CN109573985A

CN109573985A - A kind of method of microwave separation enriched semiconductor single-walled carbon nanotube

Info

Publication number: CN109573985A
Application number: CN201811212460.5A
Authority: CN
Inventors: 官轮辉; 吴初新; 缪育明
Original assignee: Fujian Institute of Research on the Structure of Matter of CAS
Current assignee: Fujian Institute of Research on the Structure of Matter of CAS
Priority date: 2018-10-18
Filing date: 2018-10-18
Publication date: 2019-04-05

Abstract

The present invention relates to the technical field of single-walled carbon nanotube separating-purifying, especially a kind of method of separation and concentration semi-conductive single-walled carbon nanotubes.By original solid phase single-walled carbon nanotube complete wetting, hydrone is set to sufficiently achieve every single pipe surface, then tempestuously oxide etch selectively occurs with metallicity SWCNT under microwave radiation to react, until reaction stops, the separation and concentration of high-purity semi-conductive single-walled carbon nanotubes of magnanimity is finally realized in a short time.

Description

A kind of method of microwave separation enriched semiconductor single-walled carbon nanotube

Technical field

The present invention relates to the technical field of single-walled carbon nanotube separating-purifying, especially a kind of separation and concentration semiconductive list The method of wall carbon nano tube.

Background technique

Single-walled carbon nanotube (SWCNT) is receiving with one-dimensional hollow tubular structure made of being crimped as single-layer graphene film Rice carbon material.Due to its unique structure and excellent characteristic, have in electronics, calorifics and mechanics related fields wide Application prospect.However, the single-walled carbon nanotube that the preparation method of existing maturation obtains all is metallicity and semiconductive list The mixture of wall carbon nano tube composition, affects the performance of single-walled carbon nanotube intrinsic property, also limits single-walled carbon nanotube In the practice of numerous areas.Especially production of the semi-conductive single-walled carbon nanotubes in flexible and ultra-thin field of microelectronic devices Industryization is applied and is greatly restricted.Therefore, the characteristic of single-walled carbon nanotube semiconductor is made full use of, it just must be to original mixed The single-walled carbon nanotube of conjunction carries out separating-purifying.Nearly ten years, researcher mostly uses greatly following two separating pathway to obtain high-purity Semi-conductive single-walled carbon nanotubes.First kind method is liquid phase method, i.e., carries out in liquid-phase system, and separation and concentration it It goes to toward first by the supplementary means such as the auxiliary reagents such as surfactant, polymer or strong ultrasound, ultracentrifugation by SWCNT The solution for forming high degree of dispersion, is then effectively separated enrichment to SWCNT solution again.Due to SWCNT be usually randomly with The closely packed bundles of bundles of tubes of hexagonal exists, and is very difficult to disperse and dissolve in a solvent.Therefore, although such method The semiconductive SWCNT purity for being finally separating enrichment is higher (usually 95% or more), but since experimentation is related to surpassing Sound dispersion, ultracentrifugation process and more complicated experimental facilities and operating process, so cost costly and is handled Measure fairly limited, general single treatment amount is limited in microgram magnitude, seriously limits the efficiency of scale separation and concentration.Second Class method is directly to carry out separation and concentration under the conditions of solid phase SWCNT using solid phase method, usually will be by some etching property gas Body such as sulfur dioxide, nitrogen dioxide, carbon dioxide etc. carries out selective etch reaction at high temperature, although this method can be real The treating capacity of existing milligram magnitude, however, as original SWCNT be not with existing for single discrete form, but manage with Exist between pipe with the closely packed bundles of bundles of tubes of hexagonal, is again to stack at random between tube bank, mutually winds；And metallicity and half Conducting SWCNT be randomly dispersed among tube bank and random coil together；And metallicity and semiconductive SWCNT it Between chemical reaction otherness it is very faint.So that when using above-mentioned approach processing magnanimity SWCNT, in selective etch metallicity While SWCNT, inevitably adjacent thereto or reactive similar semiconductive SWCNT is damaged, is seriously affected The efficiency and yield of semiconductive SWCNT separation and concentration, simultaneously because the problem of above problem and reaction efficiency causes to obtain SWCNT inevitably introduce more faults of construction.In addition to this, this method is related to hot environment, and not only energy consumption is high And also have corrosiveness to equipment, it also will affect the practical popularization of this method.

