CN104399431B - Amino-modified and thiol-group-modified magnetic carbon nanotube composite material and preparation method thereof - Google Patents
Amino-modified and thiol-group-modified magnetic carbon nanotube composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an amino-modified and thiol-group-modified magnetic carbon nanotube composite material and a preparation method thereof and aims to overcome the defects of poor dispersity, low introduction efficiency of functional groups and low degree of functionalization of carbon nanotubes. The composite material adopts a tubular structure, ferroferric oxide particles with the diameters being 10-20nm are uniformly deposited on the surfaces of the carbon nanotubes, and the outer surfaces of the ferroferric oxide nano-particles and the carbon nanotubes are coated with a layer of 5-10nm of film containing amino and thiol groups. The method comprises the following steps: dispersing the carbon nanotubes into a solution containing ferrous and ferric iron ions, adding ammonia water, and thus obtaining a ferroferric oxide/carbon nanotube composite material with superparamagnetism; after magnetic separation, dispersing into a mixed solution containing acetic acid, acetone and trimethoxysilylpropanethiol; after reaction, centrifugally separating and drying, and then dispersing into an ethanol solution; adding hydrazine under the protection of nitrogen; after reaction, respectively washing with water and ethanol; after vacuum drying, obtaining the amino-modified and thiol-group-modified magnetic carbon nanotube composite material.
Description
Technical field
The invention belongs to technical field of nano material is and in particular to the magnetic carbon nano-tube of a kind of amino and mercapto modification is multiple
Condensation material and preparation method.
Background technology
, after 1991 find CNT first, this material is with unique hollow for Japanese Electronic Speculum scholar Iijima S
Tubular structure, excellent electric conductivity, large specific surface area, lighter mass density and relatively pretend use and contaminant molecule between
Cause rapidly the extensive concern of each field scholar both at home and abroad.But CNT is due to surface hydrophobic and ultra-high surface energy, phase
Easily reunite between mutually and be wound around, be not readily dissolved in all kinds of solvents, therefore strongly limit its application.In order to improve the dispersion of CNT
Property improve its application power simultaneously, typically adopt chemical modification and physical adsorption process.Chemical modification is due to can be greatly improved it
Dispersibility, completely retains the performances such as its mechanics, electricity, therefore suffers from extensive concern.And physical absorption surface adsorption is organic
Macromolecule, biomacromolecule easily come off, and heat stability is poor.Additionally, chemical modification generally introduces one kind in carbon nano tube surface
Functional group, but because group introducing rate is poor, the low shortcoming of efficiency, therefore if introducing two kinds of groups then greatly in carbon pipe surface
Improve its absorbability, improve its dispersibility.Based on considerations above, introduce amino and two kinds of officials of mercapto in carbon nano tube surface
Can roll into a ball, both can improve CNT dispersibility, and improve its group introducing rate again, and therefore cause some scholars to note in recent years.
Patent [CN103041773] discloses that a kind of to be heated to 200～300 DEG C of reaction 8～24h using ethylenediamine dry
To amido modified magnetic Fe3O4- carbon nano tube compound material, this material can be used for Adsorption organic acid and phenolic compound.Patent
[CN101774573] disclose a kind of to add ethylenediamine using supercritical reaction kettle be 340～350 DEG C in temperature, pressure is 6～
11MPa obtains the CNT after amination, improves the introducing efficiency of nitrogen functional group.Document [Cheng Zhang, Jiehe
Sui,Jing Li, Yilun Tang, Wei Cai, Efficient removal of heavy metal ions by
thiol-functionalized superparamagnetic carbon nanotubes, Chemical Engineering
Journal,210(2012):45-52] report with mercapto functional magnetic carbon nano-tube material, and it is used for Adsorption of Heavy Metals
Ion.
All there is method of modifying complexity in the amination reported at present, the method for mercaptan carbon nano tube, introduce functional group
The shortcomings of efficiency is low, functionalization degree is high.Additionally due to introducing functional group efficiency is low, the ferroso-ferric oxide of carbon nano tube surface
Granule easily comes off and the shortcomings of easy oxidation stain.
