours.Be cooled to room temperature, again carbon nanotube be dispersed in HNO
3: H
2O is in the dilute nitric acid solution of 2:1 (vol/vol), 100 ℃ of reflow treatment were removed metallic iron and remaining ferric oxide in 2 hours, it is 6 that cooling back is diluted to pH value with deionized water, filters, washs and in 80 ℃ of dryings 6 hours, the short carbon nanometer tube of finally being sheared.Gained short carbon nanometer tube images of transmissive electron microscope is similar to embodiment 1, and length of carbon nanotube is at 200～500nm, and both ends open is dispersed.
Embodiment 3
Carbon nanotube 1 gram ultra-sonic dispersion in the copperas solution 100mL of 0.5M, is dripped 30% hydrogen peroxide 400mL in 80 ℃ of water bath processing processes, react and finished in 4 hours then to filter, wash in reactor, in 120 ℃ of dryings 4 hours with embodiment 1.With tile quartz boat and place silica tube thermal treatment of the above-mentioned even carbon nanotube that obtains, feed argon shield, be warming up to 500 ℃ with 5 ℃/minute speed, under this temperature, kept 2 hours, the quality percentage composition of the ferric oxide that obtains is 80%.Be warming up to 900 ℃ with same speed again, and be incubated 2 hours.Be cooled to room temperature, again carbon nanotube be dispersed in HNO
3: H
2O is in the dilute nitric acid solution of 2:1 (vol/vol), 100 ℃ of reflow treatment were removed metallic iron and remaining ferric oxide in 3 hours, it is 7 that cooling back is diluted to pH value with deionized water, filters, washs and in 100 ℃ of dryings 4 hours, the short carbon nanometer tube of finally being sheared.Gained short carbon nanometer tube images of transmissive electron microscope is similar to embodiment 1, and length of carbon nanotube is at 200～500nm, and both ends open is dispersed.
Claims (10)
1. the cutting method of a multi-walled carbon nano-tubes is characterized in that, the method that adopts wet-chemical is utilized the reaction of carbon reduction ferric oxide again at carbon nano tube surface deposition of iron oxide particle, and carbon nanotube is carried out chemical shearing.
2. the cutting method of multi-walled carbon nano-tubes according to claim 1 is characterized in that, may further comprise the steps:
(1) the ferric oxide presoma is in the deposition of carbon nano tube surface: with the multi-walled carbon nano-tubes ultra-sonic dispersion in the aqueous solution of ferrous salt, violent stirring and drip hydrogen peroxide liquid under 80 ℃ of water bath condition, keep thermotonus after-filtration, drying, obtain the carbon nanotube powder that tube wall adheres to the ferric oxide presoma;
(2) shearing of multi-walled carbon nano-tubes: the carbon nanotube that adheres to the ferric oxide presoma that step (1) is obtained heat temperature raising to 400～500 ℃ under the protection of inert gas in silica tube; under this temperature, keep making presoma be converted into ferric oxide; be warming up to 800～900 ℃ afterwards once more reduction reaction takes place; and under this temperature, be incubated; cooling back gained powder reflow treatment in rare nitric acid; to remove metallic iron and residue ferric oxide, after filtration, the carbon nanotube after obtaining shearing after the washing, drying.
3. the cutting method of multi-walled carbon nano-tubes according to claim 2 is characterized in that, in the step (1), the concentration of aqueous solution of described ferrous salt is 0.5M, and ferrous salt is selected from iron vitriol or iron protochloride.
4. according to the cutting method of claim 2 or 3 described multi-walled carbon nano-tubes, it is characterized in that in the step (1), the organic millipore filtration of F type polyvinylidene difluoride (PVDF) is adopted in described filtration, its filter opening diameter is 0.45 μ m; Described drying was meant: 100～120 ℃ of dryings 2～4 hours.
5. according to the cutting method of claim 2 or 3 described multi-walled carbon nano-tubes, it is characterized in that in the step (1), the ratio of the aqueous solution of described carbon nanotube and ferrous salt is: 0.01～0.02g/ml; The volume ratio of the aqueous solution of described hydrogen peroxide liquid and ferrous salt is: 3～5, and wherein the concentration of hydrogen peroxide liquid is 30%, the concentration of aqueous solution of ferrous salt is 0.5M.
6. according to the cutting method of claim 2 or 3 described multi-walled carbon nano-tubes, it is characterized in that, in the step (1), described maintenance thermotonus, the reaction times is 4 hours.
7. the cutting method of multi-walled carbon nano-tubes according to claim 2 is characterized in that, in the step (2), and described heat temperature raising to 400～500 ℃, its temperature rise rate is 5～10 ℃/minute, soaking time is 2～3 hours under this temperature; Describedly be warming up to 800～900 ℃, its temperature rise rate is 5～10 ℃/minute, and soaking time is 2～3 hours under this temperature.
8. according to the cutting method of claim 2 or 7 described multi-walled carbon nano-tubes, it is characterized in that, in the step (2), described in rare nitric acid reflow treatment, be meant: ultra-sonic dispersion in rare nitric acid, and under 100～120 ℃ temperature back flow reaction 2～3 hours.
9. according to the cutting method of claim 2 or 7 described multi-walled carbon nano-tubes, it is characterized in that in the step (2), described cooling is meant: be cooled to room temperature under inert atmosphere, rare gas element is argon gas or nitrogen.
10. according to the cutting method of claim 2 or 7 described multi-walled carbon nano-tubes, it is characterized in that in the step (2), the organic millipore filtration of F type polyvinylidene difluoride (PVDF) is adopted in described filtration, its filter opening diameter is 0.45 μ m; Described drying was meant: 80～100 ℃ of dryings 2～6 hours.
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| CN103332672B (en) * | 2013-05-15 | 2015-03-04 | 杭州锐杭科技有限公司 | Preparation technology of homogeneous carbon nanotube material |
| CN105668544B (en) * | 2016-01-19 | 2017-11-24 | 南京信息工程大学 | A kind of preparation method of oxidation multi-wall carbon nano-tube tube |
| KR101766156B1 (en) * | 2016-09-06 | 2017-08-07 | 에스케이이노베이션 주식회사 | Method for purifying carbon nanotubes |
| CN106430153A (en) * | 2016-10-18 | 2017-02-22 | 江南大学 | Preparing method of ultrashort carbon nano tube with high dispersibility |
| CN109052370B (en) * | 2018-08-28 | 2022-01-25 | 常州大学 | Carbon nano tube surface modification method |
| CN109603813B (en) * | 2019-01-03 | 2021-09-07 | 江西理工大学 | Preparation method of micro/nano spherical tungsten oxide high-efficiency photocatalyst |
| CN116789108A (en) * | 2023-07-19 | 2023-09-22 | 烯格沃(上海)纳米技术有限公司 | Composition and method for improving yield of single-walled carbon nanotubes |
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