CN104399431A - 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, be specifically related to magnetic carbon-nano tube composite material and the preparation method of a kind of amino and mercapto modification.
Background technology
Japan Electronic Speculum scholar Iijima S after Late Cambrian CNT in 1991, this material with the hollow tubular structures of uniqueness, excellent electric conductivity, compared with bigger serface, lighter mass density and and contaminant molecule between comparatively pretend extensive concern with causing rapidly domestic and international each field scholar.But CNT is due to surface hydrophobic and ultra-high surface energy, winding of easily reuniting each other, is not soluble in all kinds of solvent, therefore strongly limit its application.In order to the dispersiveness improving CNT improves its application power simultaneously, general employing chemical modification and physical adsorption process.Chemical modification is owing to can greatly improve its dispersibility, and its performance such as mechanics, electricity of complete reservation, is therefore subject to extensive concern.And the organic polymer of physical absorption adsorption, large biological molecule easily come off, poor heat stability.In addition, chemical modification introduces a kind of functional group in carbon nano tube surface usually, but due to group introducing rate variance, the shortcomings such as efficiency is low, therefore if introduce two kinds of groups at carbon tube-surface then greatly improve its adsorption capacity, improve its dispersiveness.Based on above consideration, introduce amino and mercapto Liang Zhong functional group in carbon nano tube surface, both can improve carbon nanotube dispersed, and improve again its group introducing rate, and therefore cause some scholars to note in recent years.
Patent [CN103041773] discloses one and utilizes ethylenediamine to be heated to 200 ~ 300 DEG C of reaction 8 ~ 24h dryings to obtain amido modified magnetic Fe
3o
4-carbon nano tube compound material, this material can be used for Adsorption organic acid and phenolic compound.Patent [CN101774573] discloses one, and to utilize supercritical reaction still to add ethylenediamine in temperature be 340 ~ 350 DEG C, and pressure is the CNT after 6 ~ 11MPa obtains 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 for Adsorption of Heavy Metal Ions.
All there is method of modifying complexity in the amination reported at present, the method for Thiolation CNT, introduces the shortcomings such as functional group's efficiency is low, functionalization degree is not high.In addition low owing to introducing functional group's efficiency, the ferriferrous oxide particles of carbon nano tube surface easily comes off and the shortcomings such as easy oxidation stain.
Summary of the invention
The object of the invention is to solve the shortcoming that carbon nanotube dispersed is poor, introducing functional group efficiency is low, functionalization degree is not high.
The present invention is magnetic carbon-nano tube composite material and the preparation method of amino and mercapto modification, described composite in tubular construction, diameter is that 10 ~ 20nm ferriferrous oxide particles is deposited on carbon nano tube surface equably, and ferroferric oxide nano granules and CNT outer surface wrap up the film containing amino and thiol group of one deck 5 ~ 10nm.