Content of the invention
It is an object of the invention to solving CNT bad dispersibility, introducing that functional group efficiency is low, functionalization degree is not high
Shortcoming.
The present invention is the magnetic carbon-nano tube composite material and preparation method that amino and mercapto are modified, described composite
In tubular construction, diameter is that 10～20nm ferriferrous oxide particles are uniformly deposited on carbon nano tube surface, and ferroso-ferric oxide is received
Rice grain and the thin film containing amino and thiol group of CNT outer surface one layer of 5～10nm of parcel.
The preparation method of the magnetic carbon-nano tube composite material that amino and mercapto are modified, its step is：
（1）CNT is distributed in mixed acid solution, reaction at 60～80 DEG C carries out pretreatment in 1～3 hour, then mistake
Filter washing drying for standby；
（2）Add pretreated CNT, sonic oscillation in the solution containing ferrous ion and ferric ion
After 10～30 minutes, it is added dropwise over ammonia pH and controls 11～12, stirring 30～60 minutes at a temperature of 40～60 DEG C, wherein in advance
The CNT processing is 1 with the mass ratio of Ferrous ammonium sulfate:2～1:10；
（3）The magnetic carbon nano-tube Magnet of generation is separated, be put in 60～120 DEG C of dryings of vacuum drying oven 6～
20 hours, obtain superparamagnetic carbon nanotube material；
（4）Super magnetic carbon nano-tube material is dispersed in dehydrated alcohol, mechanical agitation under nitrogen protection, adds acetic acid
With 3- mercaptopropyl trimethoxysilane, stir 2～4 hours at a temperature of 30～60 DEG C, add acetone reaction 3 hours, then
Centrifugation is vacuum dried 4～8 hours at a temperature of 40～80 DEG C, and the superparamagnetic carbon nanotube obtaining mercapto modification is combined
Material；
（5）The superparamagnetic carbon nanotube composite that mercapto is modified is dispersed in dehydrated alcohol, and sonic oscillation 5～
15min, adds hydrazine, reacts 6～10h under nitrogen protection under mechanical agitation, Magnetic Isolation go out sample again through distilled water and
Absolute ethanol washing, in 60～100 DEG C of degree vacuum drying 8～20 hours, obtains the magnetic carbon nanometer that amino and mercapto are modified
Pipe composite.
Usefulness of the present invention is：（1）A kind of amino provided by the present invention and the magnetic carbon nano-tube of mercapto modification
Composite, dentate excellent to the absorption property of CNT and mercapto, amino is combined, makes magnetic carbon nanomaterial
To heavy metal ions in sewage, organic pollution, there is fine captivation, mainly by CNT, functional group, four oxidations
The physicochemical properties of three-iron three combine, and are a kind of carriers of good function nano granule.（2）It is super that the present invention obtains
Paramagnetic nanoparticles composite, the ferroso-ferric oxide of 10～20nm is dispersed in carbon nano tube surface, has fine magnetic property；
5nm～10nm thin film of ferriferrous oxide particles and carbon nano tube surface has a large amount of mercaptan and amino group, heavy metal from
Son has excellent absorption and separation process, thus being conducive to heavy metal ion adsorbed；
The preparation method process is simple of the present invention, easy to operate and mild condition, prepare product adsorption capacity have greatly excellent
Different biocompatibility.In fields such as biological medicine, environmental conservation, there is potential using value.
Brief description
Fig. 1 is the specific embodiment of the invention 1 CNT cladding Fe3O4Superparamagnetic carbon nanotube composite afterwards
High-resolution-ration transmission electric-lens（TEM）.Fig. 2 is that the magnetic carbon nano-tube of amino and mercapto modification in the specific embodiment of the invention 1 is multiple
The high-resolution-ration transmission electric-lens of condensation material（TEM）；Fig. 3 is the magnetic carbon of amino and mercapto modification in the specific embodiment of the invention 1
Fourier-the infrared spectrogram of nanometer tube composite materials.
