CN102515142A - Method for purification of low-purity single-wall carbon nano-tubes - Google Patents
Method for purification of low-purity single-wall carbon nano-tubes Download PDFInfo
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- CN102515142A CN102515142A CN2011104285177A CN201110428517A CN102515142A CN 102515142 A CN102515142 A CN 102515142A CN 2011104285177 A CN2011104285177 A CN 2011104285177A CN 201110428517 A CN201110428517 A CN 201110428517A CN 102515142 A CN102515142 A CN 102515142A
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Abstract
The invention relates to a method for purification of low-purity single-wall carbon nano-tubes. The method provided by the invention can realize purification of low-purity single-wall carbon nano-tubes by atmospheric oxidation, ultrasonic dispersion, centrifugal separation at different speeds, and hydrogen peroxide refluxing. Concretely, the method provided by the invention comprises the following steps of adding single-wall carbon nano-tube products subjected to atmospheric oxidation into a surfactant solution, carrying out ultrasonic dispersion, carrying out low-speed centrifugal separation and high-speed centrifugal separation to remove impurity particles, carrying out pressure filtration of the supernatant obtained by the high-speed centrifugal separation, mixing the filtrate and hydrogen peroxide, carrying out addition refluxing of the mixture, and carrying out vacuum filtration, flushing and drying to obtain the low-purity single-wall carbon nano-tubes. Compared with the prior art, the method provided by the invention avoids that waste liquid pollution is produced because of single utilization of hydrochloric acid in catalyst removal, and realizes removal of a catalyst according to a principle that the increasing of the weight of an oxidized catalyst is conducive to centrifugal separation. In purification, the centrifugal separation is a main process and oxidation adopting a weak oxidant H2O2 is an auxiliary process and thus the damage on a structure of the single-wall carbon nano-tube is small.
Description
Technical field
The invention belongs to carbon nanotube Technology field, especially relate to a kind of method of purification of low-purity SWCN.
Background technology
(Carbon Nanotubes is a kind of novel hollow tubular nanostructure that is bent to form by two-dimentional graphene film CNTs) to carbon nanotube, is the 4th kind of important allotropic substance of carbon except that graphite, diamond, soccerballene.Multi-walled carbon nano-tubes (Multi-walled carbon nanotubes; MWNTs) in the arc-over cathode deposit, find first in 1991 by Sumio Iijima professor (Iijima); Especially after 2 years SWCN (Single-walled carbon nanotubes, discovery SWNTs) has caused the extensive concern of numerous areas such as comprising physics, chemistry and Materials science.
The direct current arc electric discharge is the efficient production technology of a kind of high quality SWNTs; Prepared SWNTs has percent crystallinity height, few, the electronic mobility advantages of higher of defective; But this technology of preparing is significant disadvantages also; Also be that prepared SWNTs purity is not high, carbon granule or the like the impurity that has more decolorizing carbon, graphite particle, catalyzer in the product and be enclosed with catalyst particle.Therefore the SWNTs product being carried out purification processes is the prerequisite step with the SWNTs widespread use.At present common carbon pipe method of purification can be divided into three major types: 1. chemical method: comprise vapor phase process (air, Cl
2Handle), liquid phase method (HNO
3, H
2O
2, nitration mixture, KMnO
4Deng processing) etc.; 2. physics method: comprise filtration, spinning, high-temperature calcination, red, orange, green, blue, yellow (ROGBY) etc.; 3. synthetic method: filtration-oxidation-ultrasonic-spinning combines, filtration/magnetic filtration-oxidation-methods such as calcining combination.Though these methods can obtain the higher SWNTs of purity, there are shortcomings such as the SWNTS structure deteriorate is serious, purification efficiency is low, the purification cycle is long.Especially aspect purification degree SWNTs, use existing purification techniques to be difficult to realize that SWNTs purifies effectively.Therefore,, need a kind of practicable purifying technique of exploitation, can either obtain highly purified SWNTs, avoid this body structure of SWNTS to be seriously damaged again to the purification of low-purity SWNTs.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of method of purification to the less low-purity SWCN of SWNTs structure deteriorate to be provided.
