CN101863463A - Method for preparing water dispersible carbon nano tube - Google Patents
Method for preparing water dispersible carbon nano tube Download PDFInfo
- Publication number
- CN101863463A CN101863463A CN 201010174962 CN201010174962A CN101863463A CN 101863463 A CN101863463 A CN 101863463A CN 201010174962 CN201010174962 CN 201010174962 CN 201010174962 A CN201010174962 A CN 201010174962A CN 101863463 A CN101863463 A CN 101863463A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- carbon nano
- aqueous solution
- nitration mixture
- walled carbon
- 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.)
- Pending
Links
Images
Abstract
The invention discloses a method for preparing a water dispersible carbon nano tube, which belongs to the technical field of carbon nano tube material preparation. A single-wall or multi-wall carbon nano tube is placed in aqueous solution of mixed acid of sulfuric acid and nitric acid to perform hydrothermal reaction, and carboxyl can be generated on the surface of the carbon nano tube so that the carbon nano tube has good water dispersibility. The method has the advantages of simple process and easily controlled process parameters, and the prepared water dispersible carbon nano tube has higher length-diameter ratio and high dispersion concentration in water.
Description
Technical field
The invention belongs to the carbon nano-tube material preparing technical field, particularly relate to a kind of preparation method of water decentralized carbon nano-tube, adopt the nitration mixture hydro-thermal reaction to prepare water decentralized carbon nano-tube.Place the nitration mixture aqueous solution of sulfuric acid and nitric acid to carry out hydro-thermal reaction single wall or multi-walled carbon nano-tubes, can generate carboxyl in carbon nano tube surface, thereby make carbon nanotube have superior water dispersibility.
Background technology
Since Japanese scientist professor Iijima in 1991 found carbon nanotube, carbon nanotube was just with its particular structure and good optics, electricity and mechanical characteristic and be subjected to numerous investigators' favor in the field of nanometer technology application prospects.Yet, owing to there is the heavy molecular weight that Van der Waals force and carbon nanotube itself are had between extremely strong pipe between the carbon nanotube, the many pencil forms that form side by side with a large amount of single-root carbon nano-tubes of carbon nanotube exist, make carbon nanotube almost can not be scattered in all solvents, this has greatly limited the practical application of carbon nanotube.Therefore, the carbon nanotube Study on dispersity is the important content in the carbon nano-tube material applied research.
At document (1) Science, 1998,280 (22): among the 1253-1255, people such as Jie Liu carry out shearing treatment with Single Walled Carbon Nanotube in the mixed acid solution of the vitriol oil and concentrated nitric acid, the length of Single Walled Carbon Nanotube can shorten greatly, and forms carboxyl at the end of carbon nanotube; But the Single Walled Carbon Nanotube after should handling needs down auxiliary at tensio-active agent sodium laurylsulfonate or Triton X-100, could form the colloidal solution of stable existence in water.
At document (2) J Am Chem Soc, 2006,128 (32): among the 10568-10571, people such as Zheyi Chen soaked Single Walled Carbon Nanotube 12 hours in oleum, add 65 ℃ of concentrated nitric acids again and stirred 2 hours, after filtration, washing, vacuum-drying, obtain the Single Walled Carbon Nanotube of carboxyl-functional, Single Walled Carbon Nanotube after the processing does not need the auxiliary of tensio-active agent, just can be dispersed in well in polar organic solvent, acid solution and the water.But the mode that should handle carbon nanotube is too fierce, Single Walled Carbon Nanotube be cut into extremely short carbon nanotube (＜60nm).
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of water decentralized carbon nano-tube adopts the nitration mixture hydro-thermal reaction to prepare water decentralized carbon nano-tube.This preparation method's characteristics are to place the nitration mixture aqueous solution of sulfuric acid and nitric acid to carry out hydro-thermal reaction single wall or multi-walled carbon nano-tubes, can generate carboxyl in carbon nano tube surface, thereby make carbon nanotube have superior water dispersibility.Concrete processing step is as follows:
Get the nitration mixture aqueous solution of a certain amount of sulfuric acid and nitric acid, placing with the tetrafluoroethylene is the hydrothermal reaction kettle of liner, and wherein sulfuric acid concentration is 6～13molL
-1, concentration of nitric acid is 2～6molL
-1According to carbon nanotube quality/nitration mixture aqueous solution volume is the ratio of 1g/1L, and single wall or multi-walled carbon nano-tubes are joined in the nitration mixture aqueous solution; The above-mentioned nitration mixture aqueous solution that contains carbon nanotube after 3～12 hours, is naturally cooled to room temperature 100～140 ℃ of hydrothermal treatment consists; The nitration mixture aqueous solution that contains carbon nanotube of hydrothermal treatment consists is joined 8～10 times in the deionized water of mixed acid solution volume with the speed of 0.5～1mL/s, leave standstill fully up to the carbon nanotube precipitation, remove supernatant liquid, lower sediment is the cellulose acetate membrane filtration of 0.4～0.8 μ m with the aperture, being precipitated to filtrate pH value with washing with alcohol is 6～7, obtains carbon nanotube black filter cake; Filter cake 40～70 ℃ of vacuum-dryings 4～12 hours, is obtained water decentralized carbon nano-tube.
