CN100384522C - MnO film for filtering carbon nanotube effluent, its prepn. and use - Google Patents
MnO film for filtering carbon nanotube effluent, its prepn. and use Download PDFInfo
- Publication number
- CN100384522C CN100384522C CNB2006100243598A CN200610024359A CN100384522C CN 100384522 C CN100384522 C CN 100384522C CN B2006100243598 A CNB2006100243598 A CN B2006100243598A CN 200610024359 A CN200610024359 A CN 200610024359A CN 100384522 C CN100384522 C CN 100384522C
- Authority
- CN
- China
- Prior art keywords
- film
- manganese oxide
- thin film
- inorganic thin
- carbon nanotube
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a method for preparing an inorganic manganese oxide film for filtering the waste liquid of a carbon nanotube and an application thereof. The present invention is characterized in that the film is composed of thin manganese oxide nanometer lines, the length of the film can reach more than ten micrometers, and the diameter of the film is from 20 to 40 nanometers; nanometer beams composed of nanometer lines combined tightly can be formed easily, and a gap less than 1 micrometer between the beams can allow a thin and small substance to pass. The appearance of the film is charcoal grey, just like a shape of a piece of paper, and the film can be arbitrarily folded. The thickness of the thin film is changed from 0.1 to 0.8 millimeter, and the shape and the size of the film can be adjusted as required. The MnO2 film of the present invention is synthesized by a hydrothermal method after potassium sulfate, potassium persulfate and manganese sulphate as raw materials are added to distilled water to be mixed. Experimental results indicate that the inorganic film can intercept the truncated carbon nanotubes on the surface of the film, wherein the truncated carbon nanotubes exist in a carbon nanotube solution which has high dispersion and contains a surface active agent. The method of the present invention is used for the purification treatment of the carbon nanometer solution, and has wide application prospects in environmental protection, special filtering devices and nanometer devices.
Description
Technical field
The invention relates to a kind of inorganic nano thin-film material preparation method and application, relate to a kind of synthetic manganese oxide (MnO that can be used for handling filtering carbon nanotube effluent or rather
2) film process.Prepared film is used to handle carbon nanotube effluent, belongs to field of nanometer material technology.
Technical background
Since S.Iijima since finding CNT in 1991, because of it has peculiar electricity, optics and mechanical property have caused that people pay close attention to greatly, the field of its research relates to electronic device, catalyst carrier, display, fields such as drug delivery and storage hydrogen.But thing followed problem is the generation and the handling problem of carbon nanotube effluent.CNT has been proved to be to know from experience the people in up-to-date research and has produced harm, and suck the back than carbon black and quartzy consequence more serious (Lam C.W, James, J.T Toxicol.Sic.77 (2004), 126-134); The result of study of Ding etc. shows: the toxicity of carbon pipe can also by with the contacting of Skin Cell, unit cell with promptly can be dead after the pipe of wall carbon more than tens contacts.(Lianghao?Ding，Jackie?Stilwll，Tingting?Zhang?et?al，Nanoletters，nl051748o)。Therefore must be to the harm and the protective approach of CNT, and liquid waste processing is paid attention to and is studied.Yuan etc. use potassium peroxydisulfate, potassium sulfate, manganese sulfate and water are the OMS-2 film that raw material has synthesized the paper shape, and synthesis temperature is at 250 ℃, and product need be in distilled water 85 ℃ of oven dry 24 hours naturally, and successfully catch the gold particle (Jikang Yuan, Kate Laubernds, advanced materials, 16 (2004), 1729-1732), but be not used to the processing of carbon pipe solution.The paper of the liquid waste processing aspect research of carbon current pipe also seldom, the laboratory is generally adopted organic polymer miillpore filter or centrifugation method to separate and is reclaimed the carbon pipe, and these two kinds of methods all are not suitable for recycling on a large scale carbon nanotube effluent, and organic film itself also might be by some organic solvent dissolution.Can seek a kind of simple and effectively, the filtration that the filtration membrane of reusable anti-organic matter dissolving and corrosion is used for carbon pipe waste liquid has meaning very much.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who can be used in the inorganic thin film of carbon nanotube effluent processing, this film is used to filter the carbon pipe waste liquid that contains surfactant and organic solvent, can alleviate harm environment and human health.
