CN100469691C - Method of improving chemical activity of carbon nano-tube - Google Patents
Method of improving chemical activity of carbon nano-tube Download PDFInfo
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- CN100469691C CN100469691C CNB2006100897898A CN200610089789A CN100469691C CN 100469691 C CN100469691 C CN 100469691C CN B2006100897898 A CNB2006100897898 A CN B2006100897898A CN 200610089789 A CN200610089789 A CN 200610089789A CN 100469691 C CN100469691 C CN 100469691C
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Abstract
The invention designs a method which can change the appearance of the carbon nanotubes and the surface functional groups through electrooxidation to improve the chemical activity. By adopting the organic supporting membrane, the carbon nanotubes are prepared into membrane with thickness of 0.2mm to 5mm, which is connected with platinum wire as anode; a platinum sheet is used as cathode; chloride solution is used as electrolytic solution; a potentiostat is used to control the open potential in 1.50V to 2.5V (relative to saturated calomel electrode) to carry out constant potential electrolysis in three-electrode electrolytic cell. The electrolytic oxidation treatment process is controllable with low cost and light pollution. The invention has good purification effect on the carbon nanotubes and the chemical activity of the carbon nanotubes after oxidation treatment is obviously improved.
Description
Invention field
The present invention relates to a kind of purifying of carbon nanotube and the method for surface modification, particularly relate to and a kind ofly change carbon nanotube pattern and surface functional group, to improve its chemically active method by potentiostatic deposition.
Background technology
Carbon nanotube is that a kind of radial dimension is a nanometer scale, and axial dimension is the One-dimensional Quantum material that all seal basically at micron dimension, pipe two ends.It mainly is made of one or more layers coaxial pipe the carbon atom that is hexagonal array, diameter is no more than 100nm.Because its particular structure, the research of carbon nanotube has important in theory meaning and potential using value, as: electrochemical catalysis, molecular wire, nano semiconductor material, support of the catalyst, molecular absorption agent, minisize mould and near field emissive material etc.
At present, carbon nanotube mainly contains three kinds of preparation methods, i.e. arc discharge method, laser ablation method and fixed-bed catalytic cracking process.No matter be the carbon nanotube which kind of method is produced, wherein all have a large amount of impurity, typical impurity is agraphitic carbon and as the nano-metal particle of carbon nano tube growth carrier.In addition, the mouth of pipe of the carbon nanotube of new production is generally closed, and the result causes its specific surface area less.When being applied to electrochemical catalysis, carbon nano tube surface functional group, the content of particularly hydrophilic oxygen-containing functional group such as hydroxyl, carboxyl is very big for the catalytic activity influence, and the carbon nano tube surface that commercial run is prepared lacks these oxygen-containing functional groups, and chemically reactive is not high.So, take suitable treatment process to remove impurity in the carbon nanotube, open its two ends mouth of pipe, increase oxygen-containing functional group content, be to improve its chemically active effective ways.
At present, the treatment process of carbon nanotube mainly is a chemical oxidization method, the most frequently used is exactly high density strong acid oxidation style (as Chinese patent CN1613755, CN1733602), cyano group method of substitution (as Chinese patent CN1587031) and high-temperature calcination (as Chinese patent CN1436722, CN1277148), high density strong acid oxidation style can significantly improve the chemically reactive of carbon nanotube, but high density strong acid generally has very strong corrodibility, operation has certain danger, and need to consume a large amount of strong acid, cost an arm and a leg and cause environmental pollution easily; Though the cyano group method of substitution can controlling carbon nanotube surface carboxyl quantity, the operation more complicated is controlled also underaction, and needs to use the azo material of cyano-containing, easily contaminate environment; High-temperature calcination needs higher temperature, and is also more limited for the chemically active raising of carbon nanotube.
In a word, what chemical oxidization method relied on is spontaneously oxide/carbon nanometer tube of oxygenant, and its process control underaction is unfavorable for producing in batches the purifying carbon nano-tube of different purposes, and yield is lower, the production cost height.
