CN103316594B - Preparation method of carbon-nanotube hollow fiber membranes - Google Patents
Preparation method of carbon-nanotube hollow fiber membranes Download PDFInfo
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Abstract
The invention belongs to the technical field of nano-material assembling, and relates to a preparation method of carbon-nanotube hollow fiber membranes. The method is characterized in that the preparation method is implemented through the following steps of: 1, acidifying carbon nanotubes in a concentrated acid solution, and introducing hydrophilic groups; 2, dispersing the acidified carbon nanotubes in monohydric alcohol, and depositing the carbon nanotubes on a metal template through electrophoretic deposition; 3, calcining and solidifying the obtained object under anaerobic conditions; and 4, removing the metal template, so that an independently self-supported carbon-nanotube hollow fiber membrane can be obtained. The method has the advantages that a preparation process is simple, no expensive equipment is required, and the method is flexible and controllable.
Description
Technical field
The present invention relates to a kind of preparation method of CNT hollow-fibre membrane, belong to nanomaterial assembly technical field.
Background technology
CNT has outstanding physical chemistry, engineering properties, comprises excellent electrical and thermal conductivity performance, overstable chemical inertness, the specific area of super large, the mechanical strength of superelevation etc.Along with the development of nano material technology of preparing and perfect, the production cost of CNT constantly reduces.These factors all stimulating researchers attempt these invisible fiber fines be assembled into can be practical, high performance material, to the excellent properties Single Carbon Nanotubes, be incorporated in macro object.As typical monodimension nanometer material, add that it is antibacterial, the ability of antiacid alkali, CNT is the ideal material of preparing diffusion barrier.
At present, carbon nano-tube film mainly obtains by the method for vacuum filtration.Although this preparation method is simply efficient,, still there are some outstanding problems, be mainly manifested in: the one, the carbon nano-tube film of preparing mostly is paper shape, and structure is single, is restricting it and is further developing; The 2nd,, the carbon nano-tube film of preparing is essential supporter in running, and this is the simplification to membrane module just, and miniaturization is intensive very unfavorable.Comparatively speaking, hollow-fibre membrane is with its higher loading density, and excellent self-supporting performance, becomes the principal mode of membrane filtration compared with large membrane area in unit volume.Therefore, development CNT hollow-fibre membrane is particularly important.But, about the technology of preparing of CNT hollow-fibre membrane, have not been reported.
Summary of the invention
The present invention is mainly the shortcoming existing for existing CNT membrane preparation technology, and the CNT membrane structure of preparing is single, and operation needs supporter, is difficult to meet development need, and proposes a kind of preparation method of CNT hollow-fibre membrane.Preparation method proposed by the invention, technique is simple, and without expensive equipment, method is controlled flexibly.
Basic conception of the present invention is to utilize electrophoretic deposition technique to be fixed on metal matrix the CNT of acidifying, removes metal matrix and obtain full CNT hollow-fibre membrane after high temperature is fixing.
Preparation method's step of a kind of CNT hollow-fibre membrane proposed by the invention is as follows:
(1) acidifying of CNT: CNT is placed in the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, is incubated 2～6 hours under 40～80 ° of C.Then mixed liquor is diluted, and carbon nanotube separation out.
(2) electrophoretic deposition: the carbon nanotube dispersed after acidifying, in saturated monohydroxy alcohol, and is added to the magnesium nitrate of 20～200mg/L.After this, this carbon nano tube dispersion liquid is poured in electrodeposit reaction device.Wire is as masterplate, and as the negative electrode of electrophoretic deposition system.Voltage is set as 30～160V, and the electrophoretic deposition time is made as 1～10 minute, can successive sedimentation repeatedly.
(3) anaerobic calcining: after deposition process completes, the wire that surface is covered with to carbon nanotube layer, at oxygen free condition, is calcined 0.5～4 hour under 200～1000 ° of C, naturally cools to afterwards room temperature.
