CN105733317A - Preparation method of functionalized carbon nanotube powder - Google Patents
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Abstract
The invention relates to a preparation method of carbon nanotube powder, in particular to a preparation method of functionalized carbon nanotube powder.The method aims at solving the problems that in an existing preparation method of functionalized carbon nanotube powder, the reaction dangerousness is high and difficult to control, the grafting ratio of surface-functionalized groups is difficult to control, and the binding force of a product and a composite is small.The method includes the steps that firstly, carbon nanotubes are put into a tube furnace to be heated and then cooled, and purified carbon nanotubes are obtained; secondly, a FeSO4 solution is prepared, and the pH is regulated; thirdly, the purified carbon nanotubes are put into the FeSO4 solution, suspension is formed, oil bath treatment is carried out, H2O2 is added into the suspension, standing is carried out after the reaction is finished, and a product is obtained; fourthly, washing is carried out, an organic solvent is adopted for replacement, a muddy product is obtained after centrifugation, freeze-drying is carried out, and the functionalized carbon nanotube powder is obtained.According to the method, the reaction is controllable, and the prepared powder can be dispersed in some organic solvents to form a uniform and stable system and has certain orientation capability under specific field intensity.The preparation method is used for preparing functionalized carbon nanotubes.
Description
Technical field
The preparation method that the present invention relates to a kind of carbon nanotube powder.
Background technology
CNT has high intensity, toughness and elastic modelling quantity, great draw ratio and specific surface area, and heat-conductive characteristic is excellent, is the Nano filling of great application potential.CNT has typical stratiform hollow structure feature, and pipe shaft is director circle tubular construction, how to be made up of pentagonal section, there is certain angle between synusia each other.There are some researches show: the difference according to the spiral angle of CNT and diameter structure probably has 1/3 aobvious metallicity, it is possible to conduction, and 2/3 is quasiconductor.Owing to CNT shows the performance of excellence, have broad application prospects in structural material with functional material, but it is insoluble that CNT self structure causes, and it is prone to reunite and lack the practical problems such as surface functional group, significantly limit its application.In recent years, Chinese scholars, in order to solve the problems such as CNT dispersibility and stability, has done a series of research, and different according to functionalization means, the functionalization for CNT is broadly divided into covalent functionalization and non-covalent functionalization two class.
Covalent functionalization is mainly applied chemistry and modifies means, hydroxyl, carboxyl isopolarity group are received end and the surface of CNT, reach the purpose of functionalization, owing to carbon nano tube structure is more stable, this type of reaction kinetic is often with vigorous reaction phenomenon, and the microstructure of CNT can produce certain impact, and what current industry adopted mostly is acid oxidation process CNT.
Non-covalent functionalization is primarily referred to as and CNTs surface is carried out physical treatment, the effects such as intermolecular force, hydrogen bond and electrostatic attraction that rely primarily on promote the dispersion of CNTs, such processing method can make the uniform and stable dispersion of CNT in a solvent, do not damage the one-dimensional electronic structure of CNTs simultaneously, but experiment condition is required harsher, and the repeatability of experiment is poor.
At the production field of finished product functionalized carbon nano-tube powder, carbon nanotube molecule intermolecular forces prepared by first non-state-set prices functionalization is more weak, it is impossible to realize volume production and long-term preservation, is therefore subject to certain limitation in application；Microwave-assisted liquid phase oxidation (acidization) is one of method relatively common in covalent functionalization, and carboxyl can be grafted to the surface of CNT by the method effectively, and after process, the dissolubility of CNT strengthens.At present, commercially available functionalized carbon nano-tube mostly is this kind of method and is prepared from, and this kind of product has the disadvantage that: 1, and owing to technique is limited to, finished product powder still has higher reunion rate；2, surface-functionalized group percent grafting difference is obvious；3, surface is excessively smooth, and between polymer, adhesion is weak；4, almost without microcosmic operability.