The preparation method of the magnetic carbon-nano tube composite material that amino and mercapto is modified, the steps include:
(1) by carbon nanotube dispersed in mixed acid solution, at 60 ~ 80 DEG C reaction within 1 ~ 3 hour, carry out pretreatment, then filtration washing drying for standby;
(2) in the solution containing ferrous ion and ferric ion, pretreated CNT is added, sonic oscillation is after 10 ~ 30 minutes, dropwise adding ammoniacal liquor pH controls 11 ~ 12, stir 30 ~ 60 minutes at 40 ~ 60 DEG C of temperature, wherein pretreated CNT and the mass ratio of iron ammonium sulfate are 1:2 ~ 1:10;
(3) the magnetic carbon nano-tube magnet of generation is separated, be put in vacuum drying chamber 60 ~ 120 DEG C of dryings 6 ~ 20 hours, obtain superparamagnetic carbon nanotube material;
(4) magnetic carbon nano-tube dispersion of materials will be surpassed in absolute ethyl alcohol, mechanical agitation under nitrogen protection, add acetic acid and 3-mercaptopropyl trimethoxysilane, stir 2 ~ 4 hours at 30 ~ 60 DEG C of temperature, add acetone again and react 3 hours, then centrifugation vacuum drying 4 ~ 8 hours at 40 ~ 80 DEG C of temperature, obtains the superparamagnetic carbon nanotube composite that mercapto is modified;
(5) the superparamagnetic carbon nanotube composite that mercapto is modified is dispersed in absolute ethyl alcohol; sonic oscillation 5 ~ 15min; add hydrazine; 6 ~ 10h is reacted under nitrogen protection under mechanical agitation; Magnetic Isolation goes out sample again through distilled water and absolute ethanol washing; 60 ~ 100 DEG C of degree vacuum drying 8 ~ 20 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
Usefulness of the present invention is: the magnetic carbon-nano tube composite material that (1) a kind of amino provided by the present invention and mercapto are modified, the absorption property of CNT and mercapto, amino excellent dentate are combined, magnetic carbon nano material is made to have fine attraction to heavy metal ions in sewage, organic pollution, mainly the physicochemical properties of CNT, functional group, tri-iron tetroxide three being combined, is a kind of carrier of good function nano particle.(2) superparamagnetic nano composite material that obtains of the present invention, the tri-iron tetroxide of 10 ~ 20nm is dispersed in carbon nano tube surface, has fine magnetic property; 5nm ~ 10nm film of ferriferrous oxide particles and carbon nano tube surface has a large amount of mercaptan and amino group, and heavy metal ion has excellent absorption and separation process, thus is conducive to heavy metal ion adsorbed;
Preparation method's technique of the present invention is simple, easy to operate and mild condition, prepares product adsorption capacity and has greatly excellent biocompatibility.In the field such as biological medicine, environmental protection, there is potential using value.
Accompanying drawing explanation
Fig. 1 is the coated Fe of the specific embodiment of the invention 1 CNT
3o
4after the high-resolution-ration transmission electric-lens (TEM) of superparamagnetic carbon nanotube composite.Fig. 2 is amino in the specific embodiment of the invention 1 and the high-resolution-ration transmission electric-lens (TEM) of the magnetic carbon-nano tube composite material of mercapto modification; Fig. 3 is amino in the specific embodiment of the invention 1 and Fourier-the infrared spectrogram of the magnetic carbon-nano tube composite material of mercapto modification.
Detailed description of the invention
The present invention is magnetic carbon-nano tube composite material and the preparation method of amino and mercapto modification, described composite in tubular construction, diameter is that 10 ~ 20nm ferriferrous oxide particles is deposited on carbon nano tube surface equably, and ferroferric oxide nano granules and CNT outer surface wrap up the film containing amino and thiol group of one deck 5 ~ 10nm.
The preparation method of the magnetic carbon-nano tube composite material that amino and mercapto is modified, the steps include:
(1) by carbon nanotube dispersed in mixed acid solution, at 60 ~ 80 DEG C reaction within 1 ~ 3 hour, carry out pretreatment, then filtration washing drying for standby;
(2) in the solution containing ferrous ion and ferric ion, pretreated CNT is added, sonic oscillation is after 10 ~ 30 minutes, dropwise adding ammoniacal liquor pH controls 11 ~ 12, stir 30 ~ 60 minutes at 40 ~ 60 DEG C of temperature, wherein pretreated CNT and the mass ratio of iron ammonium sulfate are 1:2 ~ 1:10;
(3) the magnetic carbon nano-tube magnet of generation is separated, be put in vacuum drying chamber 60 ~ 120 DEG C of dryings 6 ~ 20 hours, obtain superparamagnetic carbon nanotube material;
(4) magnetic carbon nano-tube dispersion of materials will be surpassed in absolute ethyl alcohol, mechanical agitation under nitrogen protection, add acetic acid and 3-mercaptopropyl trimethoxysilane, stir 2 ~ 4 hours at 30 ~ 60 DEG C of temperature, add acetone again and react 3 hours, then centrifugation vacuum drying 4 ~ 8 hours at 40 ~ 80 DEG C of temperature, obtains the superparamagnetic carbon nanotube composite that mercapto is modified;
(5) the superparamagnetic carbon nanotube composite that mercapto is modified is dispersed in absolute ethyl alcohol; sonic oscillation 5 ~ 15min; add hydrazine; 6 ~ 10h is reacted under nitrogen protection under mechanical agitation; Magnetic Isolation goes out sample again through distilled water and absolute ethanol washing; 60 ~ 100 DEG C of degree vacuum drying 8 ~ 20 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
Described mixed acid solution is the concentrated sulfuric acid and red fuming nitric acid (RFNA), and volume ratio is 3:1.