(4) remove template: the wire that is covered with carbon nanotube layer after calcining is put into FeCl
3in/HCl etching liquid, the wire that melts away, can obtain the CNT hollow-fibre membrane of independent self-supporting, finally with a large amount of water, cleans to remove metal ion.
In the present invention, described in step (1), in nitration mixture, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 1:0～5.
In the present invention, described in step (1), the separation method of CNT is vacuum filtration or high speed centrifugation.
In the present invention, described in step (2), saturated monohydroxy alcohol is absolute ethyl alcohol, anhydrous isopropyl alcohol or anhydrous normal butyl alcohol.
In the present invention, described in step (2), the dosage of magnesium nitrate is 20～200mg/L.
In the present invention, described in step (2), in carbon nano tube dispersion liquid, the content of CNT is 100～500mg/L.
In the present invention, wire described in step (2) is iron wire, copper wire, aluminium wire, titanium silk or nickel wire.
In the present invention, described in step (2), frequency of depositing is 1～20 time.
In the present invention, described in step (3), oxygen free condition is vacuum or inert gas shielding.
In the present invention, described in step (4), etching liquid composition consists of 0.5～5mol/L FeCl
3/ 0.1～1mol/LHCl.
Preparation technology of the present invention is simple, without expensive equipment; Method is flexible, and the CNT hollow fiber film structure of preparation is controlled; The CNT hollow-fibre membrane agent structure of preparation is attractive in appearance, well-balanced.
Accompanying drawing explanation
Fig. 1 is the ESEM picture of the different CNT hollow-fibre membrane side of 3 external diameters utilizing the technology that the present invention relates to prepare.In figure, the external diameter of 3 CNT hollow-fibre membranes is from left to right followed successively by 240 μ m, 295 μ m and 342 μ m.Fig. 2 utilizes the technology the present invention relates to prepare the ESEM picture in CNT hollow-fibre membrane cross section.In figure, the external diameter of CNT hollow-fibre membrane is 465 μ m, internal diameter 150 μ m.
These ESEM pictures are to adopt Hitachi S-4800 type ESEM, under the condition that is 10kV, take at accelerating potential.
The specific embodiment
Below by specific embodiment, further illustrate the preparation details of CNT hollow-fibre membrane, but the present invention is not only confined to following examples.
Embodiment 1:
Take copper wire as masterplate, and the preparation method of the CNT hollow-fibre membrane that isopropyl alcohol is dispersant is as follows:
The first step takes 1g CNT, and to pour the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid (volume ratio 1:3) into inner, is heated to 60 ℃, is incubated 3 hours.Then by concentrated acid solution dilution, CNT is separated by vacuum filtration;
Second step in 200mL isopropyl alcohol, and adds the magnesium nitrate of 40mg by the carbon nanotube dispersed after 100mg acidifying.The copper wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 160V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 6 times;
The wire that the 3rd step is covered with carbon nanotube layer by surface is put into tube type resistance furnace, at 500 ℃ of argon shields, calcines 1 hour, naturally cools to afterwards room temperature;
The 4th step is put into 2.5mol/L FeCl by the copper wire that is covered with carbon nanotube layer after calcining
3in/0.5mol/LHCl solution, copper wire melts away.The CNT hollow-fibre membrane obtaining cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 320 μ m.
Embodiment 2:
Take copper wire as masterplate, and the preparation method of the CNT hollow-fibre membrane that ethanol is dispersant is as follows:
The first step takes 1g CNT, and to pour the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid (volume ratio 1:2) into inner, is heated to 40 ℃, is incubated 4 hours.Then by concentrated acid solution dilution, CNT is separated by the high speed centrifugation of 6000 rpms.
Second step in 200mL ethanol, and adds the magnesium nitrate of 40mg by the carbon nanotube dispersed after 100mg acidifying.The copper wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 160V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 6 times;
The copper wire that the 3rd step is covered with carbon nanotube layer by surface is put into tube type resistance furnace, at 300 ℃, vacuum, calcines 1 hour, naturally cools to afterwards room temperature;
The 4th step is with the 4th step in embodiment 1.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 287 μ m.
