CN101559940B - Processing method for electrochemically modifying carbon nano tube - Google Patents
Processing method for electrochemically modifying carbon nano tube Download PDFInfo
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- CN101559940B CN101559940B CN2009100395467A CN200910039546A CN101559940B CN 101559940 B CN101559940 B CN 101559940B CN 2009100395467 A CN2009100395467 A CN 2009100395467A CN 200910039546 A CN200910039546 A CN 200910039546A CN 101559940 B CN101559940 B CN 101559940B
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Abstract
The invention discloses a processing method for electrochemically modifying a carbon nano tube, belonging to the field of modifying nano functional materials. The invention has the steps that the carbon nano tube is used as an electrode material in electrolytic solution, and various electrochemical methods are used for applying voltage or current to the carbon nano tube by an electromechanical instrument so as to modify the carbon nano tube. After the carbon nano tube is modified by the method of the invention, the area of the specific surface of the carbon nano tube is enlarged, the hydrophilicity is obviously enhanced, and the capacitive properties, such as charge volume, charge-discharge current density, cycle number and the like, are also obviously improved. Besides, the modified carbon nano tube can still maintain the original unique and efficient electron transfer characteristic. The carbon nano tube modified by the method of the invention can be used as an efficient electro-catalysis material, a supercapacitor material, a novel carrier of surface functional compound materials, and the like in the field of nano functional materials.
Description
Technical field
The invention belongs to nano-functional material modification field, be specifically related to the processing method for electrochemically modifying of carbon nanotube.
Background technology
Since 1991, the Iijima report found that carbon nanotube is the focus of nano-functional material area research since the carbon nanotube.Nanotube is seamless, the hollow tube body that is rolled into by the graphene film that carbon atom forms, and generally is divided into SWCN (SWNTs) and multi-walled carbon nano-tubes (MWNTs).Carbon nanotube has broad application prospects in many fields because of its particular structure, electricity, optics, magnetic property and mechanical property.But because the water insoluble and common organic solvent of carbon nanotube makes its application receive very big restriction, so carbon nanotube is modified to improve the very big interest that its solvability has caused numerous researchists.In order to obtain the carbon nanotube of solubility, the original intention that a lot of modifying method propose is to make it ability homodisperse in some solution environmental or nano composite material through introducing the appropriate functional group.Through the modification to carbon nanotube, with some wetting abilities, lipophilic group is introduced carbon nanotube, and its solvability is much improved.At present, modal modification route carries out s.t. to carbon nanotube exactly, promptly through carbon nanotube being refluxed in nitric acid or with its ultrasonic concussion in the mixture of sulfuric acid and nitric acid, carboxyl being introduced carbon nanotube.Except that utilizing acid oxidase, can also adopt the method for sulfuric acid and hydrogen peroxide oxidation in carbon nanotube, to introduce carboxyl.The product that obtains by this method need not the help of tensio-active agent, and directly ultrasonic 1～2min in water just can obtain steady suspension.Make the wetting ability of carbon nanotube obtain very big improvement behind the carboxyl-functional.The introducing of carboxyl also makes the carbon nanotube can be through other many functional groups on the organic reaction bonding.In addition, can also utilize noncovalent interactions such as πDian Zi interaction between carbon nanotube and other functional molecular, hydrophobic interaction, can be fixed on the carbon nanotube outer wall to the long-chain organic molecule, thereby obtain the carbon nanotube of solubility.