Described CNT is many walls or SWCN.
Described ferrous ion and ferric ion amount of substance ratio are 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 10
2~ 10
3g/L.
The rate of charge of the superparamagnetic carbon nanotube composite that described mercapto is modified and hydrazine is 200 ~ 500g/L.
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples only for illustration of the present invention but not for limiting scope of the present invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after reading the present invention tells about content.
Embodiment 1:
The pretreatment of step 1 CNT:
Be distributed in the mixed acid solution of the 60ml concentrated sulfuric acid and 20ml red fuming nitric acid (RFNA) by multi-walled carbon nano-tubes (chemical vapour deposition technique preparation) original for 1g, at 60 DEG C, stirring reaction 3 hours, is washed till pH=7 with distilled water, and 80 DEG C of vacuum drying are for subsequent use after 12 hours.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs:
Pretreated for 0.1g multi-walled carbon nano-tubes is joined in the mixed solution of 0.17g iron ammonium sulfate and 0.25g ammonium ferric sulfate, sonic oscillation 10 minutes; Dropwise add the ammonia spirit of 8mol/L, the pH of mixed solution is controlled at 11-12; Separate from suspension with the superparamagnetic carbon nanotube material of magnet by generation, wash 5 times with distilled water; 80 degree of vacuum drying 8h, after dry, grinding is for subsequent use, and obtain superparamagnetic carbon nanotube material, as shown in Figure 1, about 20nm tri-iron tetroxide is dispersed in the surface of CNT.
The preparation of the superparamagnetism composite that step 3 mercapto is modified:
By 0.1g superparamagnetic carbon nanotube dispersion of materials in 80ml absolute ethyl alcohol, slowly add 0.25ml acetic acid; Dropwise add 100 microlitre MPTs again; By lower for mixed solution 50 degree stirring 3 hours; Add 50ml acetone; Continue reaction obtains mercapto modification magnetic carbon nano-tube material after 3 hours.
The preparation of the superparamagnetism composite that step 4 amino and mercapto are modified:
The superparamagnetic carbon nanotube composite that 1g mercapto is modified is dispersed in 100ml absolute ethyl alcohol; sonic oscillation 15min; add 3ml hydrazine; 10h is reacted under nitrogen protection under mechanical agitation; isolate sample with magnet and use distilled water and absolute ethanol washing 5 ~ 10 times more respectively; 100 DEG C of vacuum drying 12 hours; obtain magnetic carbon-nano tube composite material that is amino and mercapto modification; as shown in Figure 2, to have an appointment the amino of 5nm and mercapto film at CNT and ferriferrous oxide particles area load.Shown in Fig. 3, there is Si-N key in infrared spectrogram proves that amino grafting is on mercapto, and-NH exists proves amino existence, and Fe-O key proves the generation of tri-iron tetroxide.