Specific embodiment
The present invention is the magnetic carbon-nano tube composite material and preparation method that amino and mercapto are modified, described composite
In tubular construction, diameter is that 10～20nm ferriferrous oxide particles are uniformly deposited on carbon nano tube surface, and ferroso-ferric oxide is received
Rice grain and the thin film containing amino and thiol group of CNT outer surface one layer of 5～10nm of parcel.
The preparation method of the magnetic carbon-nano tube composite material that amino and mercapto are modified, its step is：
（1）CNT is distributed in mixed acid solution, reaction at 60～80 DEG C carries out pretreatment in 1～3 hour, then mistake
Filter washing drying for standby；
（2）Add pretreated CNT, sonic oscillation in the solution containing ferrous ion and ferric ion
After 10～30 minutes, it is added dropwise over ammonia pH and controls 11～12, stirring 30～60 minutes at a temperature of 40～60 DEG C, wherein in advance
The CNT processing is 1 with the mass ratio of Ferrous ammonium sulfate:2～1:10；
（3）The magnetic carbon nano-tube Magnet of generation is separated, be put in 60～120 DEG C of dryings of vacuum drying oven 6～
20 hours, obtain superparamagnetic carbon nanotube material；
（4）Super magnetic carbon nano-tube material is dispersed in dehydrated alcohol, mechanical agitation under nitrogen protection, adds acetic acid
With 3- mercaptopropyl trimethoxysilane, stir 2～4 hours at a temperature of 30～60 DEG C, add acetone reaction 3 hours, then
Centrifugation is vacuum dried 4～8 hours at a temperature of 40～80 DEG C, and the superparamagnetic carbon nanotube obtaining mercapto modification is combined
Material；
（5）The superparamagnetic carbon nanotube composite that mercapto is modified is dispersed in dehydrated alcohol, and sonic oscillation 5～
15min, adds hydrazine, reacts 6～10h under nitrogen protection under mechanical agitation, Magnetic Isolation go out sample again through distilled water and
Absolute ethanol washing, in 60～100 DEG C of degree vacuum drying 8～20 hours, obtains the magnetic carbon nanometer that amino and mercapto are modified
Pipe composite.
Described mixed acid solution is concentrated sulphuric acid and concentrated nitric acid, and volume ratio is 3:1.
Described CNT is many walls or SWCN.
The amount ratio of described ferrous ion and ferric ion material is 0.20～1.0, and the percentage by volume of ammonia spirit is
5%.
The rate of charge of described super magnetic carbon nano-tube material and 3- mercaptopropyl trimethoxysilane is 102～103g/L.
The superparamagnetic carbon nanotube composite that described mercapto is modified is 200～500g/L with the rate of charge of hydrazine.
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for restriction the scope of the present invention.In addition, it is to be understood that after reading the told about content of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1：
Step 1 CNT pretreatment:
By multi-walled carbon nano-tubes original for 1g（Prepared by chemical vapour deposition technique）It is distributed to 60ml concentrated sulphuric acid and the dense nitre of 20ml
Acid mixed acid solution in, stirring reaction 3 hours at 60 DEG C, with distillation be washed to pH=7,80 DEG C vacuum drying 12 hours after standby.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs：
Pretreated for 0.1g multi-walled carbon nano-tubes is added to the mixed of 0.17g Ferrous ammonium sulfate and 0.25g ammonium ferric sulfate
Close in solution, sonic oscillation 10 minutes；It is added dropwise over the ammonia spirit of 8mol/L, the pH of mixed solution is controlled in 11-12；With
The superparamagnetic carbon nanotube material of generation is separated from suspension by Magnet, with distilled water wash 5 times；80 degree of vacuum are done
Dry 8h, grinds standby after being dried, obtain superparamagnetic carbon nanotube material, as shown in figure 1, about 20nm ferroso-ferric oxide uniformly divides
It is dispersed in the surface of CNT.