Summary of the invention
The present invention is to solve existing method prepare functionalized carbon nano-tube and have that reactivity hazard is difficult to control to greatly, surface-functionalized group percent grafting is difficult to control to, product and the weak problem of composite adhesion, it is provided that the preparation method of a kind of functionalized carbon nano-tube powder.
The preparation method of functionalized carbon nano-tube powder of the present invention, sequentially includes the following steps:
One, by CNT as in tube furnace, 350～500 DEG C of heating heating 1～1.5h under protective atmosphere, removal remains in amorphous carbon and the remaining metallic catalyst on surface, is cooled to room temperature, obtains the CNT after purification after process；
Two, with deionized water for solvent, FeSO4·7H2O is solute, adopts sonic oscillation method to prepare FeSO4Solution, regulates the pH value of solution with dilute sulfuric acid；
Three, the CNT after step one purification is placed in FeSO4In solution, sonic oscillation 30min, form stable carbon nano-tube suspension, then in 15 DEG C of constant temperature oil baths, by H2O2Being added dropwise in carbon nanotube suspension, carry out mechanic whirl-nett reaction under ultra violet lamp, reaction stands after terminating, and obtains product；
Four, by product deionized water wash to neutrality, employing organic solvent replaces deionized water, obtains pureed product, obtain F-CNTs powder after pureed product lyophilization after Centrifugal dispersion.
CNT described in step one is multi-walled carbon nano-tubes, and caliber specification is 10-20 type, 20-40 type or 40-60 type.
Protective atmosphere described in step one is nitrogen atmosphere.
Deionized water described in step 2 and FeSO4·7H2The amount of substance of O is than being (1～10): 1.
The pH value of solution is regulated to 2.0～3.0 described in step 2.
In step 2, the concentration of dilute sulfuric acid is 1.5g/mL.
Mechanic whirl-nett reaction time described in step 3 is 30min～600min.
FeSO in carbon nanotube suspension described in step 34And H2O2Mol ratio be 1: (10～100).
Organic solvent described in step 4 is the organic solvent of both water-soluble, alcohol-soluble and ether dissolubility, or the mixture of several both water-soluble, alcohol-soluble and ether solubleness organic solvent.
Beneficial effects of the present invention:
1, the present invention adopted Fenton oxidation method functionalization CNT, Fe in acid condition2+Can catalysis H2O2Decomposing, the OH, the OH that produce to have Strong oxdiative ability belong to electron deficiency group, and therefore Fenton reagent can attack the unsaturated bond in MWNTs (multi-walled carbon nano-tubes) structure and defective locations, thus realizing the functionalization to MWNTs.The functionalized carbon nano-tube surface of preparation has connected the group such as hydroxyl, carboxyl, can form chemical bond with some substrate molecule, and interface binding power is higher, and the enhancing of matrix material performance is more notable.
2, preparation process of the present invention is simple and easy to do, and this is swift in response, spontaneous chain reaction, and condition requires low to external world.Method is easily operated, and controllability is strong.
3, the present invention can obtain the functionalized carbon nano-tube of hydroxyl, carboxyl grafting, improves CNT dispersibility in some organic solvent, efficiently reduces the reunion between CNT and entanglement.Additionally adopt lyophilization, effectively maintain the dispersibility of functionalized carbon nano-tube, reduce its reunion rate in re-dissolved process, solve CNT agglomeration traits again in roasting and process of lapping.
4, the present invention adopts one-step method can prepare organic group functionized CNT, and can at its area load iron sesquioxide crystal.
5, in functionalization process, regulate the degree of oxidation of CNT by controlling the concentration of OH, it is possible to achieve CNT carries out the cutting of nano-scale, and after cutting, length of carbon nanotube diminishes, but still keep tubular structure.