Embodiment 2:
The pretreatment of step 1 CNT:
Multi-walled carbon nano-tubes (chemical vapour deposition technique preparation) original for 0.3g is put in the sand core funnel that aperture is 20-30 micron, the sand core funnel that original multi-walled carbon nano-tubes is housed being placed on volume is in the Teflon container of 50 milliliters, wherein Teflon container bottom is placed with the red fuming nitric acid (RFNA) of 3ml, the container of Teflon is put into the reactor of volume 100ml, sealing, put it in drying box, drying box temperature is 200 DEG C again, and the duration is 5 hours.Take out reactor and be cooled to room temperature, open reactor and take out sand core funnel, CNT is put into clean beaker, use 100ml distilled water diluting, pouring the CNT after dilution into be lined with ordinary filter paper diameter is in the cloth funnel of 10 centimetres, 10 times are washed respectively, until washings pH is close to neutral with water and absolute ethyl alcohol.Peeled off from Buchner funnel by CNT, put into drying box inner drying 12 hours, wherein dry the temperature inside the box is 80 DEG C, and the solid black patch obtained after drying is the multi-walled carbon nano-tubes after purifying.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs:
Pretreated for 0.2g CNT is joined in the mixed solution of 0.4g iron ammonium sulfate and 0.5g ammonium ferric sulfate, sonic oscillation 30 minutes; Dropwise add the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 11; Separate from suspension with the superparamagnetic carbon nanotube material of magnet by generation, wash 5 times with distilled water; 80 degree of vacuum drying 12h, after dry, grinding is for subsequent use, obtains superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified:
By 0.2g superparamagnetic carbon nanotube dispersion of materials in 100ml absolute ethyl alcohol, slowly add 0.5ml acetic acid; Dropwise add 0.4ml MPTs again; By lower for mixed solution 60 degree stirring 3 hours; Add 100ml acetone; Continue reaction obtains mercapto modification magnetic carbon nano-tube material after 5 hours.
The preparation of the superparamagnetism composite that step 4 amino and mercapto are modified:
The superparamagnetic carbon nanotube composite that 1g mercapto is modified is dispersed in 100ml absolute ethyl alcohol; sonic oscillation 15min; add 5ml hydrazine; 10h is reacted under nitrogen protection under mechanical agitation; isolate sample with magnet and use distilled water and absolute ethanol washing 5 ~ 10 times more respectively; 100 DEG C of vacuum drying 12 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
Embodiment 3:
The pretreatment of step 1 CNT:
Be distributed in the mixed acid solution of the 30ml concentrated sulfuric acid and 10ml red fuming nitric acid (RFNA) by multi-walled carbon nano-tubes (chemical vapour deposition technique preparation) original for 0.5g, at 80 DEG C, stirring reaction 5 hours, is washed till pH=7 with distilled water, and 80 DEG C of vacuum drying are for subsequent use after 12 hours.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs:
Pretreated for 0.3g CNT is joined in the mixed solution of 0.68g iron ammonium sulfate and 0.75g ammonium ferric sulfate, sonic oscillation 10 minutes; Dropwise add the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 12; Separate from suspension with the superparamagnetic carbon nanotube material of magnet by generation, wash 5 times with distilled water; 80 degree of vacuum drying 12h, after dry, grinding is for subsequent use, obtains superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified:
By 0.3g superparamagnetic carbon nanotube dispersion of materials in 100ml absolute ethyl alcohol, slowly add 0.75ml acetic acid; Dropwise add 0.5 milliliter of MPTs again; By lower for mixed solution 60 degree stirring 4 hours; Add 150ml acetone; Continue reaction obtains mercapto modification magnetic carbon nano-tube material after 3 hours.