Embodiment 3:
Take iron wire as masterplate, and the preparation method of the CNT hollow-fibre membrane that isopropyl alcohol is dispersant is as follows:
The first step is with the first step in embodiment 1;
Second step in 200mL isopropyl alcohol, and adds the magnesium nitrate of 40mg by the carbon nanotube dispersed after 100mg acidifying.The iron wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 85V, and the electrophoretic deposition time is made as 8 minutes, successive sedimentation 6 times;
The iron wire that the 3rd step is covered with carbon nanotube layer by surface is put into tube type resistance furnace, at 500 ℃ of nitrogen protections, calcines 1 hour, naturally cools to afterwards room temperature;
The 4th step is put into 2.5mol/L FeCl by the iron wire that is covered with carbon nanotube layer after calcining
3in/0.5mol/LHCl solution, iron wire melts away.The CNT hollow-fibre membrane obtaining cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 245 μ m.
Embodiment 4:
Take iron wire as masterplate, and the preparation method of the CNT hollow-fibre membrane that n-butanol is dispersant is as follows:
The first step is with the first step in embodiment 2;
Second step in 150mL n-butanol, and adds the magnesium nitrate of 40mg by the carbon nanotube dispersed after 100mg acidifying.The iron wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 85V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 8 times;
The 3rd step is with the 3rd step in embodiment 3;
The 4th step is put into 3mol/L FeCl by the iron wire that is covered with carbon nanotube layer after calcining
3in/1mol/L HCl solution, iron wire melts away.The full CNT hollow-fibre membrane obtaining cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 298 μ m.
Embodiment 5:
Take aluminium wire as masterplate, and the preparation method of the CNT hollow-fibre membrane that isopropyl alcohol is dispersant is as follows:
The first step is with the first step in embodiment 1;
Second step in 200mL isopropyl alcohol, and adds the magnesium nitrate of 40mg by the carbon nanotube dispersed after 100mg acidifying.The aluminium wire of diameter 450 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 160V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 6 times;
The aluminium wire that the 3rd step is covered with carbon nanotube layer by surface is put into tube type resistance furnace, at 500 ℃ of argon shields, calcines 2 hours, naturally cools to afterwards room temperature;
The 4th step is put into 2.5mol/L FeCl by the aluminium wire that is covered with carbon nanotube layer after calcining
3in/0.5mol/LHCl solution, aluminium wire melts away.The CNT hollow-fibre membrane obtaining cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 450 μ m, external diameter 605 μ m.
Embodiment 6:
Take nickel wire as masterplate, and the preparation method of the CNT hollow-fibre membrane that isopropyl alcohol is dispersant is as follows:
The first step is with the first step in embodiment 1;
Second step in 250mL isopropyl alcohol, then adds the magnesium nitrate of 50mg by 100mg carbon nanotube dispersed.The nickel wire of diameter 450 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 85V, and the electrophoretic deposition time is made as 10 minutes.Successive sedimentation 8 times;
The nickel wire that the 3rd step is covered with carbon nanotube layer by surface is put into tube type resistance furnace, at 800 ℃ of argon shields, calcines 30 hours, naturally cools to afterwards room temperature;
The 4th step is put into 2.5mol/L FeCl by the nickel wire that is covered with carbon nanotube layer after calcining
3in/1mol/L HCl solution, nickel wire melts away.The CNT hollow-fibre membrane obtaining cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 450 μ m, external diameter 560 μ m.
