CN102424382B - Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature - Google Patents
Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature Download PDFInfo
- Publication number
- CN102424382B CN102424382B CN 201110276666 CN201110276666A CN102424382B CN 102424382 B CN102424382 B CN 102424382B CN 201110276666 CN201110276666 CN 201110276666 CN 201110276666 A CN201110276666 A CN 201110276666A CN 102424382 B CN102424382 B CN 102424382B
- Authority
- CN
- China
- Prior art keywords
- graphite oxide
- graphene
- acidifying
- specific surface
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a method for preparing graphene under the conditions of normal pressure and low temperature, which comprises the following steps that: firstly, volatile acid is used for treating graphite oxide so that volatile acid molecules are adsorbed between sheet layers of the graphite oxide, acidized graphite oxide is obtained, then, a heat treatment expansion method is adopted for preparing the graphene, experiments prove that the acidized graphite oxide generates a large amount of acid gas in the heat expansion process, and the peeling of the graphite oxide is prompted, so the graphite oxide can generate the expansion peeling in the normal-pressure and low-temperature atmosphere, the graphene can be obtained, and in addition, the obtained graphene has high specific surface area. Therefore, the preparation method provided by the invention is simple, is easy to implement and overcomes the defect of vacuum or low-pressure condition limitation required during the graphene preparation in the prior art, the assurance is provided for the large-scale production of the graphene, and wide market application prospects are realized.
Description
Technical field
The present invention relates to the Graphene technical field, relate in particular to a kind of dilatometry that under the atmospheric low-temperature condition, utilizes and prepare the method for graphene with high specific surface.
Background technology
Graphene is a kind of in recent years emerging, carbon material with special two-dirnentional structure.Excellent calorifics, mechanics and electrical properties; and the ratio of width to height of superelevation and specific surface area make Graphene at electron device, inhale the various fields such as ripple, conductive plastics and have wide potential application foreground, how low-cost, mass-producing ground preparation graphene nano carbon material is one of focus of paying close attention to of present researchist.
Disclosed graphene preparation method comprises chemical method, for example document: STANKOVICH S, DIKIN D A, DOMMETT G H B, et al.Nature, 2006,442,282; Mechanically peel method, for example document: NOVOSELOV KS, GEIM A K, MOROZOV S V, et al.Science, 2004,306,666; Basic metal intercalation and plavini, for example document: VICULIS L M, MACL JJ, KANER R B.Science, 2003,299,1361; Prepared by microwave plasma chemical vapor deposition method, for example document: WANG X B, YOU H J, LIU F M, et al.Chem Vapor Depos, 2009,15,53; And the thermal expansion stripping method of graphite oxide, for example document: SCHNIEPP H C, LI J L, MCALLISTER M J, etal.J Phys Chem B, 2006,110,8535. etc.In these methods, the thermal expansion stripping method of graphite oxide has the prospect of mass-producing preparation and obtains investigator's extensive concern.
The thermal expansion stripping method of graphite oxide is normally carried out under high-temperature pressure.This technology crucial part be: the high temperature atmosphere makes the contained a large amount of oxy radical fast decoupleds of graphite oxide, the speed that the speed of decomposition generation gas diffuses out from graphene sheet layer much larger than gas, this causes the formed pressure of graphene film interlayer far above the Van der Waals force of graphene film interlayer, thereby impels graphene sheet layer successfully to peel off.According to document: McAllister MJ, et al.Chemistry of Materials.2007,19,4396. the calculated results, in the normal pressure atmosphere, graphite oxide success hot soarfing is 550 degree from required minimum temperature, but the thermal expansion temperature of actually operating generally will be higher than 1000 degree.Graphene is in thermal expansion process, its volume will expand dozens or even hundreds of times, high thermal expansion temperature has significantly increased manufacturing cost on the one hand, also be unfavorable on the other hand extensive preparation, and high treatment temp like this, graphite oxide is burnt after reduction is peeled off, not only reduce production efficiency, and cause danger easily.