The preparation of the superparamagnetism composite that step 4 amino and mercapto are modified:
The superparamagnetic carbon nanotube composite that 0.5g mercapto is modified is dispersed in 100ml absolute ethyl alcohol; sonic oscillation 15min; add 1.25ml hydrazine; 10h is reacted under nitrogen protection under mechanical agitation; isolate sample with magnet and use distilled water and absolute ethanol washing 5 ~ 10 times more respectively; 100 DEG C of vacuum drying 18 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
Embodiment 4:
The pretreatment of step 1 CNT:
Be distributed to by SWCN original for 0.1g in the mixed acid solution of the 30ml concentrated sulfuric acid and 10ml red fuming nitric acid (RFNA), at 80 DEG C, stirring reaction 6 hours, is washed till pH=7 with distilled water, and 80 DEG C of vacuum drying are for subsequent use after 12 hours.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs:
Pretreated for 0.05g CNT is joined in the mixed solution of 0.085g iron ammonium sulfate and 0.125g ammonium ferric sulfate, sonic oscillation 15 minutes; Dropwise add the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 11; Separate from suspension with the superparamagnetic carbon nanotube material of magnet by generation, wash 10 times with distilled water; 80 degree of vacuum drying 10h, after dry, grinding is for subsequent use, obtains superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified:
By 0.05g superparamagnetic carbon nanotube dispersion of materials in 40ml absolute ethyl alcohol, slowly add 0.12ml acetic acid; Dropwise add 80 microlitre MPTs again; By lower for mixed solution 50 degree stirring 5 hours; Add 25ml acetone; Continue reaction obtains mercapto modification magnetic carbon nano-tube material after 5 hours.
The preparation of the superparamagnetism composite that step 4 amino and mercapto are modified:
The superparamagnetic carbon nanotube composite that 0.1g mercapto is modified is dispersed in 50ml absolute ethyl alcohol; sonic oscillation 15min; add 2ml hydrazine; 10h is reacted under nitrogen protection under mechanical agitation; isolate sample with magnet and use distilled water and absolute ethanol washing 5 ~ 10 times more respectively; 80 DEG C of vacuum drying 12 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
Embodiment 5:
The pretreatment of step 1 CNT:
Be distributed to by SWCN original for 0.1g in the mixed acid solution of the 30ml concentrated sulfuric acid and 10ml red fuming nitric acid (RFNA), at 80 DEG C, stirring reaction 6 hours, is washed till pH=7 with distilled water, and 80 DEG C of vacuum drying are for subsequent use after 12 hours.
The preparation of step 2 superparamagnetic carbon nanotube material MagCNTs:
Pretreated for 0.1g CNT is joined in the mixed solution of 0.25g iron ammonium sulfate and 0.25g ammonium ferric sulfate, sonic oscillation 15 minutes; Dropwise add the ammonia spirit of 8mol/L, the pH of mixed solution is controlled 11; Separate from suspension with the superparamagnetic carbon nanotube material of magnet by generation, wash 10 times with distilled water; 80 degree of vacuum drying 10h, after dry, grinding is for subsequent use, obtains superparamagnetic carbon nanotube material.
The preparation of the superparamagnetism composite that step 3 mercapto is modified:
By 0.05g superparamagnetic carbon nanotube dispersion of materials in 40ml absolute ethyl alcohol, slowly add 0.15ml acetic acid; Dropwise add 0.5 milliliter of MPTs again; By lower for mixed solution 50 degree stirring 5 hours; Add 25ml acetone; Continue reaction obtains mercapto modification magnetic carbon nano-tube material after 5 hours.
The preparation of the superparamagnetism composite that step 4 amino and mercapto are modified:
The superparamagnetic carbon nanotube composite that 0.02g mercapto is modified is dispersed in 50ml absolute ethyl alcohol; sonic oscillation 15min; add 66ml hydrazine; 12h is reacted under nitrogen protection under mechanical agitation; isolate sample with magnet and use distilled water and absolute ethanol washing 10 times more respectively; 80 DEG C of vacuum drying 18 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
Claims (7)
1. the magnetic carbon-nano tube composite material of amino and mercapto modification, it is characterized in that, described composite in tubular construction, 10 ~ 20nm ferriferrous oxide particles is deposited on carbon nano tube surface equably, and ferroferric oxide nano granules and CNT outer surface wrap up the film containing amino and thiol group of one deck 5 ~ 10nm.
2. preparation method according to claim 2, is characterized in that: described CNT be in many walls, SWCN one or both.