Summary of the invention

The purpose of the present invention is to some shortcomings of the prior art, provide a kind of semi-conductive single-walled carbon nanotubes The method of separation and concentration realizes the enrichment of the efficient magnanimity of semi-conductive single-walled carbon nanotubes.

The present invention is achieved by the following technical solutions, by original SWCNT complete wetting, sufficiently achieves hydrone The every surface SWCNT, then under microwave radiation, the hydrone of SWCNT tube wall surface is dissociated into rapidly a large amount of active oxygen certainly By base, which tempestuously oxide etch selectively occurs with metallicity SWCNT and reacts, until reaction stops, finally existing The separation and concentration of the semi-conductive single-walled carbon nanotubes of magnanimity is realized in short time.

The method of the present invention includes the following steps:

The SWCNT of solid phase is sufficiently soaked with suitable water, is then placed it under microwave irradiation, moment is being irradiated, Violent etching reaction occurs for the surface SWCNT, until etching reaction stops, the SWCNT remained is obtained semiconductor Property single-walled carbon nanotube；

The abundant wetting, referring to can be completely by SWCNT moistened surface；

The solid phase SWCNT, solid that can be film-form, sheet, powdery or cotton-shaped.

The microwave irradiation, the time of irradiation are 5s~30min, preferably 5s-120s.

The caliber of the SWCNT is 0.5-2.0nm.

The characteristics of method for separating and concentrating of semi-conductive single-walled carbon nanotubes provided by the invention is different from the prior art exists It directly utilizes to inhale wave microwave radiation strongly in the hydrone of SWCNT molecular surface and be dissociated into oxygen radical in: the present invention and directly exist In situ to be etched with high selectivity to metallicity SWCNT, a step realizes the separation and concentration of high-purity semiconductive SWCNT；The skill Art can effectively solve to exist between Guan Yuguan with the closely packed bundles of bundles of tubes of hexagonal, be again to stack at random between tube bank, mutually The separation problem of the original SWCNT of winding successfully avoids in liquid phase approach in the prior art and solid phase approach to having The original SWCNT wound existing for bundles of bundles of tubes and mutually separates problem hard to work, while passing through quick etching reaction The surface for the semiconductive SWCNT that can be effectively avoided introduces additional fault of construction.The equal energy of energy consumption needed for the invention It makes full use of, energy conservation and environmental protection, and related equipment is simple, it is low in cost.

The invention has the benefit that

1. directly using solid phase SWCNT diaphragm as original material, what is be related to when avoiding the single discrete SWCNT of production is super The complicated processes such as sound dispersion or ultracentrifugation, substantially increase treating capacity and yield.Single treatment amount is from the micro- of the prior art Gram quantity grade is promoted to milligram magnitude, as long as and original SWCNT it is enough, place capacity and production capacity are sufficiently large, and treating capacity is held very much It easily carries out amplifying without limitation；The semiconductive SWCNT purity being finally enriched with still can reach 95% or more, and the semiconductive collected The structure of SWCNT is still intact, and surface defect degree is suitable with original SWCNT, and there is no introduce volume to SWCNT for this method Outer fault of construction.

2. the period of a separation and concentration only uses a few minutes, and instrument and equipment and step that entirely separation process is related to are simple Easy, energy conservation and environmental protection is low in cost, very with the prospect of large-scale production.

Detailed description of the invention

Fig. 1 is the stereoscan photograph of original SWCNT.

The stereoscan photograph for the semiconductive SWCNT that Fig. 2 is.

Fig. 3 is the visible suction of near-infrared-of original SWCNT film (curve A) and obtained semiconductive SWCNT film (curve B) Receive spectrum atlas.