The method of chemically modified, though can improve the solvability of carbon nanotube greatly, these treatment process processes are complicated, condition is harsh, has many hidden danger during operation, particularly in large-scale industrial production.In addition, though the carbon nanotube that chemical modification method is handled improves,, break other character of having encircled carbon nanotube aspect solvability with also making the carbon pipe produce many defectives.This is that chemical modification method is handled the greatest drawback that the carbon pipe exists.The non covalent bond bonding like πDian Zi interaction, hydrophobic interaction, though can be fixed on the carbon nanotube outer wall to the long-chain organic molecule, obtains the carbon nanotube of solubility.But organic molecule is in the absorption of carbon pipe outer wall, and gathering also will inevitably cause the active site of carbon tube-surface to be capped, thereby has reduced the catalytic activity of carbon pipe, electron transport speed.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of processing method for electrochemically modifying of carbon nanotube is provided, method is simple to operate; Utilize electrochemical method to apply a certain voltage, the electric current that perhaps feeds certain intensity carries out modification to carbon nano-tube material to be handled, and the wetting ability of carbon nano-tube material is strengthened; Improve original characteristic simultaneously; Like electron transport ability, electro catalytic activity, electrical capacity etc.
The object of the invention realizes through following technical scheme:
The processing method for electrochemically modifying of carbon nanotube in electrolyte solution, as electrode materials, adopts electrochemical method that carbon nanotube electrode is applied voltage or electric current with carbon nanotube;
Said electrolyte solution is inorganic or organic electrolyte solution, comprises acidity, alkalescence and neutral electrolyte solution; Like sulphuric acid soln; Pottasium Hydroxide and Klorvess Liquid, organic electrolyte solution comprise the electrolyte system of various organic solutions, like the acetonitrile solution of hexadecyl brometo de amonio.
Said electrochemical method is in the above electrode system of two electrodes, utilizes the voltage and current output on the electrochemical apparatus controlling carbon nanotube material electrode, and said electrochemical method comprises potentiostatic method, cyclic voltammetry or galvanostatic method.
The above electrode system of said two electrodes is meant that with the carbon nano-tube material electrode as working electrode, conducting metal is as counter electrode; Perhaps on two electrode system bases, use extra reference electrode, said reference electrode comprises silver-silver chloride electrode, SCE.
When said inorganic electrolyte solution is acidic electrolyte solution, carbon nanotube electrode is applied 0.5～3V constant voltage handled 3～5 minutes; Perhaps applying 0.1～3mA continuous current handled 5～10 minutes; Perhaps adopt cyclic voltammetry to make voltage between 0.5～3V, use different scanning speed, like 50mV/s, 100mV/s handles the carbon nanotube arbitrary number of times.
When said inorganic electrolyte solution is alkaline electrolyte solution, carbon nanotube electrode is applied 0.8～5V constant voltage handled 3～5 minutes; Perhaps applying 1～4mA continuous current handled 5～10 minutes; Perhaps adopt cyclic voltammetry to make voltage between 0.8～5V, use different scanning speed, like 50mV/s, 100mV/s handles the carbon nanotube arbitrary number of times.
When said inorganic electrolyte solution is neutral electrolyte solution, carbon nanotube electrode is applied 0.8～2V constant voltage handled 3～5 minutes; Perhaps applying 0.5～2mA continuous current handled 1～5 minute; Perhaps adopt cyclic voltammetry to make voltage between 0.8～2V, use different scanning speed, like 50mV/s, 100mV/s handles the carbon nanotube arbitrary number of times.
In said organic electrolyte solution, adopt electrochemical method that carbon nanotube electrode is applied 1～10V constant voltage, handled 1～10 minute; Perhaps apply 0.5～2mA continuous current place 1～5 minute; Perhaps adopt cyclic voltammetry to make voltage between 1～10V, use different scanning speed, like 50mV/s, 100mV/s handles the carbon nanotube arbitrary number of times.
The carbon nano-tube material that the processing method for electrochemically modifying of described carbon nanotube obtains is as the application of function of surface formed material, catalystic material and capacitor electrode material.
Said electrochemical apparatus comprises continuous current instrument, constant potential instrument or electrochemical workstation.
The present invention is with respect to the advantage and the beneficial effect of prior art:
(1) the inventive method is simple to operate, and treatment condition relax.