The object of the invention can be realized through following technical scheme:
A kind of method of purification of low-purity SWCN may further comprise the steps:
(1) the low-purity SWCN is handled back and tensio-active agent mixing ultra-sonic dispersion through atmospheric oxidation, one side is removed the decolorizing carbon that is produced in the preparation process; On the other hand catalyst oxidation is formed its oxide compound, increase the catalyst pellets protonatomic mass;
(2) finely dispersed SWCN solution is carried out low speed, ultra-sonic dispersion-high speed centrifugation separation respectively, remove impurity such as impurity such as comprising catalyst oxidation thing, big graphite particle and little graphite particle respectively;
(3) with mixing and reflux with ydrogen peroxide 50 after the supernatant press filtration behind the high speed centrifugation;
(4) with SWCN solution suction filtration to neutral, be drying to obtain pure SWCN.
Atmospheric oxidation described in the step (1) is treated to puts into air furnace with the arc-over product that contains SWCN, at 360～450 ℃ of following oxide treatment 30～60min.
Tensio-active agent described in the step (1) is sodium lauryl sulphate (SDS), X 2073 (SDBS) or commercially available triton x-100.
It is ultra-sonic dispersion 30～60min under the 3W/mL condition that ultra-sonic dispersion described in the step (1) is treated at power.
Low-purity SWCN described in the step (1) is 1～2wt% at the content of tensio-active agent.
Low-speed centrifugal described in the step (2) is separated into 6000～9000rpm spinning, 30～60min.
Ultra-sonic dispersion-high speed centrifugation described in the step (2) is separated into elder generation to the supernatant ultra-sonic dispersion 10～20min behind the low-speed centrifugal, and then carries out 12000～14000rpm spinning, 30～60min.
Mix the back at 100 ℃ of 4～8h that reflux with ydrogen peroxide 50 after the supernatant press filtration described in the step (3).
Compared with prior art, the present invention need not to utilize hydrochloric acid to remove catalyzer in purification process and causes waste liquor contamination, but weightening finish more helps spinning, its removal the most at last after utilizing catalyst oxidation.Secondly, owing to be main with spinning in the purification process, auxiliary weak oxidant (H
2O
2) oxidation, so purification process is less to the structure deteriorate of SWNTs.
Description of drawings
Fig. 1 is a pure process flow sheet of the present invention;
Fig. 2 is the ESEM picture of SWCN before purifying among the embodiment 1;
Fig. 3 is the ESEM picture of SWCN after purifying among the embodiment 1;
Fig. 4 is the transmission electron microscope picture of SWCN before purifying among the embodiment 1;
Fig. 5 is the transmission electron microscope picture of SWCN after purifying among the embodiment 1;
Fig. 6 is the ESEM picture of resultant SWCN when centrifugal among the embodiment 1;
Fig. 7 is the ESEM picture of resultant SWCN when centrifugal among the embodiment 2.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
According to schema shown in Figure 1,0.5g low-purity SWNTs initial product joined behind 370 ℃ of atmospheric oxidation 30min carry out ultrasonic 30min in the 2wt%SDS solution, then the finely dispersed SWNTs aqueous solution is carried out 9000rpm spinning 30min; Centrifugal end back is taken out supernatant and with the ultrasonic once more 10min of supernatant, is carried out 12000rpm spinning 60min then; The SWCN ESEM picture that obtains is as shown in Figure 6.Next the SDS tensio-active agent is removed in the flushing of the SWNTs supernatant press filtration after centrifugal; The SWNTs product and the 100ml H that come out press filtration then
2O
2Mix and be incorporated in 100 ℃ of heating 5h.At last with SWNTs solution suction filtration to neutral, be drying to obtain pure SWNTs.Fig. 2-5 is respectively stereoscan photograph and the transmission electron microscope photo before and after purifying, and can know that by figure present method can be purified to low-purity SWNTs effectively.