Fig. 4 is the Raman spectrum under 785nm optical maser wavelength of original SWCNT film and obtained semiconductive SWCNT film Map, curve A represent the spectrum line of original SWCNT film, the spectrum line for the semiconductive SWCNT film that curve B is represented.

Specific embodiment

Embodiment 1:

(1) selectively metallicity SWCNT is performed etching:

Original SWCNT diaphragm (carbon pipe diameter be 1.1-2.0nm) is placed in quartz glass substrate, then with it is suitable go from Sub- water soaks SWCNT substantially uniformity, then places them in and carries out microwave irradiation in micro-wave oven, and irradiation process reaction is fast Etching reaction can be completed in speed in 5~120s, then the SWCNT finally remained is obtained semi-conductive single-walled carbon Nanotube.

(2) characterization and analysis of SWCNT sample before and after the processing:

Original SWCNT diaphragm and finally obtained semiconductive SWCNT diaphragm scanning electron microscope, close red has been subjected to respectively The detection of outside-visible absorption spectra, laser capture microdissection Raman spectrum.Fig. 1,2 be respectively original SWCNT and processing after obtain partly lead The stereoscan photograph of body SWCNT, can determine to obtain semiconductive SWCNT from figure and still maintain the intrinsic knot of SWCNT Structure.Fig. 3 is to obtain near-infrared-visible absorption spectra spectrogram of semiconductive SWCNT film after original SWCNT film, processing respectively.From In figure it can be found that after handling by above-mentioned steps, the peak of the metallicity SWCNT in original SWCNT is disappeared, and semiconductor The peak of property SWCNT still retains, and shows that the metallicity SWCNT in SWCNT is almost completely removed, semiconductive SWCNT by Function enrichment is calculated by the relative peak area of absorption peak, and the purity for obtaining semiconductive SWCNT is 95wt%.The Raman light of Fig. 4 Spectrum analysis has further demonstrated that metallicity SWCNT is almost completely removed, and semiconductive SWCNT is successfully enriched with, and can demonstrate,prove Bright obtained semiconductive SWCNT surface defect is suitable with original SWCNT there is no increase.

Embodiment 2:

This embodiment differs from embodiment 1 in that: original SWCNT respectively choice of powder shape, cotton-shaped try It tests, the microwave reaction time is 30s-30min, the semi-conductor type single-walled carbon nano tube of same available 95% or more purity.

Embodiment 3:

This embodiment differs from embodiment 1 in that: it disperses original SWCNT in aqueous phase solution, then by it After the wetting SWCNT obtained after filtering, then carry out same microwave treatment.

Embodiment 6:

This embodiment differs from embodiment 1 in that: the original SWCNT caliber of selection is (0.5~1.3nm).

Claims

1. a kind of method of microwave separation enriched semiconductor single-walled carbon nanotube, which is characterized in that complete by microwave irradiation The single-walled carbon nanotube of wetting, being rapidly selected property etching remove metallic SWNTs therein, obtain semi-conductor type Single-walled carbon nanotube.

2. the method according to claim 1, wherein the following steps are included:

Solid phase single-walled carbon nanotube is sufficiently soaked with suitable water, then places it under microwave irradiation and rapidly etches Reaction, until etching reaction stops, retaining the single-walled carbon nanotube to get off is obtained semi-conductive single-walled carbon nanotubes.

3. according to the method described in claim 2, it is characterized in that, the purity of high-purity single-walled carbon nanotube 95% with On.

4. according to the method described in claim 2, referring to can be completely it is characterized in that, suitable water sufficiently soaks By single-walled carbon nanotube moistened surface.

5. according to the method described in claim 2, it is characterized in that, the solid phase single-walled carbon nanotube, can be film-form , sheet, powdery or cotton-shaped solid.

6. according to the method described in claim 2, it is characterized in that, the microwave irradiation, the time of irradiation be 5s~ 30min, preferably 5s-120s.

7. according to the method described in claim 2, it is characterized in that, the single-walled carbon nanotube, caliber is in 0.5- 2.0nm。