Chinese patent CN101935035A discloses the method that a kind of low pressure thermal expansion graphite oxide prepares graphene with high specific surface, and the thermal expansion temperature is 0～1000pa but require simultaneously the vacuum tightness of environment below 200 degree in the method.Therefore, the booster action of vacuum or low pressure environment has reduced the expansion temperature of graphite oxide on the one hand, but on the other hand because Graphene is fluffy fine hair shape material, density is little, so vacuum or low pressure condition cause difficulty to the collection of Graphene, also exist production cost high, be unsuitable for the problem of scale operation.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned the deficiencies in the prior art, the method for preparing graphene with high specific surface under a kind of atmospheric low-temperature condition is provided, the method can prepare the Graphene with high-ratio surface under the condition of normal pressure, low temperature, be applicable to the scale operation of Graphene, be with a wide range of applications.
The present invention solves the problems of the technologies described above the technical scheme that adopts: prepare the method for graphene with high specific surface under a kind of atmospheric low-temperature condition, comprise the steps:
Step 1: it is in 0～6.8 the volatile aqueous acid that graphite oxide is immersed pH value, and the volatile acid molecule is adsorbed between the lamella of graphite oxide, then takes out graphite oxide, obtains the graphite oxide of acidifying after the drying;
Perhaps, in comprising the neutral solution of graphite oxide, add the volatile aqueous acid, take the pH value of regulating mixing solutions as 0～6.8, the volatile acid molecule is adsorbed between the lamella of graphite oxide, then with the graphite oxide that obtains acidifying after deionized water wash, filtration, the drying;
Step 2: under normal pressure, kept constant temperature 1 minute～12 hours after the graphite oxide of the acidifying that step 1 is obtained is warming up to 100 ℃～200 ℃, the graphite oxide of acidifying expands and obtains Graphene.
In the technique scheme, graphite oxide can adopt existing preparation method to obtain with the neutral solution that comprises graphite oxide, for example, in reaction vessel, concentrated nitric acid solution, concentrated sulfuric acid solution are evenly mixed with graphite, the an amount of Potcrate of adding or potassium permanganate react under the cooling conditions, obtain solid intermediate product; Then, with this solid intermediate product of deionized water wash, add again the neutralization of an amount of basic solution, obtain pH value and be the neutral solution of 7 graphite oxide; At last, the neutral solution of filtration, dry this graphite oxide obtains graphite oxide.
Described volatile acid includes but not limited to one or more in hydrochloric acid, nitric acid, acetic acid, the oxalic acid.
As preferably, in step 2, the graphite oxide of described acidifying is warming up to 120 ℃～180 ℃.
As preferably, in step 2, after heating up, the graphite oxide of described acidifying kept constant temperature 1 minute～60 minutes.
Utilize the specific surface area of the Graphene that above-mentioned preparation method obtains to reach 500～1000m
2/ g.
Compare with the existing method that under vacuum or low pressure condition, prepares Graphene, the present invention proposes a kind of method that under the atmospheric low-temperature condition, prepares Graphene, the method is at first used volatile acid treatment graphite oxide, the volatile acid molecule is adsorbed between the lamella of graphite oxide, obtain the graphite oxide of acidifying, then adopt the thermal treatment plavini to prepare Graphene, the graphite oxide that experimental results show that acidifying produces a large amount of sour gas in thermal expansion process, promoted peeling off of graphite oxide, graphite oxide can be expanded peel off in the atmosphere of atmospheric low-temperature and obtain Graphene, and the Graphene that obtains has high-specific surface area.Therefore, preparation method provided by the invention is simple, required vacuum or the restriction of low pressure condition when having overcome preparation Graphene in the prior art, for the scale operation of Graphene provides assurance, has widely market application foreground.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the Graphene for preparing of the embodiment of the invention 1.
Embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played any restriction effect.
Embodiment 1:
Step 1: reaction vessel places ice-water bath, and before the reaction beginning, logical high pure nitrogen is got rid of the air in the container first; Then add 90ml concentrated nitric acid and the 175ml vitriol oil, stirring obtains mixed acid solution; Add 10g graphite after the mixed acid solution cooling, stir, then slowly add 110g Potcrate powder, reacted 120 hours; After reaction finishes, with the solid intermediate product that obtains with a large amount of washed with de-ionized water to remove remaining sulfate ion, then neutralize with 1% aqueous sodium hydroxide solution, the pH of adjusting mixing solutions is 7, namely obtains the neutral solution of graphite oxide.