3. the preparation method of the magnetic carbon-nano tube composite material of amino and mercapto modification, it is characterized in that, concrete steps are as follows:
(1) by carbon nanotube dispersed in mixed acid solution, at 60 ~ 80 DEG C reaction within 1 ~ 3 hour, carry out pretreatment, then filtration washing drying for standby;
(2) in the solution containing ferrous ion and ferric ion, pretreated CNT is added, sonic oscillation is after 10 ~ 30 minutes, dropwise adding ammonia spirit makes pH value of solution control 11 ~ 12, mechanical agitation 30 ~ 60 minutes at 40 ~ 60 DEG C of temperature, wherein pretreated CNT and the mass ratio of iron ammonium sulfate are 1:2 ~ 1:10;
(3) the magnetic carbon nano-tube magnet of generation is separated, be put in vacuum drying chamber 60 ~ 120 DEG C of dryings 6 ~ 20 hours, obtain superparamagnetic carbon nanotube material;
(4) magnetic carbon nano-tube dispersion of materials will be surpassed in absolute ethyl alcohol, mechanical agitation under nitrogen protection, add acetic acid and 3-mercaptopropyl trimethoxysilane, stir 2 ~ 4 hours at 30 ~ 60 DEG C of temperature, add acetone again and react 3 hours, then centrifugation vacuum drying 4 ~ 8 hours at 40 ~ 80 DEG C of temperature, obtains the superparamagnetic carbon nanotube composite that mercapto is modified;
(5) the superparamagnetic carbon nanotube composite that mercapto is modified is dispersed in absolute ethyl alcohol; sonic oscillation 5 ~ 15min; add hydrazine; 6 ~ 10h is reacted under nitrogen protection under mechanical agitation; Magnetic Isolation goes out sample again through distilled water and absolute ethanol washing; 60 ~ 100 DEG C of degree vacuum drying 8 ~ 20 hours, obtain magnetic carbon-nano tube composite material that is amino and mercapto modification.
4. preparation method according to claim 2, is characterized in that: described mixed acid solution is the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), and the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1.
5. preparation method according to claim 2, is characterized in that: described ferrous ion and ferric ion amount of substance ratio are 0.20 ~ 1.0, and the percentage by volume of ammonia spirit is 5%.
6. preparation method according to claim 2, is characterized in that: the rate of charge of described super magnetic carbon nano-tube material and 3-mercaptopropyl trimethoxysilane is 10
2~ 10
3g/L.
7. preparation method according to claim 2, is characterized in that: the rate of charge of the superparamagnetic carbon nanotube composite that described mercapto is modified and hydrazine is 200 ~ 500g/L.
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| CN106582532A (en) * | 2017-01-03 | 2017-04-26 | 兰州理工大学 | Thiol-modified graphene/carbon nanotube composite material and preparation method therefor |
| CN106582533A (en) * | 2017-01-03 | 2017-04-26 | 兰州理工大学 | Amino and thiol-modified graphene/carbon nanotube composite material and preparation method therefor |
| CN109928521A (en) * | 2019-04-24 | 2019-06-25 | 成都纳海川环境工程有限公司 | Inorganic microparticle scale dispersing agent and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106582532A (en) * | 2017-01-03 | 2017-04-26 | 兰州理工大学 | Thiol-modified graphene/carbon nanotube composite material and preparation method therefor |
| CN106582533A (en) * | 2017-01-03 | 2017-04-26 | 兰州理工大学 | Amino and thiol-modified graphene/carbon nanotube composite material and preparation method therefor |
| CN106582532B (en) * | 2017-01-03 | 2019-01-22 | 兰州理工大学 | The Graphene/carbon nanotube composite material and preparation method of mercapto modification |
| CN109928521A (en) * | 2019-04-24 | 2019-06-25 | 成都纳海川环境工程有限公司 | Inorganic microparticle scale dispersing agent and preparation method thereof |
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