The length of the ferrous oxide crystal grown for substrate with CNT by controlling the mol ratio of ferrous iron and hydrogen peroxide to control and density.The quality of carbon nanotube loaded ferrous oxide is more big, and paramagnetism strengthens relatively, and orientation can occur under additional the action of a magnetic field.The paramagnetism of application ferrous oxide, it is possible to make functionalized carbon nano-tube align along outer magnetic force direction in liquid matrix material, the performance in certain direction of composite effectively can be strengthened after overcuring.
F-CNTs powder prepared by the present invention, some organic solvent can be scattered in, form uniform and stable system, and under particular field strength, there is certain alignment capability, as Nano filling can be uniform sequential be scattered in matrix material, the present invention is applicable to the preparation of composite, can be used for improving the aspect performances such as the power of matrix material, heat, electricity.
Accompanying drawing explanation
Fig. 1 is untreated CNTs stereoscan photograph；
Fig. 2 is the F-CNTs stereoscan photograph that embodiment 1 obtains；
Fig. 3 stands 15 days after the F-CNTs powder DMAc solvent re-dissolved that embodiment 1 obtains, the photo of macroscopic view deployment conditions；
Fig. 4 is the stereoscan photograph of the F-CNTs that embodiment 2 obtains；
Fig. 5 is the transmission electron microscope photo of the F-CNTs that embodiment 3 obtains；
Fig. 6 is the energy spectrogram of the whisker part of the functionalized carbon nano-tube powder that embodiment 3 obtains；
Fig. 7 stands 15 days after the F-CNTs powder DMAc solvent re-dissolved that embodiment 3 obtains, the photo of macroscopic view deployment conditions.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes the combination in any between each detailed description of the invention.
Detailed description of the invention one: the preparation method of present embodiment functionalized carbon nano-tube powder, sequentially includes the following steps:
One, by CNT as in tube furnace, under protective atmosphere, 350～500 DEG C of heating 1～1.5h, are cooled to room temperature, obtain the CNT after purification after process；
Two, with deionized water for solvent, FeSO4·7H2O is solute, adopts sonic oscillation method to prepare FeSO4Solution, then regulates the pH value of solution；
Three, the CNT after step one purification is placed in FeSO4In solution, sonic oscillation, form stable carbon nano-tube suspension, then in 15 DEG C of constant temperature oil baths, by H2O2Being added dropwise in carbon nanotube suspension, carry out mechanic whirl-nett reaction under ultra violet lamp, reaction stands after terminating, and obtains product；
Four, by product deionized water wash to neutrality, employing organic solvent replaces deionized water, obtains pureed product, namely obtain functionalized carbon nano-tube powder after pureed product lyophilization after Centrifugal dispersion.
Adopting dilute sulfuric acid to regulate pH value in step 2, the concentration of dilute sulfuric acid is 1.5g/mL.
Present embodiment reaction is simple and easy to do, it is easy to operation, controllability is strong.
Present embodiment adopted Fenton oxidation method functionalization CNT, Fe in acid condition2+Can catalysis H2O2Decomposing, the OH, the OH that produce to have Strong oxdiative ability belong to electron deficiency group, and therefore Fenton reagent can attack the unsaturated bond on carbon nano tube structure and defective locations, thus realizing the functionalization to CNT.This reaction response is rapid, spontaneous chain reaction, and condition requires low to external world.
Present embodiment can obtain the functionalized carbon nano-tube of hydroxyl, carboxyl grafting, improves CNT dispersibility in some organic solvent, efficiently reduces the reunion between CNT and entanglement.
Present embodiment adopts lyophilization, effectively maintains the dispersibility of functionalized carbon nano-tube, reduces its reunion rate in re-dissolved process.