(2) the inventive method processed carbon nanotubes has bigger specific surface area, and good electron transfer rate and excellent hydrophilic can stably be dispersed in the water equably.In addition, improved charge capacity, strengthened charging and discharging currents density, obtained cycle charge-discharge and waited outstanding capacitive properties often.
(3) carbon nanotube of handling through the inventive method, the wetting ability unique because of its surface is easy to carry out surface-functionalized modification very much, like the depositing nano material, absorption hydrophilic substance etc.
Description of drawings
Fig. 1 is the sem photograph of untreated carbon nanotube;
Fig. 2 is the sem photograph of the inventive method processed carbon nanotubes;
Fig. 3 is the sem photograph of the inventive method processed carbon nanotubes;
Fig. 4 is the contact angle test pattern of untreated carbon nano tube surface;
Fig. 5 is the contact angle test pattern on the inventive method processed carbon nanotubes surface;
Fig. 6 is untreated and the cyclic voltammogram of the inventive method processed carbon nanotubes electrode in potassium ferricyanide solution;
Fig. 7 is untreated and the alternating-current impedance figure of the inventive method processed carbon nanotubes electrode in potassium ferricyanide solution;
Fig. 8 is the untreated cyclic voltammogram of carbon nanotube electrode in the sodium sulfate electrolyte solution of handling with the inventive method;
Fig. 9 is the charge-discharge test figure of the carbon nanotube electrode handled of untreated and the inventive method at the sodium sulfate electrolyte solution;
Figure 10 is the sem photograph of untreated carbon nano tube surface modifying semiconductor oxide compound;
Figure 11 is the sem photograph that the inventive method processed carbon nanotubes is carried out the finishing conductor oxidate.
Embodiment:
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
As substrate, on substrate, spray earlier iron as catalyzer with metal, the method carbon nano-tube on substrate through chemical vapour deposition again, Fig. 1 are the sem photographs of the carbon nanotube that on metal substrate, grows, and the diameter of carbon nanotube is about 80nm.Be cut into little tinsel to the metal substrate of the carbon nanotube of having grown, be prepared into electrode.In the potassium hydroxide solution of 1mol/L plating tank, as working electrode, through the CHI660A electrochemical workstation working electrode is applied the 0.8V constant voltage and handled 5 minutes with carbon nanotube.Fig. 2 is the sem photograph after the processing modification.As can be seen from Figure 2, carbon nanotube has been cut into many segments, and the tube wall of carbon nanotube all obviously increases with terminal defective, thereby causes specific surface area to enlarge markedly.
Embodiment 2:
The preparation of carbon nanotube electrode such as embodiment 1 are said, are cut into little tinsel to the metal substrate of the carbon nanotube of having grown, and are prepared into electrode.In the potassium hydroxide solution of 1mol/L, as working electrode, through the CHI660A electrochemical workstation working electrode is applied the 5V constant voltage and handled 3 minutes with carbon nanotube.Fig. 3 is the sem photograph after the processing modification.As can be seen from Figure 3, after present method processing, carbon nanotube originally has been cut into many segments, and the tube wall of carbon nanotube all obviously increases with terminal defective, thereby causes specific surface area to enlarge markedly, and catalytic efficiency (improves.
Embodiment 3:
The preparation of carbon nanotube electrode such as embodiment 1 are said, are cut into little tinsel to the metal substrate of the carbon nanotube of having grown, and are prepared into electrode.In the potassium hydroxide solution of 1mol/L, as working electrode, through the CHI660A electrochemical workstation working electrode is applied the 1V constant voltage and handled 4 minutes with carbon nanotube.Fig. 4 is the water droplet contact angle test picture of untreated carbon nano tube surface, and the contact angle of water droplet is 141 ° among the figure.Can know that by figure water droplet is not sprawled at the carbon tube-surface fully, the surface of carbon nanotube is super-hydrophobic.Fig. 5 is the water droplet contact angle test picture of the carbon nano tube surface after handling, and the contact angle of water droplet is 53 ° among the figure.By figure can know that water droplet can be sprawled at the carbon tube-surface, the wetting ability on the surface of the carbon nanotube after the processing be improved significantly.