The preparation of the superparamagnetism composite that step 3 mercapto is modified：
0.1g superparamagnetic carbon nanotube material is scattered in 80ml dehydrated alcohol, is slowly added to 0.25ml acetic acid；Again
It is added dropwise over 100 microlitres of MPTs；By 50 degree of lower stirrings of mixed solution 3 hours；Add 50ml acetone；Obtain after continuing reaction 3 hours
Obtain the magnetic carbon nano-tube material that mercapto is modified.
The preparation of the superparamagnetism composite of step 4 amino and mercapto modification：
The superparamagnetic carbon nanotube composite that 1g mercapto is modified is dispersed in 100ml dehydrated alcohol, ultrasonic shakes
Swing 15min, add 3ml hydrazine, under mechanical agitation, react 10h under nitrogen protection, isolate sample more respectively with steaming with Magnet
Distilled water and absolute ethanol washing 5～10 times, are vacuum dried 12 hours at 100 DEG C, obtain the magnetic carbon that amino and mercapto are modified
Nanometer tube composite materials, as shown in Fig. 2 there is amino and the sulfur of about 5nm in CNT and ferriferrous oxide particles area load
Alcohol base film.Shown in Fig. 3, infrared spectrum in figure has Si-N key proves amino grafting on mercapto, and-NH exists proves amino
Presence, Fe-O key prove ferroso-ferric oxide generation.
Embodiment 2：
Step 1 CNT pretreatment:
By multi-walled carbon nano-tubes original for 0.3g（Prepared by chemical vapour deposition technique）Put into the core that aperture is 20-30 micron
In funnel, the sand core funnel that will be equipped with original multi-walled carbon nano-tubes is placed in the Teflon container that volume is 50 milliliters, wherein
Teflon container bottom is placed with the concentrated nitric acid of 3ml, and the container of Teflon is put in the reactor of volume 100ml, sealing, then will
It puts in drying baker, and drying baker temperature is 200 DEG C, and the persistent period is 5 hours.Take out reactor and be cooled to room temperature, open anti-
Answer kettle to take out sand core funnel, CNT is put in clean beaker, uses 100ml distilled water diluting, the carbon after dilution is received
Mitron is poured into and is lined with the diameter of ordinary filter paper is in 10 centimetres of cloth funnel, washs 10 times respectively with water and dehydrated alcohol, directly
To washings pH close to neutral.CNT is peeled off from buchner funnel, puts in drying baker and be dried 12 hours, wherein dry
The temperature inside the box is 80 DEG C, the solid black patch obtaining after being dried multi-walled carbon nano-tubes as after purification.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs：
Pretreated for 0.2g CNT is added to 0.4g Ferrous ammonium sulfate and the mixed solution of 0.5g ammonium ferric sulfate
In, sonic oscillation 30 minutes；It is added dropwise over the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 11；To be given birth to Magnet
The superparamagnetic carbon nanotube material becoming is separated from suspension, with distilled water wash 5 times；80 degree of vacuum drying 12h, do
Grind standby after dry, obtain superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified：
0.2g superparamagnetic carbon nanotube material is scattered in 100ml dehydrated alcohol, is slowly added to 0.5ml acetic acid；Again
It is added dropwise over 0.4ml MPTs；By 60 degree of lower stirrings of mixed solution 3 hours；Add 100ml acetone；Obtain after continuing reaction 5 hours
Obtain the magnetic carbon nano-tube material that mercapto is modified.
The preparation of the superparamagnetism composite of step 4 amino and mercapto modification：
The superparamagnetic carbon nanotube composite that 1g mercapto is modified is dispersed in 100ml dehydrated alcohol, ultrasonic shakes
Swing 15min, add 5ml hydrazine, under mechanical agitation, react 10h under nitrogen protection, isolate sample more respectively with steaming with Magnet
Distilled water and absolute ethanol washing 5～10 times, are vacuum dried 12 hours at 100 DEG C, obtain the magnetic carbon that amino and mercapto are modified
Nanometer tube composite materials.