Step 2: in the neutral solution of graphite oxide, add the aqueous solution of hydrochloric acid, take the pH value of regulating this mixing solutions as 0, then filter this mixing solutions, obtain afterwards the graphite oxide of acidifying 80 ℃ of oven dry.
Step 3: under the normal pressure, the graphite oxide of the acidifying that step 2 is obtained is placed in the beaker that is preheated to 180 ℃ in the atmospheric air, keeps 1 minute, and the graphite oxide of acidifying expands to be peeled off, and forms the Graphene of a large amount of pluffy hair shapes.
Fig. 1 is the electromicroscopic photograph that utilizes the Graphene that above-mentioned preparation method obtains.As shown in Figure 1, graphene sheet layer has obtained peeling off fully, has formed the thin layer of nanoscale; A large amount of spaces between the lamella are the architecture basics of Graphene high-specific surface area just.Measure the BET specific surface area of this Graphene up to 955m with the nitrogen adsorption desorption method
2/ g.
The comparative example 1:
In order to compare with embodiment 1, present embodiment does not add the aqueous solution of hydrochloric acid in the neutral solution of graphite oxide, does not namely adopt the pH value of hydrochloric acid adjusting graphite oxide neutral solution and makes it to be acid, and other Step By Conditions are identical with embodiment 1.Specific as follows:
Step 1: identical with embodiment 1;
Step 2: the neutral solution of graphite oxide is filtered, then obtain graphite oxide 80 ℃ of oven dry;
Step 3: under the normal pressure, the graphite oxide that step 2 is obtained is placed in the beaker that is preheated to 180 ℃ in the atmospheric air, keeps 1 minute～12 hours, and graphite oxide expand into a small amount of pulverous Graphene.
Measure the Graphene that above-mentioned preparation method obtains with the nitrogen adsorption desorption method, the BET specific surface area that obtains this Graphene is 15m
2/ g.
The comparative example 2:
In order to compare with embodiment 1, in the present embodiment, with solid intermediate product with a large amount of washed with de-ionized water after, aqueous sodium hydroxide solution with 1% is regulated pH value, the pH that makes mixing solutions is 12, and the aqueous solution that does not also add afterwards hydrochloric acid carries out PH to be regulated, and namely graphite oxide solution is basic solution, rather than neutral solution or acidic solution, other Step By Conditions are identical with embodiment 1.Specific as follows:
Step 1: reaction vessel places ice-water bath, and before the reaction beginning, logical high pure nitrogen is got rid of the air in the container first; Then add 90ml concentrated nitric acid and the 175ml vitriol oil, stirring obtains mixed acid solution; Add 10g graphite after the mixed acid solution cooling, stir, then slowly add 110g Potcrate powder, reacted 120 hours; After reaction finishes, with the solid intermediate product that obtains with a large amount of washed with de-ionized water to remove remaining sulfate ion, then neutralize with 1% aqueous sodium hydroxide solution, the pH of adjusting mixing solutions is 7, namely obtains the basic solution of graphite oxide;
Step 2: with the filtration of alkaline solution of graphite oxide, then obtain graphite oxide 80 ℃ of oven dry;
Step 3: under the normal pressure, the graphite oxide that step 2 is obtained is placed in the beaker that is preheated to 180 ℃ in the atmospheric air, keeps 1 minute～12 hours, and graphite oxide does not expand fully.
By relatively can finding of above-described embodiment 1, comparative example 1 and comparative example 2: under the condition of normal pressure, under identical expansion temperature, regulate graphite oxide and can significantly improve graphite oxide the expand speed of peeling off and the degree that expands and peel off to acid.
Embodiment 2:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, add the aqueous solution of hydrochloric acid, take the pH value of regulating mixing solutions as 1;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 160 ℃ in the atmospheric air, kept 10 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 720m
2/ g.