Summary of the invention
The objective of the invention is in order to solve the shortcoming that existing carbon nanotube treatment process exists, develop a kind of safety, environmental protection, low cost, process is controlled, yield is higher carbon nanotube treatment process, promptly carbon nanotube is carried out oxide treatment by electrochemical method, thereby make its surface modification, finally reach purifying and activatory purpose.
The principle of the electrochemical oxidation method of processing carbon nanotube provided by the invention is as follows:
Carbon nanotube (CNTs) is made as membranaceous, and as anode, the platinized platinum electrode is a negative electrode, carries out potentiostatic deposition in the potentiostatic deposition pond, and electrolytic solution is certain density chloride soln.In electrolytic process, decolorizing carbon in the carbon nanotube (C) and metal (M) are understood oxidized and are broken away from carbon nano-tube film (wherein x is a positive integer):
C+2H
2O→CO
2↑+4H
++4e
M+xCl
-→MCl
x(aq)+xe
The functional group of carbon nano tube surface also can change:
CNTs-C-H+H
2O→CNTs-C-OH+2H
++2e
CNTs-C-OH+H
2O→CNTs—CO—OH+2H
++2e
Like this, the impurity in the carbon nanotube (decolorizing carbon and metallic particles) is removed, and carbon nano tube surface functional group changes into hydroxyl and carboxyl, thereby has reached purifying and activatory purpose.
The method of electrochemistry purifying provided by the invention and activated carbon nano-tube, its step is as follows:
1) industrial carbon nanotube being in harmonious proportion with solvent is pasty state, utilizes organic membrane as propping material, area 1～1000cm
2, with the pasty state carbon nanotube be deposited in above and floating, carbon nanotube pastes thickness is 0.2～5mm, and fixes a platinum filament therein as lead, carries out drying then under 20～80 ℃ environment, carbon nano-tube film.
2) oxidation processes is carried out in the potentiostatic deposition pond, and wherein carbon nano-tube film is an anode, and the platinized platinum electrode is a negative electrode, and the platinized platinum electrode face amasss 0.25～100cm
2, concentration of electrolyte is 0.01～3.00mol/L.During electrolysis, anode potential is controlled at 1.50～2.50V (with respect to saturated calomel electrode).
3) keep electrolytic potential constant, electrolytic process continues 0.5～600 minute.
Wherein, solvent described in the step 1) is water, methyl alcohol, ethanol, methylene bromide, trichloromethane, tetracol phenixin, methyl-sulphoxide, N, the mixture of one or more in the dinethylformamide; Described carbon nanotube is single wall, double-walled or the multi-walled carbon nano-tubes of arc discharge method, laser ablation method or the preparation of fixed-bed catalytic cracking process, and its external diameter is 1～100nm; Described organic membrane is cellulose membrane, polyethylene film or Teflon film, can use separately that wherein one or more are used with; Described dry environment is meant the artificial environment in physical environment or baking oven, incubator, vacuum drying oven, the retort furnace.
Step 2) pond of potentiostatic deposition described in is a three-electrode cell, and wherein, anode is a working electrode, and negative electrode is a counter electrode, and reference electrode is a saturated calomel electrode; Anode is that a slice carbon nano-tube film or multi-disc carbon nano-tube film compose in parallel; Described electrolytic solution is ammonium chloride, sodium-chlor or Klorvess Liquid.
The constant finger of electrolytic potential described in the step 3) adopts direct current, and the maximum potential variation is no more than 10%.
Compared with prior art, advantage of the present invention is:
Compare with the strong acid oxidation style, present method does not need strong acid, and is with low cost; Do not produce the strong acid waste liquid, clean environment firendly; The electrolytic solution nontoxicity, operational safety; The oxidation selectivity is strong, and yield is higher; Negative electrode produces hydrogen during electrolysis, can collect, and as byproduct, the added value height.Compare with the cyano group method of substitution, this treatment process need not the medicament of cyano-containing, and cost is low and safer to environment.Compare with high-temperature calcination, it is more thorough that present method is removed metallic particles, and purification effect is good; Need not high temperature, save energy.In addition, by the control electrolysis time, can controlling carbon nanotube surface oxy radical quantity, the carbon nanotube product of preparation different activities and different purposes.