Embodiment 3：
Step 1 CNT pretreatment:
By multi-walled carbon nano-tubes original for 0.5g（Prepared by chemical vapour deposition technique）It is distributed to 30ml concentrated sulphuric acid and 10ml is dense
In the mixed acid solution of nitric acid, stirring reaction 5 hours at 80 DEG C, it is washed to pH=7 with distillation, 80 DEG C of vacuum drying standby in 12 hours
With.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs：
Pretreated for 0.3g CNT is added to 0.68g Ferrous ammonium sulfate and the mixing of 0.75g ammonium ferric sulfate is molten
In liquid, sonic oscillation 10 minutes；It is added dropwise over the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 12；Will with Magnet
The superparamagnetic carbon nanotube material generating is separated from suspension, with distilled water wash 5 times；80 degree of vacuum drying 12h,
Grind standby after drying, obtain superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified：
0.3g superparamagnetic carbon nanotube material is scattered in 100ml dehydrated alcohol, is slowly added to 0.75ml acetic acid；Again
It is added dropwise over 0.5 milliliter of MPTs；By 60 degree of lower stirrings of mixed solution 4 hours；Add 150ml acetone；Obtain after continuing reaction 3 hours
Obtain the magnetic carbon nano-tube material that mercapto is modified.
The preparation of the superparamagnetism composite of step 4 amino and mercapto modification：
The superparamagnetic carbon nanotube composite that 0.5g mercapto is modified is dispersed in 100ml dehydrated alcohol, ultrasonic
Vibration 15min, adds 1.25ml hydrazine, reacts 10h under nitrogen protection, isolate sample with Magnet and divide under mechanical agitation
Not Yong distilled water and absolute ethanol washing 5～10 times, be vacuum dried 18 hours at 100 DEG C, obtain amino and mercapto modifies
Magnetic carbon-nano tube composite material.
Embodiment 4：
Step 1 CNT pretreatment:
SWCN original for 0.1g is distributed in 30ml concentrated sulphuric acid and the mixed acid solution of 10ml concentrated nitric acid, 80 DEG C
Lower stirring reaction 6 hours, with distillation be washed to pH=7,80 DEG C vacuum drying 12 hours after standby.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs：
Pretreated for 0.05g CNT is added to 0.085g Ferrous ammonium sulfate and the mixing of 0.125g ammonium ferric sulfate
In solution, sonic oscillation 15 minutes；It is added dropwise over the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 11；Use Magnet
The superparamagnetic carbon nanotube material of generation is separated from suspension, with distilled water wash 10 times；80 degree of vacuum drying
10h, grinds standby after being dried, obtain superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified：
0.05g superparamagnetic carbon nanotube material is scattered in 40ml dehydrated alcohol, is slowly added to 0.12ml acetic acid；Again
It is added dropwise over 80 microlitres of MPTs；By 50 degree of lower stirrings of mixed solution 5 hours；Add 25ml acetone；Obtain after continuing reaction 5 hours
The magnetic carbon nano-tube material that mercapto is modified.
The preparation of the superparamagnetism composite of step 4 amino and mercapto modification：
The superparamagnetic carbon nanotube composite that 0.1g mercapto is modified is dispersed in 50ml dehydrated alcohol, ultrasonic shakes
Swing 15min, add 2ml hydrazine, under mechanical agitation, react 10h under nitrogen protection, isolate sample more respectively with steaming with Magnet
Distilled water and absolute ethanol washing 5～10 times, are vacuum dried 12 hours at 80 DEG C, obtain amino and magnetic carbon that mercapto is modified is received
Mitron composite.