Characteristics of the present invention are: prepared well behaved inorganic oxide manganese film, and the processing that is used for carbon nanotube effluent of success.
Concrete steps are:
(1) with potassium sulfate, potassium peroxydisulfate, manganese sulfate (it is pure to be analysis) proportionally joins and is mixed with solution in the distilled water, and the molar concentration scope of each reagent is respectively 0.175-0.195M, 0.175-0.195M, 0.11-0.138M: change in the autoclave after magnetic agitation is even.
(2) the autoclave hydrothermal treatment consists adopts two-step method, and the first step is that 160 ℃ of heating are warming up to 220-240 ℃ of heating 3 days after 30 hours.
The oxidation equation formula can be expressed as:
MnSO
4+K
2S
2O
8+2H
2O＝MnO
2+K
2SO
4+2H
2SO
4
(3) in the product that obtains, add 200-1000ml distilled water magnetic agitation after 2 hours with vacuum filtration device filtering and washing.
(4) the grey black coloured paper shape film formed for very thin nano wire of the product that obtains by (3), film thickness is between 0.1 to 0.8 millimeter, and size shape can be regulated as required.Nanowire length can reach tens microns, and diameter is between 20 to 40 nanometers.And formed the nanometer bundle of being made up of the nano wire of combining closely, bundle can allow tiny material pass through with slit (less than 1 micron) between the bundle, then being retained down of CNT (general length all above micron).This film was put into 70 ℃ of vacuum drying ovens dry 10-15 hour.
(5) this film is used for the vacuum filtration device as filter membrane, pours the carbon nano-tube solution vavuum pump suction filtration of the brachymemma that contains surfactant then into.Shortening carbon nano-tube is that solution is that to adopt volume ratio be 3: 1 the concentrated sulfuric acid and 140 ℃ of reflow treatment multi-walled carbon nano-tubes of red fuming nitric acid (RFNA) 10 hours, washing and drying then.Add the ultrasonic processing of surfactant 2198A and deionized water 1 hour again.
(6) film that will contain CNT takes off in 500 ℃ muffle furnace that roasting can remove the carbon elimination pipe in 5 hours and film itself can remain intact.
Description of drawings
The SEM photo of the inorganic thin film before Fig. 1 filters,
Fig. 2 handled film (60 ℃ of oven dry) the SEM photo (a) after the carbon nano-tube solution and (b) can see a large amount of clean inorganic thin film surfaces of the CNT that contains surfactant (c) under the different amplification.
The TEM photo of the CNT of the brachymemma of Fig. 3 usefulness 2198A surfactant-dispersed
The photo of Fig. 4 inorganic filter film
The specific embodiment
Further specify embodiment and effect with following non-limiting embodiment; Thereby set off out substantive distinguishing features of the present invention and obvious improvement.
Embodiment 1
To be total to the potassium sulfate of 20mmol, potassium peroxydisulfate, manganese sulfate joins in the 40ml distilled water according to 3: 3: 2 molar ratio, changes in the autoclave after magnetic agitation is even.Hydrothermal treatment consists 160 ℃ of heating before this is warming up to 220 ℃ of heating 3 days after 30 hours.In the product that obtains, add 500ml distilled water magnetic agitation after 2 hours with vacuum filtration device filtering and washing.The product pattern is that diameter is the grey black coloured paper shape film of the nano wire composition of 20-40nm, this film is put into dry 12 hours (Fig. 1) of 70 ℃ of vacuum drying ovens, but the product any direction is folding do not rupture (Fig. 4).