Description of drawings
Carbon nanotube infrared spectrogram before and after Fig. 1 electrolysis treatment
(a. potentiostatic deposition is handled the carbon nanotube after 10 minutes; B. undressed carbon nanotube)
Embodiment
Embodiment 1
Adopt cellulose membrane as the carbon nanotube support membrane, it is cut to the rectangle of 1cm * 3cm, wear the platinum filament of a 50mm * 0.1mm on it, an end directly contacts with carbon nanotube, and the other end stretches out outside the cellulose membrane, as lead; Get Single Walled Carbon Nanotube 0.2g, being in harmonious proportion with the 0.5mL ultrapure water is pasty state, evenly is applied to the cellulose membrane surface, with the platinum filament lid below, the about 0.5mm of carbon nanotube layer thickness, standing and drying 3h under room temperature (25 ℃) makes anode I.
Add 1.0mol/L KCl solution as electrolytic solution in the potentiostatic deposition pond, anode I is positioned in the potentiostatic deposition pond, carbon nano-tube film submerges below the liquid level fully.With the platinized platinum electrode is negative electrode, and saturated calomel electrode is as reference electrode, and it is 2.00V that anode potential is set, and keeps constant potential 10 minutes, takes out carbon nano-tube film.By Infrared spectroscopy (Fig. 1), this moment, the carbon nano tube surface group was mainly hydroxyl.After measured, the carbon nanotube yield is 95%.Adopt this method to handle the carbon nanotube that obtains and be suitable for use as the electrochemical sensing modulator material.
Embodiment 2:
Adopt polyethylene film as the carbon nanotube support membrane, it is cut to the rectangle of 2cm * 10cm, wear the platinum filament of a 150mm * 0.1mm on it, an end directly contacts with carbon nanotube, and the other end stretches out outside the polyethylene film, as lead; Get double-walled carbon nano-tube 3.0g, use 3.0mL N, dinethylformamide is in harmonious proportion to pasty state, evenly is applied to the polyethylene film surface, with the platinum filament lid below, the about 1.2mm of carbon nanotube layer thickness, dry 2h in 60 ℃ of baking ovens makes anode II.
In the potentiostatic deposition pond, add 2.0mol/LNH
4Cl solution is positioned over anode II in the potentiostatic deposition pond as electrolytic solution, and carbon nano-tube film submerges below the liquid level fully.With the platinized platinum electrode is negative electrode, and saturated calomel electrode is as reference electrode, and it is 1.70V that anode potential is set, and keeps constant potential 180 minutes, takes out carbon nano-tube film.By transmission electron microscope observation, this moment, the mouth of pipe of most of carbon nanotube was opened, and specific surface area improves.After measured, the carbon nanotube yield is 89%.Adopt this method to handle the carbon nanotube that obtains and be suitable for use as support of the catalyst.
Embodiment 3:
Adopt the Teflon film as the carbon nanotube support membrane, it is cut to the square of 10cm * 10cm, wear the platinum filament of a 150mm * 0.1mm in the middle of the film, an end directly contacts with carbon nanotube, and the other end stretches out outside the Teflon film, as lead; Get multi-walled carbon nano-tubes 5.0g, being in harmonious proportion with the 3.0mL tetracol phenixin is pasty state, evenly is applied to Teflon film surface, with the platinum filament lid below, the about 2.0mm of carbon nanotube layer thickness, dry 2h in 80 ℃ of baking ovens makes anode III.
Add 2.5mol/L NaCl solution as electrolytic solution in the potentiostatic deposition pond, 10 anode III parallel connection is positioned in the potentiostatic deposition pond, carbon nano-tube film submerges below the liquid level fully.With the platinized platinum electrode is negative electrode, and saturated calomel electrode is as reference electrode, and it is 1.90V that anode potential is set, and keeps constant potential 500 minutes, takes out carbon nano-tube film.By the Fourier infrared spectrum analysis, the carbon nano tube surface oxy radical is very abundant.This kind carbon nanotube is easy to be uniformly dispersed in pure water under the condition that does not have tensio-active agent to exist.After measured, the carbon nanotube yield is 79%.Adopt this method to handle the electrocatalysis material that the carbon nanotube that obtains is suitable for use as electrochemical treatment waste water.
