CN1613754A - Preparation of high-specific surface area nanometer carbon tube - Google Patents
Preparation of high-specific surface area nanometer carbon tube Download PDFInfo
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- CN1613754A CN1613754A CN 200310105040 CN200310105040A CN1613754A CN 1613754 A CN1613754 A CN 1613754A CN 200310105040 CN200310105040 CN 200310105040 CN 200310105040 A CN200310105040 A CN 200310105040A CN 1613754 A CN1613754 A CN 1613754A
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Abstract
A production of high specific superficial area nanometer carbon tube is carried out by taking sodium hydroxide and potion as activating agent, mixing and dispersing nanometer carbon and activating agent by mechanical ball milling, and activating treating the ball milled nanometer tube mixture under high temperature. It achieves simple process and high specific superficial area for wide application.
Description
Technical field
The present invention relates to CNT (carbon nano-tube), specifically a kind of high-specific area nano carbon tube preparation method.
Background technology
Since Mr. Iijima in 1991 prepares CNT (carbon nano-tube), caused that people pay close attention to widely. because of it has particular structure, quasi-one-dimensional nanometer material, high-specific surface area, good electroconductibility, high stability, also have unique one dimension hollow tubular structure etc., be expected to be used for matrix material, support of the catalyst, the field emission is used for catalyzer and support of the catalyst, lithium-ion secondary cell anode material, electrical condenser, high-efficiency adsorbent, separating agent, adsorbent and hydrogen storage material etc.But the CNT (carbon nano-tube) of preparing generally is sealing two ends, the big and winding mutually of length-to-diameter ratio, so specific surface area is less.These have limited the application of CNT (carbon nano-tube), particularly in fields such as electrical condenser, high-efficiency adsorbent, separating agent, adsorbents, all need to have the CNT (carbon nano-tube) of high-specific surface area.Absorption is the strong interaction between gas molecule and the adsorbent surface molecule, so the size of specific surface area directly influences its adsorptive capacity.The absorption property of carbon absorbent depends on its special surface and pore texture, and also these special surface and pore textures just make carbon absorbent have high specific surface and loading capacity.This just gives the credit to and wherein has a large amount of micropores.The specific surface area of the CNT (carbon nano-tube) of preparation, the CNT (carbon nano-tube) behind the purifying is generally less at present, is approximately 25～280m
2/ g.And through the CNT (carbon nano-tube) behind mechanical disintegration or the chemical activation, since the influence of dispersiveness, activator and technological factor etc., complicated operating process, and its specific surface area effect is also undesirable.
Summary of the invention
The purpose of this invention is to provide the simple relatively high-specific area nano carbon tube preparation method of a kind of operation.
To achieve these goals, technical scheme of the present invention is: adopting sodium hydroxide or potassium hydroxide is activator, add CNT (carbon nano-tube) and add activator simultaneously, adopt the mode of mechanical ball milling that activator and CNT (carbon nano-tube) are mixed and dispersion uniformly fully, and carry out preliminary activation; Mixture with CNT (carbon nano-tube) behind the ball milling and activator carries out priming reaction under 873K～1273K temperature again, then adds hydrochloric acid and removes deactivator and catalyzer (bringing in the original CNT (carbon nano-tube)); Until neutrality, filtration, drying get final product through flushing.
Wherein: CNT (carbon nano-tube) is 1: 1～5 with the ratio of the quality of activator; Ball (steel ball) material (CNT (carbon nano-tube) and activator) mass ratio is: 1～10: 1; The priming reaction time can be 0.5～3 hour; The ball milling time can be 5～60min; The specific surface area of CNT (carbon nano-tube) can be controlled with the processing parameters such as ratio, ratio of grinding media to material and temperature of activator by regulating CNT (carbon nano-tube).
Compare with activated carbon with other method purifying, activatory CNT (carbon nano-tube), the present invention has more following beneficial effect:
1. have the high-specific surface area characteristics, the specific surface area of prepared CNT (carbon nano-tube) can reach 785.2m
2/ g is original CNT (carbon nano-tube) (65m
2/ g) 12 times.
2. technology is simple.The present invention be a kind of both be different from mechanical ball milling or ultrasonication to the simple weak point of CNT (carbon nano-tube) cut, opening, only also be different from and carry out chemically treated a kind of novel method with activator, it effectively used mechanical ball milling to the weak point of CNT (carbon nano-tube) cut, opening and the effect of construction defective, again CNT (carbon nano-tube) and activator are carried out maximum blending dispersion, simultaneously CNT (carbon nano-tube) has been carried out first chemical activation.Then high temperature (as 873K～1273K) further activation, in CNT (carbon nano-tube), produce abundant microporous, prepare the CNT (carbon nano-tube) of high-specific surface area, easy to operate, technology is simple.