Embodiment 2
According to schema shown in Figure 1,1g low-purity SWNTs initial product joined behind 360 ℃ of atmospheric oxidation 60min carry out ultrasonic 60min in the 2wt%SDBS solution, then the finely dispersed SWNTs aqueous solution is carried out 6000rpm spinning 50min; Centrifugal end back is taken out supernatant and is said the ultrasonic once more 15min of supernatant, carries out 14000rpm spinning 30min then; The SWCN ESEM picture that obtains is as shown in Figure 7.Next the SDBS tensio-active agent is removed in the flushing of the SWNTs supernatant press filtration after centrifugal; The SWNTs product and the 200ml H that come out press filtration then
2O
2Mix and be incorporated in 100 ℃ of heating 4h.At last with SWNTs solution suction filtration to neutral, be drying to obtain pure SWNTs.Can find out in the stereoscan photograph of products therefrom under the different centrifugal speed situation, select different centrifugal speeds to remove gritty particle effectively, make SWNTs purity further improve.
Embodiment 3
According to schema shown in Figure 1,1.2g low-purity SWNTs initial product joined behind 400 ℃ of atmospheric oxidation 30min carry out ultrasonic 30min in the 1wt%SDS solution, then the finely dispersed SWNTs aqueous solution is carried out 6000rpm spinning 40min; Centrifugal end back is taken out supernatant and is said the ultrasonic once more 20min of supernatant, carries out 12000rpm spinning 30min then; Next the SDS tensio-active agent is removed in the flushing of the SWNTs supernatant press filtration after centrifugal; The SWNTs product and the 400ml H that come out press filtration then
2O
2Mix and be incorporated in 100 ℃ of heating 8h.At last with SWNTs solution suction filtration to neutral, be drying to obtain pure SWNTs.
Embodiment 4
According to schema shown in Figure 1; 1.5g low-purity SWNTs initial product joined behind 450 ℃ of atmospheric oxidation 30min in the 2wt% triton x-100 solution carry out ultrasonic 40min, then the finely dispersed SWNTs aqueous solution is carried out 7200rpm spinning 30min; Centrifugal end back is taken out supernatant and with the ultrasonic once more 10min of supernatant, is carried out 13500rpm spinning 30min then; Next the SDS tensio-active agent is removed in the flushing of the SWNTs supernatant press filtration after centrifugal; The SWNTs product and the 350mlH that come out press filtration then
2O
2Mix and be incorporated in 100 ℃ of heating 6h.At last with SWNTs solution suction filtration to neutral, be drying to obtain pure SWNTs.
Embodiment 5
A kind of method of purification of low-purity SWCN may further comprise the steps:
The arc-over product that (1) will contain SWCN is put into air furnace; At 360 ℃ of following oxide treatment 60min; Mix ultra-sonic dispersion 30min with tensio-active agent sodium lauryl sulphate (SDS) then; The low-purity SWCN is 1wt% at the content of tensio-active agent, and it is 3W/mL that ultra-sonic dispersion is treated at power, removes the decolorizing carbon that is produced in the preparation process on the one hand; On the other hand catalyst oxidation is formed its oxide compound, increase the catalyst pellets protonatomic mass;
(2) finely dispersed SWCN solution is carried out low speed, ultra-sonic dispersion-high speed centrifugation separation respectively; Low-speed centrifugal is separated into 6000rpm; Spinning 60min; Ultra-sonic dispersion-high speed centrifugation is separated into elder generation to the supernatant ultra-sonic dispersion 10min behind the low-speed centrifugal, and then carries out 12000rpm spinning 60min, removes impurity such as impurity such as comprising catalyst oxidation thing, big graphite particle and little graphite particle respectively;
(3) with being blended in 100 ℃ of backflow 4h with ydrogen peroxide 50 after the supernatant press filtration behind the high speed centrifugation;
(4) with SWCN solution suction filtration to neutral, be drying to obtain pure SWCN.