Embodiment 2
To be total to the potassium sulfate of 40mmol, potassium peroxydisulfate, manganese sulfate joins in the 80ml distilled water according to 3.1: 3.1: 2.1 molar ratio, changes in the autoclave after magnetic agitation is even.Hydrothermal treatment consists 160 ℃ of heating before this is warming up to 220 ℃ of heating 3 days after 30 hours.In the product that obtains, add 1000ml distilled water magnetic agitation after 2 hours with vacuum filtration device filtering and washing.The product pattern is a grey black coloured paper shape film, and this film was put into 70 ℃ of vacuum drying ovens dry 12 hours.(Fig. 2 c) is used for the vacuum filtration device as filter membrane with this film, pours the carbon nano-tube solution (Fig. 3) of the brachymemma that contains the 2198A surfactant then into, uses the vavuum pump suction filtration.The film that will contain the carbon pipe takes off that (Fig. 2 a, b), roasting 5 hours can remove the carbon elimination pipe and film itself remains intact and can utilize once more in 500 ℃ muffle furnace.
Claims (4)
1. the application of manganese oxide inorganic thin film in filtering carbon nanotube effluent is characterized in that
(1) the manganese oxide inorganic thin film of Shi Yonging reaches tens microns by length, and the manganese oxide nano wire of diameter between 20-40nm formed;
(2) preparation technology of the described manganese oxide inorganic thin film of feature (1) is:
(a) with potassium sulfate, potassium peroxydisulfate, manganese sulfate are that raw material adds in the distilled water, and magnetic agitation is even;
(b) solution that step (a) is obtained joins in the autoclave, and the hydrothermal treatment consists temperature is 160-180 ℃ of heating 2 days, and 220-240 ℃ was heated 3 days again;
(c) product that step (b) is obtained joins in the distilled water and stirred 2 hours;
(d) with the solution of step (c) with vacuum filtration device suction filtration, obtain film after the distilled water washing;
(e) film of step (d) gained is dried in 70 ℃ of vacuum drying ovens.
Wherein, potassium sulfate, potassium peroxydisulfate and manganese sulfate molar concentration are respectively 0.175-0.195M, 0.175-0.195M, and 0.11-0.138M,
(3) use the described manganese oxide inorganic thin film of feature (1) when filtering carbon nanotube solution; With the manganese oxide inorganic thin film will contain surfactant high degree of dispersion and also blocked on film by the CNT of brachymemma.
2. by the application of the described manganese oxide inorganic thin film of claim 1 in filtering carbon nanometer waste liquid, it is characterized in that: the roasting in 500 ℃ of air of described film was removed CNT and film recirculation use itself after 5 hours.
3. by the application of the described a kind of manganese oxide inorganic thin film of claim 1 in filtering carbon nanotube effluent, the thickness that it is characterized in that described manganese oxide inorganic thin film is between 0.1-0.8mm.
4. by the application of the described a kind of manganese oxide inorganic thin film of claim 1 in filtering carbon nanotube effluent, it is characterized in that described nano wire combines closely into nanometer bundle, bundle with restraint between have 1 micron gap.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100243598A CN100384522C (en) | 2006-03-03 | 2006-03-03 | MnO film for filtering carbon nanotube effluent, its prepn. and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100243598A CN100384522C (en) | 2006-03-03 | 2006-03-03 | MnO film for filtering carbon nanotube effluent, its prepn. and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1833765A CN1833765A (en) | 2006-09-20 |
| CN100384522C true CN100384522C (en) | 2008-04-30 |
Family
ID=37001743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100243598A Expired - Fee Related CN100384522C (en) | 2006-03-03 | 2006-03-03 | MnO film for filtering carbon nanotube effluent, its prepn. and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100384522C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112899A (en) * | 2013-03-05 | 2013-05-22 | 广东工业大学 | Preparation method of functionalized manganese dioxide nanowire membrane |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174314B (en) * | 2015-09-02 | 2016-11-16 | 首都师范大学 | The preparation method of water solublity MnS nano-particle and this nano-particle are as the purposes of magnetic resonance imaging contrast |