3. micropore is abundant, and the aperture is little, and pore size distribution is narrow.Because in the process of mechanical ball milling, CNT (carbon nano-tube) has been carried out sufficient the mixing and dispersion with activator, and a large amount of micropores and defective in CNT (carbon nano-tube), have been produced, activator effectively disperses to have entered these micropores and defective, and activation produces abundant pore texture in follow-up high-temperature process.
4. compare with traditional activated carbon, high-specific area nano carbon pipe still has the feature of CNT (carbon nano-tube), hollow tubular structure, and length-to-diameter ratio is bigger.
5. have broad application prospects.The present invention can be applicable to energy storage material, electrical condenser, high-efficiency adsorbent, separating agent, adsorbent and hydrogen storage material etc.
Description of drawings
Fig. 1 a is the used original CNT (carbon nano-tube) transmission electron microscope photo of the present invention.
Fig. 1 b is the CNT (carbon nano-tube) transmission electron microscope photo of one embodiment of the invention 1.
Fig. 2 a is the high-resolution electron microscopy photo of the used original CNT (carbon nano-tube) of the present invention.
Fig. 2 b is the high-resolution electron microscopy photo of the CNT (carbon nano-tube) of one embodiment of the invention 1.
Fig. 3 a is the sorption isotherm of the nitrogen of the embodiment of the invention 1 CNT (carbon nano-tube).
Fig. 3 b is that the mesopore volume of the embodiment of the invention 1 CNT (carbon nano-tube) distributes.
Fig. 3 c is that the micropore pore volume of the embodiment of the invention 1 CNT (carbon nano-tube) distributes.
Fig. 4 a is the sorption isotherm of the nitrogen of the embodiment of the invention 2 CNT (carbon nano-tube).
Fig. 4 b is that the mesopore volume of the embodiment of the invention 2 CNT (carbon nano-tube) distributes.
Fig. 4 c is that the micropore pore volume of the embodiment of the invention 2 CNT (carbon nano-tube) distributes.
Fig. 5 is the sorption isotherm of the nitrogen of the embodiment of the invention 3 CNT (carbon nano-tube).
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
Employing potassium hydroxide is activator, adds CNT (carbon nano-tube) and adds activator simultaneously, with the mode of mechanical ball milling activator and CNT (carbon nano-tube) is mixed and dispersion uniformly fully, and the ball milling time is 30min.Wherein: CNT (carbon nano-tube) and activator (quality, down with) are than being 1: 4; Ball material (quality, down with) is than being 3: 1, and the priming reaction 1 hour under the 1123K temperature of the CNT (carbon nano-tube) mixture behind the ball milling is then used hydrochloric acid eccysis deactivator and catalyzer (bringing in the original CNT (carbon nano-tube)); Use a large amount of deionized water rinsings until neutrality again, filtration, drying.The specific surface area of prepared CNT (carbon nano-tube) is 785.2m
2/ g.
The principle of the invention is: in the process of mechanical ball milling, effectively used mechanical ball milling to the weak point of CNT (carbon nano-tube) cut, opening and the effect of construction defective, CNT (carbon nano-tube) and activator maximum mixing and dispersion have been carried out, cause in CNT (carbon nano-tube), having produced a large amount of micropores and defective, make activator can disperse and enter these micropores and defective effectively, CNT (carbon nano-tube) has been carried out first chemical activation, and at high temperature further activating, make and produce the abundant microporous structure in the CNT (carbon nano-tube).
Compare (as shown in Figure 1a) with the primary CNT (carbon nano-tube), Fig. 1 b is depicted as the transmission electron microscope photo of the high-ratio surface CNT (carbon nano-tube) after present embodiment ball milling and the pyroprocessing.As can be seen, CNT (carbon nano-tube) short cut, opening.Fig. 2 b is depicted as the high-resolution-ration transmission electric-lens photo of high-ratio surface CNT (carbon nano-tube) after ball is touched mill and pyroprocessing.As can be seen, produced a large amount of defectives and hole on the tube wall of CNT (carbon nano-tube), this produces under ball milling and potassium hydroxide etch effect.CNT (carbon nano-tube) of the present invention has high-specific surface area, and (referring to Fig. 3 a), micropore is abundant, and the aperture is little, and pore size distribution is narrow; Find out that from Fig. 3 b high-specific area nano carbon pipe has the pore distribution of the last one at 3-4nm, find out that high-specific area nano carbon pipe has the pore distribution of the last one at 1.6nm, and primary CNT (carbon nano-tube) micropore seldom from Fig. 3 c.The feature of CNT (carbon nano-tube), hollow tubular structure have been kept with traditional activated carbon with it.