Embodiment 6
A kind of method of purification of low-purity SWCN may further comprise the steps:
The arc-over product that (1) will contain SWCN is put into air furnace; At 450 ℃ of following oxide treatment 30min; Mix ultra-sonic dispersion 60min with tensio-active agent X 2073 (SDBS) then; The low-purity SWCN is 2wt% at the content of tensio-active agent, and it is 3W/mL that ultra-sonic dispersion is treated at power, removes the decolorizing carbon that is produced in the preparation process on the one hand; On the other hand catalyst oxidation is formed its oxide compound, increase the catalyst pellets protonatomic mass;
(2) finely dispersed SWCN solution is carried out low speed, ultra-sonic dispersion-high speed centrifugation separation respectively; Low-speed centrifugal is separated into 9000rpm; Spinning 30min; Ultra-sonic dispersion-high speed centrifugation is separated into elder generation to the supernatant ultra-sonic dispersion 20min behind the low-speed centrifugal, and then carries out 14000rpm spinning 30min, removes impurity such as impurity such as comprising catalyst oxidation thing, big graphite particle and little graphite particle respectively;
(3) with being blended in 100 ℃ of backflow 8h with ydrogen peroxide 50 after the supernatant press filtration behind the high speed centrifugation;
(4) with SWCN solution suction filtration to neutral, be drying to obtain pure SWCN.
Above-mentioned all embodiment are being to implement under the prerequisite with technical scheme of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to the above embodiments.
Claims (8)
1. the method for purification of a low-purity SWCN is characterized in that, this method may further comprise the steps:
(1) with the low-purity SWCN after atmospheric oxidation is handled with tensio-active agent mixing ultra-sonic dispersion;
(2) finely dispersed SWCN solution is carried out low speed, ultra-sonic dispersion-high speed centrifugation separation respectively;
(3) with mixing and reflux with ydrogen peroxide 50 after the supernatant press filtration behind the high speed centrifugation;
(4) with SWCN solution suction filtration to neutral, be drying to obtain pure SWCN.
2. the method for purification of a kind of low-purity SWCN according to claim 1; It is characterized in that; Atmospheric oxidation described in the step (1) is treated to puts into air furnace with the arc-over product that contains SWCN, at 360～450 ℃ of following oxide treatment 30～60min.
3. the method for purification of a kind of low-purity SWCN according to claim 1 is characterized in that, the tensio-active agent described in the step (1) is sodium lauryl sulphate (SDS), X 2073 (SDBS) or commercially available triton x-100.
4. the method for purification of a kind of low-purity SWCN according to claim 1 is characterized in that, it is ultra-sonic dispersion 30～60min under the 3W/mL condition that the ultra-sonic dispersion described in the step (1) is treated at power.
5. the method for purification of a kind of low-purity SWCN according to claim 1 is characterized in that, the low-purity SWCN described in the step (1) is 1～2wt% at the content of tensio-active agent.
6. the method for purification of a kind of low-purity SWCN according to claim 1 is characterized in that, the low-speed centrifugal described in the step (2) is separated into 6000～9000rpm spinning, 30～60min.
7. the method for purification of a kind of low-purity SWCN according to claim 1; It is characterized in that; Ultra-sonic dispersion-high speed centrifugation described in the step (2) is separated into elder generation to the supernatant ultra-sonic dispersion 10～20min behind the low-speed centrifugal, and then carries out 12000～14000rpm spinning, 30～60min.
8. the method for purification of a kind of low-purity SWCN according to claim 1 is characterized in that, mixes the back at 100 ℃ of 4～8h that reflux with ydrogen peroxide 50 after the supernatant press filtration described in the step (3).
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| WO2014015510A1 (en) * | 2012-07-27 | 2014-01-30 | 国家纳米科学中心 | Method for treating single wall carbon nanotube |
| CN109650379A (en) * | 2019-02-19 | 2019-04-19 | 厦门大学 | A kind of single-walled carbon nanotube graded oxidation purification process |
| CN111778779A (en) * | 2020-07-06 | 2020-10-16 | 上海安崎智能科技有限公司 | Whisker carbon nanotube far infrared paper and preparation method thereof |
| CN114314566A (en) * | 2021-12-29 | 2022-04-12 | 无锡碳谷科技有限公司 | Separation and purification method of carbon nano tube |
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| WO2014015510A1 (en) * | 2012-07-27 | 2014-01-30 | 国家纳米科学中心 | Method for treating single wall carbon nanotube |
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| CN114314566A (en) * | 2021-12-29 | 2022-04-12 | 无锡碳谷科技有限公司 | Separation and purification method of carbon nano tube |
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Application publication date: 20120627 |