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that: CNT described in step one is multi-walled carbon nano-tubes, and caliber specification is 10-20 type, 20-40 type or 40-60 type.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two the difference is that: protective atmosphere described in step one is nitrogen atmosphere.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are the difference is that deionized water described in step 2 and FeSO4·7H2The amount of substance of O is than being (1～10): 1.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to three are the difference is that deionized water described in step 2 and FeSO4·7H2The amount of substance ratio of O is 5: 1.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five the difference is that: regulate the pH value of solution described in step 2 to 2.0～3.0.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six the difference is that: mechanic whirl-nett reaction time described in step 3 is 30min～600min.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to six the difference is that: mechanic whirl-nett reaction time described in step 3 is 120min～240min.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight are the difference is that the FeSO in carbon nanotube suspension described in step 34And H2O2Mol ratio be 1: (10～100).Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to eight are the difference is that the FeSO in carbon nanotube suspension described in step 34And H2O2Mol ratio be 1: (20～80).Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention 11: one of present embodiment and detailed description of the invention one to eight are the difference is that the FeSO in carbon nanotube suspension described in step 34And H2O2Mol ratio be 1: 40.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention 12: one of present embodiment and detailed description of the invention one to ten one the difference is that: in step 3, the sonic oscillation time is 30～40min.Other is identical with one of detailed description of the invention one to ten one.
Detailed description of the invention 13: one of present embodiment and detailed description of the invention one to ten two the difference is that: organic solvent described in step 4 is the organic solvent of both water-soluble, alcohol-soluble and ether dissolubility, or the mixture of several both water-soluble, alcohol-soluble and ether solubleness organic solvent.Other is identical with one of detailed description of the invention one to ten two.
The organic solvent of present embodiment both water-soluble, alcohol-soluble and ether dissolubility includes ethanol, DMAc, DMF, tert-butyl group alcohol or oxolane.
Following experiment is carried out for checking beneficial effects of the present invention:
Embodiment 1:
The preparation method of the present embodiment functionalized carbon nano-tube powder, sequentially includes the following steps:
One, by 40-60 type multi-walled carbon nano-tubes as in tube furnace, 350 DEG C of heating 1h under nitrogen protection atmosphere, removal remains in amorphous carbon and the remaining metallic catalyst on surface, is cooled to room temperature, obtains the CNT after purification after process；
Two, with deionized water for solvent, FeSO4·7H2O is solute, adopts sonic oscillation method to prepare FeSO4Solution, regulates the pH value of solution to 3.0 with dilute sulfuric acid；Described deionized water and FeSO4·7H2The amount of substance ratio of O is 5: 1；
Three, the CNT after step one purification is placed in FeSO4In solution, sonic oscillation 30min, form stable carbon nano-tube suspension, then in 15 DEG C of constant temperature oil baths, by H2O2Being added dropwise in carbon nanotube suspension, under ultra violet lamp, mechanic whirl-nett reaction 120min, reaction stands after terminating, and obtains product；FeSO in described carbon nanotube suspension4And H2O2Mol ratio be 1: 10.
Four, by product deionized water wash to neutrality, employing organic solvent replaces deionized water, obtains pureed product, obtain F-CNTs powder after pureed product lyophilization after Centrifugal dispersion.Described organic solvent is the tert-butyl alcohol and the mixture of ethanol 1: 9 composition in molar ratio.
Fig. 1 is untreated CNTs scanning electron microscopic picture, Fig. 2 is the scanning electron microscopic picture of the functionalized carbon nano-tube powder that embodiment 1 obtains, from picture, we can observe that the CNT after process is more fluffy, to each other from bigger, spatial impression is higher, curvature significantly reduces, and caliber homogeneity is strong, it was demonstrated that the processing method that the present invention relates to can effectively reduce reunion and the entanglement of CNT.Carbon nano tube surface after treatment is coarse, and tubular structure is clear, illustrates that this method can keep the basic pattern of CNT.Fig. 3 stands 15 days after the functionalized carbon nano-tube powder DMAc solvent re-dissolved that embodiment 1 obtains, the photo of macroscopic view deployment conditions.Carbon nanotube powder after can proving functionalization of the present invention with this has good dispersibility and stability in organic solvent.