Claims (8)
1. a preparation method for CNT hollow-fibre membrane, is characterized in that, comprises the following steps:
(1) acidifying of CNT: CNT is placed in the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, 40 ~ 80
ounder C, be incubated 2 ~ 6 hours; Then mixed liquor is diluted, and carbon nanotube separation out;
(2) electrophoretic deposition: the carbon nanotube dispersed after acidifying, in saturated monohydroxy alcohol, and is added to the magnesium nitrate of 20 ~ 200mg/L; Then, this carbon nano tube dispersion liquid is poured in electrodeposit reaction device; Wire is as masterplate, and as the negative electrode of electrophoresis system; Voltage is set as 30 ~ 160V, and the electrophoretic deposition time is made as 1 ~ 10 minute, can successive sedimentation;
(3) anaerobic calcining: after deposition process completes, the wire that surface is covered with to carbon nanotube layer is at oxygen free condition, calcines 0.5 ~ 4 hour at 200 ~ 1000 ℃, naturally cools to room temperature;
(4) remove template: the wire that is covered with carbon nanotube layer after calcining is put into FeCl
3in/HCl etching liquid, the wire that melts away, obtains the hollow-fibre membrane that the full CNT of independent self-supporting forms.
2. preparation method according to claim 1, is characterized in that, described in step (1), in nitration mixture, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is not less than 1:5; Described in step (1), the separation method of CNT is vacuum filtration or high speed centrifugation.
3. preparation method according to claim 1 and 2, is characterized in that, described in step (2), saturated monohydroxy alcohol is absolute ethyl alcohol, anhydrous isopropyl alcohol or anhydrous normal butyl alcohol; Described in step (2), in carbon nano tube dispersion liquid, the content of CNT is 100 ~ 500mg/L; Wire described in step (2) is iron wire, copper wire, aluminium wire, titanium silk or nickel wire; Described in step (2), frequency of depositing is 1 ~ 20 time.
4. preparation method according to claim 1 and 2, is characterized in that, described in step (3), oxygen free condition is vacuum or inert gas shielding.
5. preparation method according to claim 3, is characterized in that, described in step (3), oxygen free condition is vacuum or inert gas shielding.
6. according to the preparation method described in claim 1,2 or 5, it is characterized in that, described in step (4), etching liquid composition consists of 0.5 ~ 5mol/L FeCl
3/ 0.1 ~ 1mol/L HCl.
7. preparation method according to claim 3, is characterized in that, described in step (4), etching liquid composition consists of 0.5 ~ 5mol/L FeCl
3/ 0.1 ~ 1mol/L HCl.
8. preparation method according to claim 4, is characterized in that, described in step (4), etching liquid composition consists of 0.5 ~ 5mol/L FeCl
3/ 0.1 ~ 1mol/L HCl.
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| CN104028112B (en) * | 2014-03-05 | 2016-01-13 | 大连理工大学 | The method of Carbon-nanotube hollow fiber membrane is prepared in a kind of scale |
| CN104174299B (en) * | 2014-07-30 | 2017-06-23 | 中国海洋大学 | High flux forward osmosis membrane based on ultra-thin supporting layer and preparation method thereof |
| CN106298268B (en) * | 2016-09-12 | 2018-10-26 | 东华大学 | Graphene/ conductive polymer hydridization doughnut and the preparation method and application thereof |
| CN106400077B (en) * | 2016-09-12 | 2019-03-29 | 东华大学 | A kind of graphene doughnut and its continuous preparation method |
| CN106637511B (en) * | 2016-09-12 | 2019-01-22 | 东华大学 | A kind of graphene porous fibre and its continuous preparation method |
| CN107460725B (en) * | 2017-07-13 | 2020-05-05 | 东华大学 | Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof |
| CN109022495B (en) * | 2018-09-11 | 2022-03-29 | 华东理工大学 | Method for producing methane by reducing carbon dioxide with microorganisms |
| CN110273136B (en) * | 2019-06-24 | 2021-07-09 | 大连理工大学 | Self-supporting hollow carbon fiber membrane, preparation method thereof and application thereof in lithium-sulfur battery |
| CN110327789B (en) * | 2019-07-05 | 2022-02-15 | 大连理工大学 | Carbon nano tube/nano fiber conductive composite film and preparation method thereof |
| CN111298664B (en) * | 2020-03-16 | 2020-10-27 | 中国人民解放***箭军工程设计研究院 | Hollow fiber gas separation composite membrane and preparation method thereof |
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