Claims (4)
1, a kind of method that improves chemical activity of carbon nano-tube, its step is as follows:
1) industrial carbon nanotube being in harmonious proportion with solvent is pasty state, utilizes organic membrane as propping material, area 1～1000cm
2, with the pasty state carbon nanotube be deposited in above and floating, carbon nanotube pastes thickness is 0.2～5mm, and fixes a platinum filament therein as lead, carries out drying then under 20～80 ℃ environment, carbon nano-tube film;
2) oxidation processes is carried out in the potentiostatic deposition pond, and wherein carbon nano-tube film is an anode, and the platinized platinum electrode is a negative electrode, and the platinized platinum electrode face amasss 0.25～100cm
2, concentration of electrolyte is 0.01～3.00mol/L, during electrolysis, anode potential is controlled at respect to saturated calomel electrode 1.50～2.50V;
3) keep electrolytic potential constant, electrolytic process continues 0.5～600 minute.
2, the method for raising chemical activity of carbon nano-tube according to claim 1, wherein, solvent described in the step 1) is water, methyl alcohol, ethanol, methylene bromide, trichloromethane, tetracol phenixin, methyl-sulphoxide, N, the mixture of one or more in the dinethylformamide; Described carbon nanotube is single wall, double-walled or the multi-walled carbon nano-tubes of arc discharge method, laser ablation method or the preparation of fixed-bed catalytic cracking process, and its external diameter is 1～100nm; Described organic membrane is cellulose membrane, polyethylene film or Teflon film, can use separately that wherein one or more are used with; Described dry environment is meant the artificial environment in physical environment or baking oven, incubator, vacuum drying oven, the retort furnace.
3, the potentiostatic deposition pond is a three-electrode cell the method for raising chemical activity of carbon nano-tube according to claim 1, wherein, step 2), and wherein, anode is a working electrode, and negative electrode is a counter electrode, and reference electrode is a saturated calomel electrode; Anode is that a slice carbon nano-tube film or multi-disc carbon nano-tube film compose in parallel; Described electrolytic solution is ammonium chloride, sodium-chlor or Klorvess Liquid.
4, the method for raising chemical activity of carbon nano-tube according to claim 1, wherein, the constant finger of the electrolytic potential described in the step 3) adopts direct current, and the maximum potential variation is no more than 10%.
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| CN103979526B (en) * | 2014-05-22 | 2016-08-31 | 苏州捷迪纳米科技有限公司 | The purification process of carbon nano-tube macroscopic body |
| CN106158063B (en) * | 2015-04-23 | 2018-01-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube paper, its activation method and application for chemical electric power source electrode material |
| CN105597676B (en) * | 2015-12-31 | 2018-06-12 | 环境保护部华南环境科学研究所 | The preparation method of Metal Substrate charcoal and its application in heavy metal passivation |
| CN106587011B (en) * | 2016-12-09 | 2019-04-02 | 苏州工业园区恒量咨询有限公司 | Purification devices and its method for Purification of Carbon Nanotubes |
| CN110316722B (en) * | 2019-08-13 | 2022-07-01 | 中国人民解放军军事科学院防化研究院 | Preparation method of carbon oxide nanotube |
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| CN1475437A (en) * | 2003-07-31 | 2004-02-18 | 清华大学 | Manufacturing method of carbon nano tube paper |
| CN1786036A (en) * | 2004-12-08 | 2006-06-14 | 北京大学 | Polymer/carbon mano-tube composite film and its preparation method |
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| CN1475437A (en) * | 2003-07-31 | 2004-02-18 | 清华大学 | Manufacturing method of carbon nano tube paper |
| CN1786036A (en) * | 2004-12-08 | 2006-06-14 | 北京大学 | Polymer/carbon mano-tube composite film and its preparation method |
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