Embodiment 2
Difference from Example 1 is:
Employing potassium hydroxide is activator, and activator and CNT (carbon nano-tube) are mixed and dispersion uniformly fully, and the ball milling time is 25min.CNT (carbon nano-tube) mixture behind ball milling priming reaction 3 hours under the 873K temperature then removes deactivator and catalyzer with the concentrated hydrochloric acid pickling; Wherein: CNT (carbon nano-tube) is 1: 5 with the activator ratio; Ratio of grinding media to material is 10: 1, and the specific surface area of prepared CNT (carbon nano-tube) is 542.3m
2/ g.
Referring to Fig. 4 a, 4b, 4c, CNT (carbon nano-tube) of the present invention is compared with the primary CNT (carbon nano-tube), and the identical trend of embodiment 1 is arranged.
Embodiment 3
Difference from Example 1 is:
Employing potassium hydroxide is activator, adopts the mode of mechanical ball milling that activator and CNT (carbon nano-tube) are mixed and dispersion uniformly fully, and the ball milling time is 60min.CNT (carbon nano-tube) mixture behind ball milling priming reaction 1 hour under the 1273K temperature then adds hydrochloric acid and removes deactivator and catalyzer; Wherein: CNT (carbon nano-tube) is 1: 1 with the ratio of activator; Ratio of grinding media to material is 2: 1, and the specific surface area of prepared CNT (carbon nano-tube) is 488m
2/ g.
Referring to Fig. 5, CNT (carbon nano-tube) of the present invention is compared with the primary CNT (carbon nano-tube), and the identical trend of embodiment 1 is arranged.
Claims (6)
1. high-specific area nano carbon tube preparation method is characterized in that: add CNT (carbon nano-tube) and add activator simultaneously, the mode that adopts mechanical ball milling is mixed activator and CNT (carbon nano-tube) and is disperseed, and carries out primary activation; Mixture with CNT (carbon nano-tube) behind the ball milling and activator carries out priming reaction under high-temperature again, then removes deactivator, and flushing is extremely neutral again, filtration, dry getting final product.
2. according to the described high-specific area nano carbon of claim 1 tube preparation method, it is characterized in that: the priming reaction temperature is 873K～1273K under the described high temperature, and the priming reaction time can be 0.5～3 hour.
3. according to the described high-specific area nano carbon of claim 1 tube preparation method, it is characterized in that: described activator can be sodium hydroxide or potassium hydroxide.
4. according to the described high-specific area nano carbon of claim 1 tube preparation method, it is characterized in that: described CNT (carbon nano-tube) can be 1: 1～5 with the ratio of the quality of activator.
5. according to the described high-specific area nano carbon of claim 1 tube preparation method, it is characterized in that: described ball material mass ratio can be 1～10: 1.
6. according to the described high-specific area nano carbon of claim 1 tube preparation method, it is characterized in that: the described ball milling time can be 5～60min.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101050404A CN1313365C (en) | 2003-11-07 | 2003-11-07 | Preparation of high-specific surface area nanometer carbon tube |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101050404A CN1313365C (en) | 2003-11-07 | 2003-11-07 | Preparation of high-specific surface area nanometer carbon tube |
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|---|---|
| CN1613754A true CN1613754A (en) | 2005-05-11 |
| CN1313365C CN1313365C (en) | 2007-05-02 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314584C (en) * | 2005-06-17 | 2007-05-09 | 华东师范大学 | Process for preparing nanometer carbon particles |
| CN102190293A (en) * | 2010-03-10 | 2011-09-21 | 通用汽车环球科技运作有限责任公司 | Microporous carbon material and methods of forming same |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091073C (en) * | 1998-12-25 | 2002-09-18 | 中国科学院山西煤炭化学研究所 | Preparation of active carbon adsorbing and storing methane |
-
2003
- 2003-11-07 CN CNB2003101050404A patent/CN1313365C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314584C (en) * | 2005-06-17 | 2007-05-09 | 华东师范大学 | Process for preparing nanometer carbon particles |
| CN102190293A (en) * | 2010-03-10 | 2011-09-21 | 通用汽车环球科技运作有限责任公司 | Microporous carbon material and methods of forming same |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
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|---|---|
| CN1313365C (en) | 2007-05-02 |
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Granted publication date: 20070502 Termination date: 20101107 |