Embodiment 3:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, add the aqueous solution of hydrochloric acid, take the pH value of regulating mixing solutions as 2;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 140 ℃ in the atmospheric air, kept 30 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 654m
2/ g.
Embodiment 4:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, add the aqueous solution of hydrochloric acid, take the pH value of regulating mixing solutions as 3;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 100 ℃ in the atmospheric air, kept 60 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 553m
2/ g.
Embodiment 5:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, add the aqueous solution of hydrochloric acid, take the pH value of regulating mixing solutions as 4;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 200 ℃ in the atmospheric air, kept 2 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 854m
2/ g.
Embodiment 6:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, add the aqueous solution of acetic acid, take the pH value of regulating mixing solutions as 5;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 160 ℃ in the atmospheric air, kept 15 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 724m
2/ g.
Embodiment 7:
Present embodiment is substantially the same manner as Example 6, and difference is:
In the step 2, add the aqueous solution of acetic acid, take the pH value of regulating mixing solutions as 6.5;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 140 ℃ in the atmospheric air, kept 28 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 632m
2/ g.
Embodiment 8:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, add the mixed aqueous solution of hydrochloric acid and acetic acid, take the pH value of adjusting mixing solutions as 4.3;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 140 ℃ in the atmospheric air, kept 42 minutes.
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 587m
2/ g.
Embodiment 9:
Present embodiment is substantially the same manner as Example 1, and difference is:
In the step 2, at first will obtain graphite oxide after the neutral solution washing of graphite oxide, filtration, the drying; Then graphite oxide is immersed pH value and be in the aqueous solution of 0 hydrochloric acid 1 minute, and then took out graphite oxide, obtain the graphite oxide of acidifying 80 ℃ of oven dry;
Other operations are identical with embodiment 1.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 875m
2/ g.
Embodiment 10:
Present embodiment is substantially the same manner as Example 9, and difference is:
In the step 2, graphite oxide was immersed in the aqueous solution that pH value is 1 hydrochloric acid 10 minutes, then take out graphite oxide, obtain the graphite oxide of acidifying 80 ℃ of oven dry;
In the step 3, the graphite oxide of acidifying is placed in the beaker that is preheated to 160 ℃ in the atmospheric air, kept 10 minutes.
The graphite oxide of acidifying expands with this understanding and peels off, and obtains pluffy hair shape grapheme material.The test of nitrogen adsorption desorption method shows that the specific surface area of the Graphene for preparing is 720m
2/ g.
Claims (4)
1. prepare the method for graphene with high specific surface under the atmospheric low-temperature condition, it is characterized in that: comprise the steps:
Step 1: it is in 0～6.8 the volatile aqueous acid that graphite oxide is immersed the pH value, and the volatile acid molecule is adsorbed between the lamella of graphite oxide, then takes out graphite oxide, obtains the graphite oxide of acidifying after the drying;
Perhaps, in comprising the neutral solution of graphite oxide, add the volatile aqueous acid, take the pH value of regulating mixing solutions as 0～6.8, the volatile acid molecule is adsorbed between the lamella of graphite oxide, then with the graphite oxide that obtains acidifying after deionized water wash, filtration, the drying;
Step 2: under normal pressure, kept constant temperature 1 minute～12 hours after the graphite oxide of the acidifying that step 1 is obtained is warming up to 100 ℃～200 ℃, the graphite oxide of acidifying expands and obtains Graphene;
The BET specific surface area of described Graphene is 500m
2/ g～1000m
2/ g.
2. prepare the method for graphene with high specific surface under the atmospheric low-temperature condition according to claim 1, it is characterized in that: described volatile acid is one or more in hydrochloric acid, nitric acid, the acetic acid.
3. prepare the method for graphene with high specific surface under the atmospheric low-temperature condition according to claim 1 and 2, it is characterized in that: the graphite oxide of described acidifying is warming up to 120 ℃～180 ℃.