Carbon nanotube of the present invention is a kind of in Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes.
Adopt German Cai Si Supra 55 field emission scanning electron microscopes to observe the surface topography of water dispersible single wall and multi-walled carbon nano-tubes, result such as Fig. 1 and shown in Figure 5, the carbon nanotube after the processing still keeps tubular structure, and has high length-to-diameter ratio.Adopt Britain Reinshaw RM 2000 type micro confocal Raman spectrometers that be untreated Single Walled Carbon Nanotube and water dispersible Single Walled Carbon Nanotube are characterized, test result as shown in Figures 2 and 3, as can be seen from the figure, the be untreated D/G value of Single Walled Carbon Nanotube of the D/G value of water dispersible Single Walled Carbon Nanotube obviously increases, the surface imperfection that the water dispersible Single Walled Carbon Nanotube is described increases, but the water dispersible Single Walled Carbon Nanotube still remains with 207cm
-1The characteristic peak of place's Single Walled Carbon Nanotube, this shows that the water dispersible Single Walled Carbon Nanotube structure that adopts the inventive method to prepare is not destroyed.Adopt the U.S.'s thermoelectric Nicolet8700 type Fourier transform infrared spectrometer that water decentralized carbon nano-tube is characterized, test result as shown in Figure 4, at 1709cm
-1The two key stretching vibration peaks of carboxyl C=O appear in the place, show and adopt the inventive method to make carbon nano tube surface carboxylated, and this helps improving the dispersiveness of carbon nanotube in water.The water decentralized carbon nano-tube of the inventive method preparation is carried out the dispersiveness test, and carbon nanotube dispersive concentration in water reaches 10gL
-1More than.
Effect of the present invention and advantage are: adopt the water decentralized carbon nano-tube of the inventive method preparation to have high length-to-diameter ratio and dispersive concentration height in water.In addition, the inventive method technology is simple, processing parameter is more easy to control.
Description of drawings
Fig. 1. the stereoscan photograph of embodiment 1 water dispersible Single Walled Carbon Nanotube.
Fig. 2. the Raman spectrogram of unprocessed Single Walled Carbon Nanotube.X-coordinate is Raman shift, and unit is: centimetre
-1(cm
-1), ordinate zou is a scattering strength, unit is: absolute units (a.u.).
Fig. 3. the Raman spectrogram of embodiment 1 water dispersible Single Walled Carbon Nanotube.X-coordinate is Raman shift, and unit is: centimetre
-1(cm
-1), ordinate zou is a scattering strength, unit is: absolute units (a.u.).
Fig. 4. the Fourier transform infrared spectroscopy figure of embodiment 1 water dispersible Single Walled Carbon Nanotube.X-coordinate is a wave number, and unit is: centimetre
-1(cm
-1), ordinate zou is a transmitance, unit is: percentage ratio (%).
Fig. 5. the stereoscan photograph of embodiment 3 water-dispersion multi-wall nano-carbon tubes.
Embodiment
Embodiment 1:
Getting the 30mL sulfuric acid concentration is 10.3molL
-1Concentration of nitric acid is 4.6molL
-1The nitration mixture aqueous solution, placing with the tetrafluoroethylene is the 100mL hydrothermal reaction kettle of liner, the 30mg Single Walled Carbon Nanotube is added in this mixed acid solution, 120 ℃ of hydrothermal treatment consists 3 hours, naturally cool to room temperature, the nitration mixture aqueous solution that contains carbon nanotube of the hydrothermal treatment consists speed with 0.5mL/s is joined in the 300mL deionized water, leave standstill fully up to the carbon nanotube precipitation, remove supernatant liquid, lower sediment is the cellulose acetate membrane filtration of 0.45 μ m with the aperture, being precipitated to filtrate pH value with washing with alcohol is 7, obtains Single Walled Carbon Nanotube black filter cake; Filter cake 50 ℃ of vacuum-dryings 12 hours, is obtained the water dispersible Single Walled Carbon Nanotube.
The field emission scanning electron microscope photo of water dispersible Single Walled Carbon Nanotube as shown in Figure 1, the water dispersible Single Walled Carbon Nanotube still keeps tubular structure, and has high length-to-diameter ratio.The Raman spectrum of the Single Walled Carbon Nanotube that is untreated and water dispersible Single Walled Carbon Nanotube respectively as shown in Figures 2 and 3, as can be seen from the figure, the be untreated D/G value of Single Walled Carbon Nanotube of the D/G value of water dispersible Single Walled Carbon Nanotube obviously increases, the surface imperfection that the water dispersible Single Walled Carbon Nanotube is described increases, but the water dispersible Single Walled Carbon Nanotube still remains with 207cm
-1The characteristic peak of place's Single Walled Carbon Nanotube, this shows that the water dispersible Single Walled Carbon Nanotube structure that adopts the inventive method to prepare is not destroyed.The infrared spectra of water dispersible Single Walled Carbon Nanotube as shown in Figure 4, at 1709cm
-1The two key stretching vibration peaks of carboxyl C=O appear in the place, show and adopt the inventive method to make carbon nano tube surface carboxylated, and this helps improving the dispersiveness of carbon nanotube in water.
Water dispersible Single Walled Carbon Nanotube dispersive concentration in water adopts following method test: 19.90mg water dispersible Single Walled Carbon Nanotube is joined in the 1mL deionized water ultra-sonic dispersion 1 hour.After dispersion liquid left standstill 3 days, carefully take out supernatant liquid 100 μ L on the slide glass of in advance accurate weighing quality with liquid-transfering gun, there is the dispersion liquid of Single Walled Carbon Nanotube to place 50 ℃ of baking ovens to remove moisture with dripping, quality to twice weighing slide glass does not change, the quality of deduction slide glass promptly obtains the amount that 100 μ L deionized waters disperse Single Walled Carbon Nanotube.Calculating water dispersible Single Walled Carbon Nanotube dispersive concentration in water is 12.6gL
-1
Embodiment 2:
Getting the 30mL sulfuric acid concentration is 6.2molL
-1Concentration of nitric acid is 2.8molL
-1The nitration mixture aqueous solution, placing with the tetrafluoroethylene is the 100mL hydrothermal reaction kettle of liner, the 30mg Single Walled Carbon Nanotube is added in this mixed acid solution, 140 ℃ of hydrothermal treatment consists 3 hours, naturally cool to room temperature, the nitration mixture aqueous solution that contains carbon nanotube of the hydrothermal treatment consists speed with 0.7mL/s is joined in the 240mL deionized water, leave standstill fully up to the carbon nanotube precipitation, remove supernatant liquid, lower sediment is the cellulose acetate membrane filtration of 0.8 μ m with the aperture, being precipitated to filtrate pH value with washing with alcohol is 6, obtains Single Walled Carbon Nanotube black filter cake; Filter cake 60 ℃ of vacuum-dryings 4 hours, is obtained the water dispersible Single Walled Carbon Nanotube.Infrared spectrum characterization has the existence of carboxyl.
Embodiment 3:
Getting the 30mL sulfuric acid concentration is 10.3molL
-1Concentration of nitric acid is 4.6molL
-1The nitration mixture aqueous solution, placing with the tetrafluoroethylene is the 100mL hydrothermal reaction kettle of liner, the 30mg multi-walled carbon nano-tubes is added in this mixed acid solution, 120 ℃ of hydrothermal treatment consists 8 hours, naturally cool to room temperature, the nitration mixture aqueous solution that contains carbon nanotube of the hydrothermal treatment consists speed with 1mL/s is joined in the 300mL deionized water, leave standstill fully up to the carbon nanotube precipitation, remove supernatant liquid, lower sediment is the cellulose acetate membrane filtration of 0.45 μ m with the aperture, being precipitated to filtrate pH value with washing with alcohol is 7, obtains multi-walled carbon nano-tubes black filter cake; Filter cake 70 ℃ of vacuum-dryings 6 hours, is obtained water-dispersion multi-wall nano-carbon tube.Infrared spectrum characterization has the existence of carboxyl.The field emission scanning electron microscope photo of water-dispersion multi-wall nano-carbon tube as shown in Figure 5, water-dispersion multi-wall nano-carbon tube still keeps tubular structure, and has high length-to-diameter ratio.
Embodiment 4:
Getting the 30mL sulfuric acid concentration is 12.6molL
-1Concentration of nitric acid is 5.6molL
-1The nitration mixture aqueous solution, placing with the tetrafluoroethylene is the 100mL hydrothermal reaction kettle of liner, the 30mg Single Walled Carbon Nanotube is added in this mixed acid solution, 100 ℃ of hydrothermal treatment consists 6 hours, naturally cool to room temperature, the nitration mixture aqueous solution that contains carbon nanotube of the hydrothermal treatment consists speed with 0.8mL/s is joined in the 300mL deionized water, leave standstill fully up to the carbon nanotube precipitation, remove supernatant liquid, lower sediment is the cellulose acetate membrane filtration of 0.45 μ m with the aperture, being precipitated to filtrate pH value with washing with alcohol is 7, obtains Single Walled Carbon Nanotube black filter cake; Filter cake 40 ℃ of vacuum-dryings 8 hours, is obtained the water dispersible Single Walled Carbon Nanotube.Infrared spectrum characterization has the existence of carboxyl.
Claims (2)
1. the preparation method of a water decentralized carbon nano-tube is characterized in that, processing step is as follows:
Get the nitration mixture aqueous solution of a certain amount of sulfuric acid and nitric acid, placing with the tetrafluoroethylene is the hydrothermal reaction kettle of liner, and wherein, sulfuric acid concentration is 6～13molL
-1, concentration of nitric acid is 2～6molL
-1According to carbon nanotube quality/nitration mixture aqueous solution volume is the ratio of 1g/1L, and carbon nanotube is joined in the nitration mixture aqueous solution; The above-mentioned nitration mixture aqueous solution that contains carbon nanotube after 3～12 hours, is naturally cooled to room temperature 100～140 ℃ of hydrothermal treatment consists; The nitration mixture aqueous solution that contains carbon nanotube of hydrothermal treatment consists is joined 8～10 times in the deionized water of mixed acid solution volume with the speed of 0.5～1mL/s, leave standstill fully up to the carbon nanotube precipitation, remove supernatant liquid, lower sediment is the cellulose acetate membrane filtration of 0.4～0.8 μ m with the aperture, being precipitated to filtrate pH value with washing with alcohol is 6～7, obtains carbon nanotube black filter cake; Filter cake 40～70 ℃ of vacuum-dryings 4～12 hours, is obtained water decentralized carbon nano-tube.
2. preparation method as claimed in claim 1 is characterized in that, described carbon nanotube is a kind of in Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010174962 CN101863463A (en) | 2010-05-18 | 2010-05-18 | Method for preparing water dispersible carbon nano tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010174962 CN101863463A (en) | 2010-05-18 | 2010-05-18 | Method for preparing water dispersible carbon nano tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101863463A true CN101863463A (en) | 2010-10-20 |
Family
ID=42955438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010174962 Pending CN101863463A (en) | 2010-05-18 | 2010-05-18 | Method for preparing water dispersible carbon nano tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101863463A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN102350234A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院金属研究所 | Dispersion method for carbon nanotubes |
| CN103332672A (en) * | 2013-05-15 | 2013-10-02 | 杭州锐杭科技有限公司 | Preparation technology of homogeneous carbon nanotube material |
| WO2016119568A1 (en) * | 2015-01-27 | 2016-08-04 | 中国石油化工股份有限公司 | Heteroatom-containing nanocarbon material, preparation method and use thereof, and method for dehydrogenation reaction of hydrocarbons |
| CN106185898A (en) * | 2016-07-07 | 2016-12-07 | 重庆德领科技有限公司 | Graphene goes the method for valency electron |
| CN108517006A (en) * | 2018-05-10 | 2018-09-11 | 暨南大学 | Improve carbon nanotube dispersed polypeptide material and its application in water under a kind of normal temperature and pressure conditions |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
-
2010
- 2010-05-18 CN CN 201010174962 patent/CN101863463A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of the American Chemical Society》 20051214 Yubing Wang et al. Rapidly Functionalized, Water-Dispersed Carbon Nanotubes at High Concentration 第96页"Experimental Section"部分 1-2 第128卷, 第1期 2 * |
| 《海南师范学院学报(自然科学版)》 20061231 董军等 多壁碳纳米管的羧基修饰 第342-345、375页 1-2 第19卷, 第4期 2 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN102225754B (en) * | 2011-05-11 | 2013-03-06 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN102350234A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院金属研究所 | Dispersion method for carbon nanotubes |
| CN102350234B (en) * | 2011-06-30 | 2014-03-26 | 中国科学院金属研究所 | Dispersion method for carbon nanotubes |
| CN103332672A (en) * | 2013-05-15 | 2013-10-02 | 杭州锐杭科技有限公司 | Preparation technology of homogeneous carbon nanotube material |
| WO2016119568A1 (en) * | 2015-01-27 | 2016-08-04 | 中国石油化工股份有限公司 | Heteroatom-containing nanocarbon material, preparation method and use thereof, and method for dehydrogenation reaction of hydrocarbons |
| US10537882B2 (en) | 2015-01-27 | 2020-01-21 | China Petroleum & Chemical Corporation | Heteroatom-containing nanocarbon material, preparation method and use thereof, and method for dehydrogenation reaction of hydrocarbons |
| CN106185898A (en) * | 2016-07-07 | 2016-12-07 | 重庆德领科技有限公司 | Graphene goes the method for valency electron |
| CN108517006A (en) * | 2018-05-10 | 2018-09-11 | 暨南大学 | Improve carbon nanotube dispersed polypeptide material and its application in water under a kind of normal temperature and pressure conditions |
| CN108517006B (en) * | 2018-05-10 | 2021-05-28 | 暨南大学 | Polypeptide material for improving dispersibility of carbon nano tube in water under normal temperature and pressure condition and application thereof |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101863463A (en) | Method for preparing water dispersible carbon nano tube | |
| Chen et al. | A dehydration and stabilizer-free approach to production of stable water dispersions of graphene nanosheets | |
| Xu et al. | One-pot liquid-phase exfoliation from graphite to graphene with carbon quantum dots | |
| JP4182215B2 (en) | Carbon nanotube-dispersed polar organic solvent and method for producing the same | |
| Chen et al. | Fast microwave-assisted purification, functionalization and dispersion of multi-walled carbon nanotubes | |
| JP6106339B2 (en) | Dispersant, method for producing the same, and dispersion composition of carbon-based material including the same | |
| Khanam et al. | A facile and novel synthetic method for the preparation of hydroxyl capped fluorescent carbon nanoparticles | |
| Liu et al. | Green synthesis of carbon quantum dots from lignite coal and the application in Fe3+ detection | |
| Li et al. | A new and acid-exclusive method for dispersing carbon multi-walled nanotubes in aqueous suspensions | |
| CN102350234B (en) | Dispersion method for carbon nanotubes | |
| Ng et al. | Improved functionalization and recovery of carboxylated carbon nanotubes using the acoustic cavitation approach | |
| US10995223B2 (en) | Fibrous carbon nanostructure dispersion liquid | |
| Ansón-Casaos et al. | Optical absorption response of chemically modified single-walled carbon nanotubes upon ultracentrifugation in various dispersants | |
| Lei et al. | Ionic liquid of ultralong carbon nanotubes | |
| Haryadi et al. | C dots derived from waste of biomass and their photocatalytic activities | |
| de Oliveira et al. | Engineering the surface of carbon-based nanomaterials for dispersion control in organic solvents or polymer matrices | |
| CN105540567A (en) | Single multi-wall carbon nanotube dispersion liquid and preparation method thereof | |
| Johan et al. | Physico-chemical studies of cuprous oxide (Cu2O) nanoparticles coated on amorphous carbon nanotubes (α-CNTs) | |
| JP4182214B2 (en) | Carbon nanotube dispersed polar organic solvent | |
| Arake et al. | Dispersion of multi-walled carbon nanotube using soluble polysilsesquioxane containing alkylammonium side chains and triiodide counterions | |
| Roy et al. | New insights into the spectral, thermal and morphological analysis of time dependent structural changes during open end functionalization of single walled carbon nanotubes | |
| CN104118862A (en) | Surface modification method of carbon nanotubes | |
| Im et al. | Wet spinning of multi-walled carbon nanotube fibers | |
| EP2710077A1 (en) | Method for producing carbon fillers having covalently bonded amino groups | |
| Wu et al. | Dispersion of single-walled carbon nanotubes in aqueous solution with a thermo-responsive pentablock terpolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20101020 |