Embodiment 2:
The preparation method of the present embodiment functionalized carbon nano-tube powder, sequentially includes the following steps:
One, by 40-60 type multi-walled carbon nano-tubes as in tube furnace, 500 DEG C of heating 1h under nitrogen protection atmosphere, removal remains in amorphous carbon and the remaining metallic catalyst on surface, is cooled to room temperature, obtains the CNT after purification after process；
Two, with deionized water for solvent, FeSO4·7H2O is solute, adopts sonic oscillation method to prepare FeSO4Solution, regulates the pH value of solution to 2.0 with dilute sulfuric acid；Described deionized water and FeSO4·7H2The amount of substance ratio of O is 1: 1；
Three, the CNT after step one purification is placed in FeSO4In solution, sonic oscillation 30min, form stable carbon nano-tube suspension, then in 15 DEG C of constant temperature oil baths, by H2O2Being added dropwise in carbon nanotube suspension, under ultra violet lamp, mechanic whirl-nett reaction 240min, reaction stands after terminating, and obtains product；FeSO in described carbon nanotube suspension4And H2O2Mol ratio be 1: 10.
Four, by product deionized water wash to neutrality, deionized water is replaced in employing organic solvent (tert-butyl alcohol), obtains pureed product, obtain F-CNTs powder after pureed product lyophilization after Centrifugal dispersion.
Fig. 4 is the scanning electron microscopic picture of the functionalized carbon nano-tube powder that embodiment 2 obtains, as shown in the figure: the agraphitic carbon of the carbon nano tube surface cladding after process is removed, and caliber slightly increases and essentially identical, and length substantially reduces, each other without tangling.CNT ends thereof after process, overall in shuttle type.Illustrating by the present invention relates to the method adjustment by parameter, simultaneously completing the cutting to carbon nanotube scale dimensions in functionalization, it is possible to adjust carbon nanotube sizes by this kind of method.
Embodiment 3:
The preparation method of the present embodiment functionalized carbon nano-tube powder, sequentially includes the following steps:
One, by 40-60 type multi-walled carbon nano-tubes as in tube furnace, 500 DEG C of heating 1h under nitrogen protection atmosphere, removal remains in amorphous carbon and the remaining metallic catalyst on surface, is cooled to room temperature, obtains the CNT after purification after process；
Two, with deionized water for solvent, FeSO4·7H2O is solute, adopts sonic oscillation method to prepare FeSO4Solution, regulates the pH value of solution to 3.0 with dilute sulfuric acid；Described deionized water and FeSO4·7H2The amount of substance ratio of O is 1: 1；
Three, the CNT after step one purification is placed in FeSO4In solution, sonic oscillation 30min, form stable carbon nano-tube suspension, then in 15 DEG C of constant temperature oil baths, by H2O2Being added dropwise in carbon nanotube suspension, under ultra violet lamp, mechanic whirl-nett reaction 120min, reaction stands after terminating, and obtains product；FeSO in described carbon nanotube suspension4And H2O2Mol ratio be 1: 40.
Four, by product deionized water wash to neutrality, deionized water is replaced in employing organic solvent (tert-butyl alcohol), obtains pureed product, obtain F-CNTs powder after pureed product lyophilization after Centrifugal dispersion.
Fig. 5 is the transmission electron microscope picture of the functionalized carbon nano-tube powder that embodiment 3 obtains, we can see that by the CNT that this method processes from figure, can with CNT for substrate, oriented growth whisker, the density of whisker and length can be passed through test parameters and regulate realization.Fig. 6 is the energy spectrogram of the whisker part of the functionalized carbon nano-tube powder that embodiment 3 obtains.Can drawing by calculating us, the whisker grown on the carbon nanotubes is iron sesquioxide, and therefore the CNT after functionalization has certain paramagnetism.Fig. 7 stands 15 days after the functionalized carbon nano-tube powder DMAc solvent re-dissolved that embodiment 3 obtains, the photo of macroscopic view deployment conditions.It can be seen that the functionalized carbon nano-tube of load iron sesquioxide still has good dissolubility and stability, therefore aligning of CNT can be realized under the effect of functionalized carbon nano-tube suspension outside magnetic field.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, being appreciated that and these embodiments can be carried out multiple change, amendment, replacement and modification without departing from the principles and spirit of the present invention, the scope of the present invention be defined by the appended.