Embodiment 5：
Step 1 CNT pretreatment:
SWCN original for 0.1g is distributed in 30ml concentrated sulphuric acid and the mixed acid solution of 10ml concentrated nitric acid, 80 DEG C
Lower stirring reaction 6 hours, with distillation be washed to pH=7,80 DEG C vacuum drying 12 hours after standby.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs：
Pretreated for 0.1g CNT is added to 0.25g Ferrous ammonium sulfate and the mixing of 0.25g ammonium ferric sulfate is molten
In liquid, sonic oscillation 15 minutes；It is added dropwise over the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 11；Will with Magnet
The superparamagnetic carbon nanotube material generating is separated from suspension, with distilled water wash 10 times；80 degree of vacuum drying
10h, grinds standby after being dried, obtain superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified：
0.05g superparamagnetic carbon nanotube material is scattered in 40ml dehydrated alcohol, is slowly added to 0.15ml acetic acid；Again
It is added dropwise over 0.5 milliliter of MPTs；By 50 degree of lower stirrings of mixed solution 5 hours；Add 25ml acetone；Obtain after continuing reaction 5 hours
Obtain the magnetic carbon nano-tube material that mercapto is modified.
The preparation of the superparamagnetism composite of step 4 amino and mercapto modification：
The superparamagnetic carbon nanotube composite that 0.02g mercapto is modified is dispersed in 50ml dehydrated alcohol, ultrasonic
Vibration 15min, adds 66ml hydrazine, reacts 12h under nitrogen protection, isolate sample with Magnet and use respectively under mechanical agitation
Distilled water and absolute ethanol washing 10 times, are vacuum dried 18 hours at 80 DEG C, obtain amino and magnetic carbon that mercapto is modified is received
Mitron composite.
Claims (6)
1. the magnetic carbon-nano tube composite material that amino and mercapto are modified preparation method it is characterised in that concrete steps such as
Under：
(1) CNT is distributed in mixed acid solution, reaction at 60～80 DEG C carries out pretreatment in 1～3 hour, then crosses diafiltration
Wash drying for standby；
(2) pretreated CNT, sonic oscillation 10 are added in the solution containing ferrous ion and ferric ion
After～30 minutes, being added dropwise over ammonia spirit makes pH value of solution control 11～12, at a temperature of 40～60 DEG C mechanical agitation 30～
60 minutes, wherein pretreated CNT was 1 with the mass ratio of Ferrous ammonium sulfate:2～1:10, ferrous ion derives from
Ferrous ammonium sulfate；
(3) the magnetic carbon nano-tube Magnet of generation is separated, be put in 60～120 DEG C of dryings 6～20 of vacuum drying oven little
When, obtain superparamagnetic carbon nanotube material；
(4) superparamagnetic carbon nanotube material is dispersed in dehydrated alcohol, under nitrogen protection mechanical agitation, add acetic acid and
3- mercaptopropyl trimethoxysilane, stirs 2～4 hours at a temperature of 30～60 DEG C, adds acetone and reacts 3 hours, Ran Houli
The heart separates and is vacuum dried 4～8 hours at a temperature of 40～80 DEG C, obtains the superparamagnetic carbon nanotube composite wood that mercapto is modified
Material；
(5) the superparamagnetic carbon nanotube composite that mercapto is modified is dispersed in dehydrated alcohol, sonic oscillation 5～
15min, adds hydrazine, reacts 6～10h under nitrogen protection under mechanical agitation, Magnetic Isolation go out sample again through distilled water and
Absolute ethanol washing, is vacuum dried 8～20 hours at 60～100 DEG C, obtains the magnetic carbon nano-tube that amino and mercapto are modified
Composite.
2. preparation method according to claim 1 it is characterised in that：Described CNT is many walls or single
Pipe.
3. preparation method according to claim 1 it is characterised in that：Described mixed acid solution is the mixed of concentrated sulphuric acid and concentrated nitric acid
Close solution, the volume ratio of concentrated sulphuric acid and concentrated nitric acid is 3:1.
4. preparation method according to claim 1 it is characterised in that：Described ferrous ion and ferric ion material
Amount ratio is 0.20～1.0, and the percentage by volume of ammonia spirit is 5%.
5. preparation method according to claim 1 it is characterised in that：Described superparamagnetic carbon nanotube material and 3- mercapto third
The rate of charge of base trimethoxy silane is 102～103g/L.
6. preparation method according to claim 1 it is characterised in that：The superparamagnetic carbon nanotube that described mercapto is modified
Composite is 200～500g/L with the rate of charge of hydrazine.
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