4. prepare the method for graphene with high specific surface under the atmospheric low-temperature condition according to claim 1 and 2, it is characterized in that: the time of described maintenance constant temperature is 1 minute～60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110276666 CN102424382B (en) | 2011-09-16 | 2011-09-16 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110276666 CN102424382B (en) | 2011-09-16 | 2011-09-16 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102424382A CN102424382A (en) | 2012-04-25 |
| CN102424382B true CN102424382B (en) | 2013-03-06 |
Family
ID=45958426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110276666 Active CN102424382B (en) | 2011-09-16 | 2011-09-16 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102424382B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387224A (en) * | 2012-05-07 | 2013-11-13 | 海洋王照明科技股份有限公司 | Preparation method of graphite |
| CN103779097A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene-carbon nanotube composite material, and preparation method and application thereof |
| CN103043655B (en) * | 2012-11-29 | 2014-08-13 | 东莞市翔丰华电池材料有限公司 | Preparation method of expanded graphite with high specific surface area |
| CN103011143B (en) * | 2012-12-20 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Graphene and fabrication method thereof and super capacitor |
| CN105417531A (en) * | 2015-12-17 | 2016-03-23 | 中国电子科技集团公司第十八研究所 | Method for preparing graphite at ultra-low temperature |
| CN108630447B (en) * | 2018-04-25 | 2020-04-17 | 山西大学 | Preparation method of graphene membrane electrode with tubular structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935035A (en) * | 2010-09-02 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | Ultra-low temperature thermal expansion preparation method of high specific area graphene |
| CN102153074A (en) * | 2011-03-22 | 2011-08-17 | 西北大学 | Method for preparing graphene with high specific surface area through low-temperature pyrolysis and expansion |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101006903B1 (en) * | 2008-06-03 | 2011-01-13 | 연세대학교 산학협력단 | Preparation process for hollow graphene multilayed nanospheres |
-
2011
- 2011-09-16 CN CN 201110276666 patent/CN102424382B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935035A (en) * | 2010-09-02 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | Ultra-low temperature thermal expansion preparation method of high specific area graphene |
| CN102153074A (en) * | 2011-03-22 | 2011-08-17 | 西北大学 | Method for preparing graphene with high specific surface area through low-temperature pyrolysis and expansion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102424382A (en) | 2012-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102424382B (en) | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature | |
| CN101935035B (en) | Ultra-low temperature thermal expansion preparation method of high specific area graphene | |
| CN103408000B (en) | Preparation method for oxidized grapheme in large sheet | |
| CN102153077A (en) | Method for preparing single-layer graphene with high carbon-oxygen ratio | |
| CN103613093B (en) | A kind of hydrogen reducing prepares the method for Graphene | |
| CN104071782A (en) | Preparation method of graphene | |
| CN104944392A (en) | Mass preparation method of graphite-phase carbon nitride nanosheets | |
| CN103569992A (en) | Preparation method of carbon nanotube | |
| CN104071777A (en) | Preparation method of graphene | |
| CN102009976A (en) | Method for preparing graphene film | |
| CN102923695B (en) | Graphene preparation method | |
| CN103112850B (en) | Method for preparing high-quality graphene through catalytic oxidation multiple-intercalation | |
| CN103935982B (en) | The preparation method of graphene nanobelt | |
| Wang et al. | Self-assembled graphene monoliths: properties, structures and their pH-dependent self-assembly behavior | |
| CN103359713A (en) | Preparation method of graphene | |
| CN103879988A (en) | Boron-doped graphene nano-belt preparation method | |
| Bai et al. | Large-scale preparation of graphene by Red-Al reduction under high gravity technology for supercapacitor application | |
| CN103086358A (en) | Method for preparing graphene | |
| CN103950925B (en) | A kind of preparation method of nanoscale graphite flake | |
| CN110775966B (en) | Flexible graphene film and application thereof | |
| CN103879995B (en) | The preparation method of carbon nanometer wall powder and the preparation method of graphene nanobelt | |
| CN103879991B (en) | The preparation method of graphene nanobelt | |
| CN109553090B (en) | Method for cutting carbon nano tube | |
| CN107935034B (en) | Titanium oxide with few layers and preparation method thereof | |
| CN103935975B (en) | The preparation method of carbon nanometer wall and graphene nanobelt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |