CN101745434A - Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube - Google Patents
Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube Download PDFInfo
- Publication number
- CN101745434A CN101745434A CN200810229969A CN200810229969A CN101745434A CN 101745434 A CN101745434 A CN 101745434A CN 200810229969 A CN200810229969 A CN 200810229969A CN 200810229969 A CN200810229969 A CN 200810229969A CN 101745434 A CN101745434 A CN 101745434A
- Authority
- CN
- China
- Prior art keywords
- ferric oxide
- oxide particles
- filled
- cnt
- selectivity
- 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.)
- Granted
Links
Images
Abstract
The invention relates to the selectively filling of ferric oxide particles in the hollow cavity of a carbon nanotube, in particular to a method for selectively filling ferric oxide particles in the hollow cavity of a carbon nanotube, with accurate and controllable ferric oxide particle filling amount and size, and the application of a filling compound. An anodic alumina membrane with a regular pore structure is taken as a template, and a carbon layer is evenly deposited on the template by a chemical vaporous deposition method, and then an anodic alumina membrane/carbon compound is obtained; the compound is put in a ferric nitrate solution and then is ultrasonically shaken at room temperature; the anodic alumina membrane/carbon compound is taken out and then is treated under the protective atmosphere after being dried; ferric nitrate is decomposed into ferric oxide; then the anodic alumina template is removed; and finally, a carbon nanotube that the ferric oxide particles are selectively filled in the hollow cavity of the carbon nanotube is obtained. The ferric oxide particles are selectively filled in the hollow cavity of the carbon nanotube, the content by weight of the ferric oxide particles is between 5 percent and 70 percent and is accurate, even and controllable, and the sizes of the ferric oxide particles are between 1nm and 10nm and is controllable.
Description
Technical field
The present invention relates to ferric oxide particles and fill, be specially the accurately controlled method of a kind of ferric oxide particles selectivity filling, ferric oxide particles loading and size in CNT hollow tube chamber and the purposes of filled composite in the intraluminal selectivity of CNT hollow.
Background technology
The modern humans is faced with problems such as the energy, environmental pollution, and the solution of these problems all needs to depend in large quantities catalytic process.Carrier is being played the part of important role in catalytic process, it is as the skeleton of supported catalyst, it mainly acts on and increases active surface and suitable hole is provided, the activated centre is provided, improves the thermal conductivity and the heat endurance of catalyst, improves the mechanical strength of catalyst and performance (between carrier and catalyst activity component chemical action taking place) etc.
CNT can regard that certain crooked and space topological structure of forming takes place Graphene hexagon grid as, the hollow tube chamber that have that chemical stability is good, heat shock resistance, electric conductivity uniqueness, intensity height, specific area are big, has nanoscale, with excellent properties such as biocompatible is good.Because the arrangement mode of guest molecule and related physical chemical process may be totally different in macroscopical plane in the confinement effect, the accurate one dimension hollow of CNT tube chamber, so CNT also can be used as unique " nanochemistry test tube ".Owing to have said structure and performance characteristics, CNT is considered to a kind of desirable catalyst carrier material.
Recent result of study shows, because the space confinement effect, the catalytic activity and the life-span that are filled in the intraluminal catalyst granules of CNT hollow obviously are better than the outer catalyst granules of tube wall.But it is up to the present, very limited to multiple-wall carbon nanotube both at home and abroad as the research report of catalyst carrier material.Existing in CNT hollow tube chamber the approach of catalyst filling particle be CNT to be cut off in oxidizing acid solution and opening (document 1, Pan XL, Fan ZL, Cheng W, Ding YJ, Luo HY, Bao XH.Nature Materials 6:507 (2007), document 2, Zhang J, Muller JO, Zheng WQ, Wang D, Su DS, Schlogl R.NanoLetters 8:2738 (2008)).The subject matter of this method is: catalyst particle can't selectivity be filled in the hollow tube chamber amount of uncontrollable filler particles and size.CNT as catalyst carrier is a lack of alignment, and the opening of CNT is to obtain by acidification simultaneously, and this just makes its aperture opening ratio and draw ratio be difficult to control; In addition, though most of metallic catalyst is filled in the hollow tube chamber of CNT, but still 20% the catalyst deposit of having an appointment is at outer surface, and the content of catalyst granules is less simultaneously.This both had been unfavorable for the raising of catalyst activity, also was unfavorable for furtheing investigate the confinement enhancing mechanism of the accurate one dimension hollow of CNT tube chamber to metallic catalyst.
Summary of the invention
The object of the present invention is to provide a kind of the complete selectivity of ferric oxide particles to be filled in the intraluminal method of CNT hollow, and propose its purposes.Solved at present and can't catalyst particle be filled in the hollow tube chamber selectivity amount of uncontrollable filler particles and the problem of size.
Technical scheme of the present invention is:
A kind of ferric oxide particles fully optionally is filled in the intraluminal method of CNT hollow, the ferric oxide particles weight content is accurate homogeneous and controllable between 5-70%, the ferric oxide particles size is controlled in the 1-10 nanometer, and the size of CNT that is filled with ferric oxide particles is evenly accurately controlled.
The described ferric oxide particles preparation method that selectivity is filled in CNT hollow tube chamber, be template, be that carbon source, inert gas are carrier gas, chemical vapour deposition technique uniform deposition charcoal layer on template with anodic alumina films, obtain the compound of anodic alumina films/carbon with little molecule organic molecule with regular pore structure.Compound is put into iron nitrate solution; the concentration of iron nitrate solution is 5-35wt%; ultrasonic concussion is 0.5-3 hour under the room temperature; take out the compound of anodic alumina films/carbon; at 60-140 ℃ of dry 2-6 hour; 350-500 ℃ of processing (1-5 hour) resolved into iron oxide with ferric nitrate under protective atmosphere again, removes anodic oxidation aluminium formwork then, obtains the ferric oxide particles CNT that selectivity is filled in CNT hollow tube chamber at last.
Described anodic oxidation aluminium formwork is the preparation of sulfuric acid or Oxalic Acid Method, and its aperture is the 10-100 nanometer, and length is 50 nanometers-200 micron, a both ends open or an end opening.
Described little molecule organic molecule is acetylene, ethene or propylene, and described inert gas is argon gas or nitrogen, and the vapour deposition temperature is 600-900 ℃, and heating rate is 5-30 ℃/min, and 0.5-5 hour vapour deposition time, the carbon-source gas volumetric concentration is 1-20%.
The described purposes that is filled with the CNT of ferric oxide particles in the hollow tube chamber is meant: can be used as nano catalysis reaction device and energy storage material.
Among the present invention, the thickness of chemical vapour deposition technique uniform deposition charcoal layer on template is the 2-20 nanometer.
Advantage of the present invention is:
1, the present invention can prepare the complete selectivity of ferric oxide particles and is filled in the intraluminal CNT of hollow, has solved present ferric oxide particles and can't 100% be filled in nano-sized carbon hollow tube chamber, and ferric oxide particles content and size such as can't accurately control at problem.
2, the CNT of the iron oxide filling of the present invention's preparation, can be by optimizing the accurately content and the size of control iron oxide such as iron nitrate concentration, ultrasonic time, heating rate, the weight content of iron oxide is between 5-70%, and the ferric oxide particles size is controlled in the 1-10 nanometer.
3, the multiple-wall carbon nanotube of the iron oxide selectivity filling of the inventive method preparation can be used as nano catalysis reaction device and energy storage material.
Description of drawings
Fig. 1. the even selectivity of ferric oxide particles is filled in the intraluminal transmission electron microscope photo of CNT hollow.
Fig. 2. the even selectivity of ferric oxide particles is filled in the intraluminal stereoscan photograph of CNT hollow.
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
At the 3wt% oxalic acid aqueous solution, negative electrode adopts aluminium flake, and anode adopts aluminium flake, and anodic oxidation prepares the anodic alumina films of an end opening under 20 ℃, 40V condition.600 ℃ of chemical vapour deposition (CVD)s of carrying out acetylene gas 0.5 hour, carrier gas was an argon gas after the anodic alumina films drying, and flow is 300ml/min, and heating rate is 5 ℃/min, and the acetylene gas volumetric concentration is 1.5%, and the thickness of deposit carbon layer is 2 nanometers.The post-depositional anodic alumina films of carbon is placed in the iron nitrate solution that concentration is 30wt%, and ultrasonic concussion was taken out after 2 hours, after the clean surface at 140 ℃, air drying 6 hours, the speed with 5 ℃/min is elevated to 350 ℃ under argon atmospher then, constant temperature 3 hours.Remove anodic alumina films behind the cool to room temperature, just obtained the ferric oxide particles complete filling at the intraluminal CNT of hollow, as shown in Figure 1.The content of iron oxide is about 70wt%, and particle size distribution is concentrated to be distributed in about 5 nanometers between the 3-10 nanometer.
Embodiment 2.
The anodised aluminium membrane preparation method is with embodiment 1.700 ℃ of chemical vapour deposition (CVD)s of carrying out acetylene gas 5 hours, carrier gas was a nitrogen after the anodic alumina films drying, and flow is 300ml/min, and heating rate is 5 ℃/min, and the acetylene gas volumetric concentration is 5%, and the thickness of deposit carbon layer is 20 nanometers.The post-depositional anodic alumina films of carbon is placed in the iron nitrate solution that concentration is 25wt%, and ultrasonic concussion was taken out after 0.5 hour, after the clean surface at 60 ℃, vacuum drying 2 hours, the speed with 30 ℃/min is elevated to 350 ℃ under argon atmospher then, constant temperature 1 hour.Remove anodic alumina films behind the cool to room temperature, just obtained the CNT of ferric oxide particles complete filling at the hollow tube chamber.As shown in Figure 2, there is not ferric oxide particles in the outside of CNT.The content of iron oxide is about 20wt%, and particle size distribution is concentrated to be distributed in about 3 nanometers between the 1-8 nanometer.
Embodiment 3.
At the 10wt% aqueous sulfuric acid, negative electrode adopts aluminium flake, and anode adopts aluminium flake, and anodic oxidation prepares the anodic alumina films of an end opening under 10 ℃, 20V condition.600 ℃ of chemical vapour deposition (CVD)s of carrying out acetylene gas 0.5 hour, carrier gas was an argon gas after the anodic alumina films drying, and flow is 200ml/min, and heating rate is 5 ℃/min, and the acetylene gas volumetric concentration is 5%, and the thickness of deposit carbon layer is 5 nanometers.The post-depositional anodic alumina films of carbon is placed in the iron nitrate solution that concentration is 25wt%, ultrasonic concussion was taken out after 3 hours, and at 140 ℃, drying is 3 hours under the air atmosphere after the clean surface, speed with 10 ℃/min is elevated to 350 ℃ under argon atmospher then, constant temperature 3 hours.Remove anodic alumina films behind the cool to room temperature, just obtained the CNT of ferric oxide particles complete filling at the hollow tube chamber, the content of iron oxide is about 5wt%, and average particle size particle size is about 4 nanometers.
Embodiment 4.
The anodised aluminium membrane preparation method is with embodiment 3, different is anodic alumina films is 800 ℃ of chemical vapour deposition (CVD)s of carrying out ethylene gas 3 hours after the both ends open anodic alumina films drying through post-processed, carrier gas is an argon gas, flow is 300ml/min, heating rate is 10 ℃/min, the ethylene gas volumetric concentration is 1.5%, and the thickness of deposit carbon layer is 10 nanometers.The post-depositional anodic alumina films of carbon is placed in the iron nitrate solution that concentration is 10wt%, and ultrasonic concussion was taken out after 2 hours, and 140 ℃ of air dryings 2 hours, the speed with 5 ℃/min was elevated to 450 ℃ under argon atmospher then, constant temperature 1 hour after the clean surface.Remove anodic alumina films behind the cool to room temperature, just obtained the CNT of ferric oxide particles complete filling at the hollow tube chamber, the content of iron oxide is 20wt%, and average particle size particle size is about 8 nanometers.
Embodiment 5.
The anodised aluminium membrane preparation method is with embodiment 4.900 ℃ of chemical vapour deposition (CVD)s of carrying out propylene gas 2 hours, carrier gas was a nitrogen after the anodic alumina films drying, and flow is 300ml/min, and heating rate is 5 ℃/min, and the propylene gas volumetric concentration is 1.5%, and the thickness of deposit carbon layer is 11 nanometers.The post-depositional anodic alumina films of carbon is placed in the iron nitrate solution that concentration is 25wt%, and ultrasonic concussion was taken out after 0.5 hour, and 60 ℃ of vacuum drying 6 hours, the speed with 20 ℃/min was elevated to 500 ℃ under argon atmospher then, constant temperature 3 hours after the clean surface.Remove anodic alumina films behind the cool to room temperature, just obtained the CNT of ferric oxide particles complete filling at the hollow tube chamber, the content of iron oxide is about 40wt%, and average particle size particle size is about 10 nanometers.
Embodiment result shows, the present invention can be by optimizing anodic alumina films preparation condition, chemical vapor deposition conditions, the filling condition of ferric oxide particles optionally ferric oxide particles is filled in the controlled CNT hollow tube chamber of structure, and the content of ferric oxide particles and size are accurately controlled, this structure and size can be accurately controlled and the catalyst granules selectivity be filled in the intraluminal nano-sized carbon of hollow and can be used as nano catalysis reaction device and energy storage material.
Claims (6)
1. a ferric oxide particles selectivity is filled in the intraluminal method of CNT hollow, it is characterized in that: with the anodic alumina films with regular pore structure is template, by chemical vapour deposition technique uniform deposition charcoal layer on template, obtain the compound of anodic alumina films/carbon; Compound is put into iron nitrate solution; the concentration of iron nitrate solution is 5-35wt%; ultrasonic concussion is 0.5-3 hour under the room temperature; take out the compound of anodic alumina films/carbon; at 60-140 ℃ of dry 2-6 hour, again under protective atmosphere 350-500 ℃ handled 1-5 hour, ferric nitrate is resolved into iron oxide; remove anodic oxidation aluminium formwork then, obtain the ferric oxide particles CNT that selectivity is filled in CNT hollow tube chamber at last.
2. be filled in the intraluminal method of CNT hollow according to the described ferric oxide particles selectivity of claim 1, it is characterized in that: the ferric oxide particles selectivity is filled in CNT hollow tube chamber, the ferric oxide particles weight content is accurate homogeneous and controllable between 5-70%, the ferric oxide particles size is controlled in the 1-10 nanometer, and the size of CNT that is filled with ferric oxide particles is evenly accurately controlled.
3. be filled in the intraluminal method of CNT hollow according to the described ferric oxide particles selectivity of claim 1, it is characterized in that: described anodic alumina films adopts oxalic acid or sulfuric acid process preparation.
4. be filled in the intraluminal method of CNT hollow according to the described ferric oxide particles selectivity of claim 1, it is characterized in that: described drying mode is vacuum drying or at air drying.
5. be filled in the intraluminal method of CNT hollow according to the described ferric oxide particles selectivity of claim 1, it is characterized in that: described protective atmosphere is argon gas or nitrogen.
6. be filled in the intraluminal method of CNT hollow according to the described ferric oxide particles selectivity of claim 1, it is characterized in that: complete, even, the controlled intraluminal CNT of hollow that is filled in of ferric oxide particles can be used as nano catalysis reaction device and energy storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102299690A CN101745434B (en) | 2008-12-19 | 2008-12-19 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102299690A CN101745434B (en) | 2008-12-19 | 2008-12-19 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101745434A true CN101745434A (en) | 2010-06-23 |
| CN101745434B CN101745434B (en) | 2011-08-10 |
Family
ID=42473425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102299690A Expired - Fee Related CN101745434B (en) | 2008-12-19 | 2008-12-19 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101745434B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN102274976A (en) * | 2011-05-16 | 2011-12-14 | 云南师范大学 | Method for preparing nanomaterials by using anodized aluminum oxide template |
| CN102386042A (en) * | 2011-12-04 | 2012-03-21 | 中国航天科技集团公司第五研究院第五一〇研究所 | Preparation method of carbon nanotube field emission cathode |
| CN103022451A (en) * | 2012-12-24 | 2013-04-03 | 中国科学院金属研究所 | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof |
| CN104321909A (en) * | 2012-03-26 | 2015-01-28 | 剑桥企业有限公司 | Powder comprising carbon nanostructures and its method of production |
| CN109698342A (en) * | 2018-12-28 | 2019-04-30 | 中科廊坊过程工程研究院 | A kind of metal oxide-ordered carbon nanotube composite material and preparation method and application |
| CN109778214A (en) * | 2017-11-15 | 2019-05-21 | 中国科学院金属研究所 | A kind of method in fast selective filling nanoparticle to carbon nanotubes lumen |
| WO2021223251A1 (en) * | 2020-05-06 | 2021-11-11 | 青岛理工大学 | Metal oxide nano-confined catalytic film for catalytic treatment of wastewater and method for preparation thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355940C (en) * | 2005-03-01 | 2007-12-19 | 东华大学 | Method for preparing magnetic compound material of ferric oxide cladded carbon nanotube |
| CN100344708C (en) * | 2005-04-07 | 2007-10-24 | 东华大学 | Method for preparing carbon nanotube magnetic compositematerial modified by iron oxide red |
-
2008
- 2008-12-19 CN CN2008102299690A patent/CN101745434B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102274976A (en) * | 2011-05-16 | 2011-12-14 | 云南师范大学 | Method for preparing nanomaterials by using anodized aluminum oxide template |
| CN102274976B (en) * | 2011-05-16 | 2013-05-29 | 云南师范大学 | Method for preparing nanomaterials by using anodized aluminum oxide template |
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN102263257B (en) * | 2011-06-28 | 2013-08-07 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN102386042A (en) * | 2011-12-04 | 2012-03-21 | 中国航天科技集团公司第五研究院第五一〇研究所 | Preparation method of carbon nanotube field emission cathode |
| CN102386042B (en) * | 2011-12-04 | 2014-05-28 | 中国航天科技集团公司第五研究院第五一〇研究所 | Preparation method of carbon nanotube field emission cathode |
| CN104321909A (en) * | 2012-03-26 | 2015-01-28 | 剑桥企业有限公司 | Powder comprising carbon nanostructures and its method of production |
| CN103022451A (en) * | 2012-12-24 | 2013-04-03 | 中国科学院金属研究所 | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof |
| CN103022451B (en) * | 2012-12-24 | 2015-03-25 | 中国科学院金属研究所 | Nano silicon particles filled carbon nano tube compound as well as preparation method and application thereof |
| CN109778214A (en) * | 2017-11-15 | 2019-05-21 | 中国科学院金属研究所 | A kind of method in fast selective filling nanoparticle to carbon nanotubes lumen |
| CN109698342A (en) * | 2018-12-28 | 2019-04-30 | 中科廊坊过程工程研究院 | A kind of metal oxide-ordered carbon nanotube composite material and preparation method and application |
| CN109698342B (en) * | 2018-12-28 | 2022-08-19 | 廊坊绿色工业技术服务中心 | Metal oxide-ordered carbon nanotube composite material and preparation method and application thereof |
| WO2021223251A1 (en) * | 2020-05-06 | 2021-11-11 | 青岛理工大学 | Metal oxide nano-confined catalytic film for catalytic treatment of wastewater and method for preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101745434B (en) | 2011-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101745434B (en) | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube | |
| Chandrasekaran et al. | Carbon aerogel evolution: Allotrope, graphene-inspired, and 3D-printed aerogels | |
| Couteau et al. | CVD synthesis of high-purity multiwalled carbon nanotubes using CaCO3 catalyst support for large-scale production | |
| Allahbakhsh et al. | Self-assembled and pyrolyzed carbon aerogels: an overview of their preparation mechanisms, properties and applications | |
| Fan et al. | Carbon nanosheets: synthesis and application | |
| JP5147686B2 (en) | Nano-sized carbon material-activated carbon composite | |
| Avasthi et al. | Aligned CNT forests on stainless steel mesh for flexible supercapacitor electrode with high capacitance and power density | |
| Atchudan et al. | Synthesis and characterization of graphitic mesoporous carbon using metal–metal oxide by chemical vapor deposition method | |
| Sharma et al. | Analysis on the synthesis of vertically aligned carbon nanotubes: growth mechanism and techniques | |
| JP2008535763A5 (en) | ||
| CN104925783A (en) | Production method of core-shell hierarchical structure porous carbon | |
| CN101164874B (en) | Method for purifying multi-wall carbon nano pipe | |
| JP2016538228A5 (en) | ||
| TW201240915A (en) | Novel carbon nanotube and rpoduction method of the same | |
| JP2009515812A (en) | Mixed structure of single- and multi-walled carbon nanotubes | |
| Hou et al. | Double-wall carbon nanotube transparent conductive films with excellent performance | |
| JP2008517863A (en) | Improved ozonolysis of carbon nanotubes | |
| Chen et al. | Flexible design of carbon nanotubes grown on carbon nanofibers by PECVD for enhanced Cr (VI) adsorption capacity | |
| Skaltsas et al. | Impact of the fabrication method on the physicochemical properties of carbon nanotube-based aerogels | |
| Preda et al. | A study of thermal properties of sodium titanate nanotubes synthesized by microwave-assisted hydrothermal method | |
| Elyassi et al. | Hydrogen storage behaviors by adsorption on multi-walled carbon nanotubes | |
| JPWO2018168346A1 (en) | Method for producing surface-treated carbon nanostructure | |
| CN101631744A (en) | Method for purifying carbon material containing carbon nanotube, carbon material obtained by the purification method, and resin molded body, fiber, heat sink, sliding member, field emission source mat | |
| Alayan et al. | Growth and optimization of carbon nanotubes in powder activated carbon for an efficient removal of methylene blue from aqueous solution | |
| Sridhar et al. | Direct growth of carbon nanofiber forest on nickel foam without any external catalyst |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110810 Termination date: 20201219 |