| CN105797596B (en) * | 2016-03-25 | 2018-04-24 | 河北工业大学 | A kind of preparation method of filter membrane for Water warfare |
| CN106824290B (en) * | 2017-03-03 | 2020-08-21 | 哈尔滨工业大学 | Preparation method of ultra-stable self-supporting manganese dioxide water treatment membrane |
-
2006
- 2006-03-03 CN CNB2006100243598A patent/CN100384522C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Spontaneous Formation of Inorganic Paper-Like Materials. JiKang Yuan.Advanced Material,Vol.16 No.19. 2004 |
| Spontaneous Formation of Inorganic Paper-Like Materials. JiKang Yuan.Advanced Material,Vol.16 No.19. 2004 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112899A (en) * | 2013-03-05 | 2013-05-22 | 广东工业大学 | Preparation method of functionalized manganese dioxide nanowire membrane |
| CN103112899B (en) * | 2013-03-05 | 2015-02-11 | 广东工业大学 | Preparation method of functionalized manganese dioxide nanowire membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1833765A (en) | 2006-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Razaq et al. | Review on graphene-, graphene oxide-, reduced graphene oxide-based flexible composites: From fabrication to applications | |
| Li et al. | Preparation and application of 2D MXene-based gas sensors: A review | |
| Sajjad et al. | Study of graphene oxide structural features for catalytic, antibacterial, gas sensing, and metals decontamination environmental applications | |
| Luo et al. | Preparation and dye degradation performances of self-assembled MXene-Co3O4 nanocomposites synthesized via solvothermal approach | |
| CN102066245B (en) | Process for the preparation of graphene | |
| Xu et al. | Hierarchical-oriented attachment: from one-dimensional Cu (OH) 2 nanowires to two-dimensional CuO nanoleaves | |
| Yang et al. | Additive-free synthesis of In2O3 cubes embedded into graphene sheets and their enhanced NO2 sensing performance at room temperature | |
| Zou et al. | Well-aligned arrays of CuO nanoplatelets | |
| CN103031618B (en) | Preparation method of graphene oxide hollow fiber and graphene hollow fiber | |
| Pant et al. | One-pot synthesis of CdS sensitized TiO2 decorated reduced graphene oxide nanosheets for the hydrolysis of ammonia-borane and the effective removal of organic pollutant from water | |
| Wu et al. | Hierarchical structured TiO2 nano-tubes for formaldehyde sensing | |
| CN103253656A (en) | Preparation method of graphene dispersion liquid | |
| CN106492761A (en) | A kind of preparation method of magnetic hydrogel microsphere | |
| Zhang et al. | Dimension induced intrinsic physio-electrical effects of nanostructured TiO2 on its antibacterial properties | |
| CN102557021B (en) | Nanocomposite material preparation method based on graphene oxide autocatalysis | |
| Guo et al. | The enhanced ethanol sensing properties of CNT@ ZnSnO3 hollow boxes derived from Zn-MOF (ZIF-8) | |
| CN100384522C (en) | MnO film for filtering carbon nanotube effluent, its prepn. and use | |
| Ikram et al. | Recent advances in chitin and chitosan/graphene-based bio-nanocomposites for energetic applications | |
| Hung et al. | A facile method for batch preparation of electrochemically reduced graphene oxide | |
| CN103762356B (en) | Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application | |
| Raza et al. | Room temperature NH3 gas sensor based on PMMA/RGO/ZnO nanocomposite films fabricated by in-situ solution polymerization | |
| Amarnath et al. | Selective ammonia sensing response of vanadium doped cerium oxide nanorods wrapped reduced graphene oxide electrodes at room temperature | |
| CN106676562B (en) | A method of graphene is prepared by electrochemical process reduction | |
| Li et al. | Preparation and characterization of CNTs–SrFe12O19 composites | |
| CN102649089B (en) | Preparation method of nanogold-tannin-graphene oxide nano composites |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080430 Termination date: 20120303 |