Embodiment 4:
The preparation of carbon nanotube electrode such as embodiment 1 are said.Electrode preparation back well, applies the 0.5mA continuous current through the AUTOLAB electrochemical workstation to carbon nanotube electrode and handled 5 minutes as working electrode with carbon nanotube in the neutral electrolyte solution of the Repone K of 0.1mol/L.Carbon nanotube performance characterization after the inventive method is handled adopts three-electrode system (supporting electrode, reference electrode, working electrode), in different electrolyte solutions, tests.Working electrode for for handled with the inventive method processed carbon nanotubes electrode.Fig. 6 is untreated and the cyclic voltammogram of the inventive method processed carbon nanotubes electrode in potassium ferricyanide solution; The figure dotted line is untreated carbon pipe; Solid line is the carbon pipe after handling; The peak voltage difference of oxidation peak and reduction peak is respectively before and after handling: 59mV and 63mV, the ratio of summit current is all near 1.Can know by figure, the carbon pipe electrode before and after handling, the electron transfer process of Tripotassium iron hexacyanide target molecule is all very fast, the basic no change of electron transport ability of electrode.Handle back carbon Guan Renran and kept efficient electron transfer characteristic.
Embodiment 5:
The preparation of carbon nanotube electrode such as embodiment 1 are said.Electrode preparation back well, applies the 2mA continuous current through the AUTOLAB electrochemical workstation to carbon nanotube electrode and handled 1 minute as working electrode with carbon nanotube in the neutral electrolyte solution of the Repone K of 0.1mol/L.Carbon nanotube performance characterization after the inventive method is handled adopts three-electrode system (supporting electrode, reference electrode, working electrode), in different electrolyte solutions, tests.Working electrode for for handled with the inventive method processed carbon nanotubes electrode.Fig. 7 is untreated and the alternating-current impedance figure of the inventive method processed carbon nanotubes electrode in potassium ferricyanide solution, and astragal is untreated carbon pipe, and dotted line is the carbon pipe after handling.Can know by figure, disciple's transfer impedance basically identical of carbon nanotube electrode before and after handling, also the conclusion with cyclic voltammogram is consistent for this.Carbon Guan Renran has kept efficient electron transfer characteristic after the surface treatment.
Embodiment 6:
The preparation of carbon nanotube electrode such as embodiment 1 are said.Electrode preparation back well, applies the 1mA continuous current through the AUTOLAB electrochemical workstation to carbon nanotube electrode and handled 3 minutes as working electrode with carbon nanotube in the neutral electrolyte solution of the Repone K of 0.1mol/L.Carbon nanotube performance characterization after the inventive method is handled adopts three-electrode system (supporting electrode, reference electrode, working electrode), in different electrolyte solutions, tests.Working electrode for for handled with the inventive method processed carbon nanotubes electrode.Fig. 8 is untreated and the cyclic voltammogram of the inventive method processed carbon nanotubes electrode in 1mol/L sodium sulfate electrolyte solution.Can know that by figure the capacitive current of the carbon pipe after the processing obviously increases, this also has embodiment in the test pattern of Fig. 5, show that the carbon pipe after the processing has very high charge capacity.
Embodiment 7:
The preparation of carbon nanotube electrode such as embodiment 1 are said.Electrode preparation back well as working electrode, through the CHI660C electrochemical workstation, adopts cyclic voltammetry to make voltage with 50mV/s sweep velocity circular treatment 10 times between 0.5～3V with carbon nanotube in the 1mol/L sulphuric acid soln.Handle back seasoning in air.Surface-functionalized modification is being carried out to handling carbon nano-tube material later in dry back, because that the carbon pipe is handled the back is surperficial that wetting ability is greatly improved and is highly susceptible to other material of surface-functionalized modification.Present embodiment adopts the carbon tube-surface of handling is carried out galvanic deposit modifying semiconductor oxide functional material.Figure 10 is the sem photograph of the carbon nano tube surface modifying semiconductor oxide compound of untreated mistake; Figure 11 is the sem photograph that the inventive method processed carbon nanotubes is carried out the finishing conductor oxidate.Can know that by figure compare with untreated carbon pipe, the carbon tube-surface of handling has covered the layer of semiconductor oxide compound uniformly.Therefore the carbon pipe handled of the inventive method is highly susceptible to other material of surface-functionalized modification, can be applied to surface-functionalized field of materials.
Embodiment 8:
The preparation of carbon nanotube electrode such as embodiment 1 are said.Electrode preparation well the back at the acetonitrile solution of 1mol/L hexadecyl brometo de amonio, through the CHI660C electrochemical workstation, adopt cyclic voltammetry make voltage with the 100mV/s sweep velocity at 1～10V, circular treatment carbon nanotube 3 times.Fig. 9 is untreated and the charge-discharge test figure of the inventive method processed carbon nanotubes carbon nanotube electrode in the sodium sulfate electrolyte solution, and dotted line is untreated carbon nanotube, and solid line is a processed carbon nanotubes.Can know by figure; Equally under ten charge-discharge tests; Discharge and recharge needed time basically identical, but the charging and discharging currents of processed carbon nanotubes (70 μ A) is 1000 times of untreatment carbon pipe charging and discharging currents (60nA), explains that the charge capacity of handling back carbon pipe significantly increases.Discharge and recharge the back charge capacity for 5000 times and only decayed 5%.So the carbon pipe that the inventive method was handled is splendid capacitor electrode material.
Claims (1)
1. the processing method for electrochemically modifying of carbon nanotube is characterized in that, in electrolyte solution, as electrode materials, adopts electrochemical method that carbon nanotube electrode is applied voltage or electric current with carbon nanotube;
Said electrolyte solution is sulphuric acid soln, potassium hydroxide solution or Klorvess Liquid;
Said electrochemical method is in the above electrode system of two electrodes, utilizes the voltage and current output on the electrochemical apparatus controlling carbon nanotube material electrode, and said electrochemical method is a galvanostatic method;
The above electrode system of said two electrodes is meant that with the carbon nano-tube material electrode as working electrode, conducting metal is as two electrode systems of counter electrode; Or on two electrode system bases, using extra reference electrode, said reference electrode is silver-silver chloride electrode or SCE;
When said electrolyte solution is acidic electrolyte solution, carbon nanotube electrode is applied 0.1～3mA continuous current handled 5～10 minutes;
When said electrolyte solution is alkaline electrolyte solution, carbon nanotube electrode is applied 1～4mA continuous current handled 5～10 minutes;
When said electrolyte solution is neutral electrolyte solution, carbon nanotube electrode is applied 0.5～2mA continuous current handled 1～5 minute.
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| CN101797502B (en) * | 2010-03-24 | 2012-05-30 | 南京大学 | Preparation method of noble metal-graphene nanometer composite |
| RU2474534C2 (en) * | 2011-05-06 | 2013-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" | Method of activating carbon nanofiller |
| CN102500428A (en) * | 2011-10-25 | 2012-06-20 | 华南理工大学 | Method for improving oxygen reduction performance of negative carbon catalyst of proton exchange membrane fuel cell |
| CN105731425A (en) * | 2016-05-17 | 2016-07-06 | 天津师范大学 | Preparation method for dispersing carbon nanotubes and application |
| CN109665513B (en) * | 2019-01-31 | 2020-10-27 | 中国科学院山西煤炭化学研究所 | Method and device for electrochemically treating carbon particles |
| KR102505830B1 (en) * | 2021-03-18 | 2023-03-03 | 동국대학교 산학협력단 | hydrophilic hybrid fiber, and manufacturing method micro-supercapacitor including hydrophilic hybrid fiber, and manufacturing method |
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