Claims (10)
1. the preparation method of a functionalized carbon nano-tube powder, it is characterised in that the method sequentially includes the following steps:
One, by CNT as in tube furnace, under protective atmosphere, 350～500 DEG C of heating 1～1.5h, are cooled to room temperature, obtain the CNT after purification after process；
Two, with deionized water for solvent, FeSO4·7H2O is solute, adopts sonic oscillation method to prepare FeSO4Solution, then regulates the pH value of solution；
Three, the CNT after step one purification is placed in FeSO4In solution, sonic oscillation, form stable carbon nano-tube suspension, then in 15 DEG C of constant temperature oil baths, by H2O2Being added dropwise in carbon nanotube suspension, carry out mechanic whirl-nett reaction under ultra violet lamp, reaction stands after terminating, and obtains product；
Four, by product deionized water wash to neutrality, employing organic solvent replaces deionized water, obtains pureed product, namely obtain functionalized carbon nano-tube powder after pureed product lyophilization after Centrifugal dispersion.
2. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 1, it is characterised in that CNT described in step one is multi-walled carbon nano-tubes, caliber specification is 10-20 type, 20-40 type or 40-60 type.
3. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 1 and 2, it is characterised in that protective atmosphere described in step one is nitrogen atmosphere.
4. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 3, it is characterised in that deionized water described in step 2 and FeSO4·7H2The amount of substance of O is than being (1～10): 1.
5. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 3, it is characterised in that deionized water described in step 2 and FeSO4·7H2The amount of substance of O is than for 5:1.
6. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 4, it is characterised in that regulate the pH value of solution described in step 2 to 2.0～3.0.
7. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 6, it is characterised in that mechanic whirl-nett reaction time described in step 3 is 30min～600min.
8. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 7, it is characterised in that the FeSO in carbon nanotube suspension described in step 34And H2O2Mol ratio be 1:(10～100).
9. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 8, it is characterised in that in step 3, the sonic oscillation time is 30～40min.
10. the preparation method of a kind of functionalized carbon nano-tube powder according to claim 9, it is characterized in that the organic solvent that organic solvent described in step 4 is both water-soluble, alcohol-soluble and ether dissolubility or the mixture of several both water-soluble, alcohol-soluble and ether solubleness organic solvent.
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| CN107631994A (en) * | 2017-09-13 | 2018-01-26 | 黑龙江省科学院高技术研究院 | A kind of method that functionalized carbon nano-tube modification technique is determined using infrared spectrum |
| CN109273726A (en) * | 2018-02-08 | 2019-01-25 | 成都理工大学 | A kind of carbon coated air electrode material and its preparation method and application |
| CN109052370A (en) * | 2018-08-28 | 2018-12-21 | 常州大学 | A kind of carbon nano tube surface method of modifying |
| CN109052370B (en) * | 2018-08-28 | 2022-01-25 | 常州大学 | Carbon nano tube surface modification method |
| CN109607514A (en) * | 2018-12-28 | 2019-04-12 | 宁波诺丁汉大学 | A kind of combine carbon nano-tube modified reaches environmental protection, the method for high yield and product |
| CN114011395A (en) * | 2021-11-09 | 2022-02-08 | 中国华能集团清洁能源技术研究院有限公司 | Carbon nano tube catalyst prepared by Fenton reagent, method and application |
| WO2023082628A1 (en) * | 2021-11-09 | 2023-05-19 | 中国华能集团清洁能源技术研究院有限公司 | Carbon nanotube catalyst prepared by using fenton's reagent, method and application |
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