CN107601461A - A kind of magnetic composite of Fe 3 O 4 coating carbon nanotube and preparation method thereof - Google Patents
A kind of magnetic composite of Fe 3 O 4 coating carbon nanotube and preparation method thereof Download PDFInfo
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- CN107601461A CN107601461A CN201711035583.1A CN201711035583A CN107601461A CN 107601461 A CN107601461 A CN 107601461A CN 201711035583 A CN201711035583 A CN 201711035583A CN 107601461 A CN107601461 A CN 107601461A
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Abstract
The invention provides a kind of magnetic composite of Fe 3 O 4 coating carbon nanotube, its preparation method comprises the following steps：(1) CNTs after acidifying is added in deionized water and carries out ultrasonic disperse, CNTs dispersion liquids are made；(2) by soluble ferrite/iron salt dissolved in deionized water, ferrous salt/iron salt solutions are made；(3) CNTs dispersion liquids are mixed with ferrous salt/iron salt solutions, hydrazine hydrate and surfactant is added after mixing, after mixing, is placed at 100 180 DEG C and reacts 8 16h；(4) reaction end filters after being cooled to room temperature and washing reaction product is to neutrality, finally dries and is made.Present invention process process is simple, and preparation condition is gentle, and reaction temperature is relatively low, cost is cheap, using water as solvent, does not add heavy metal salt, environmentally friendly, the magnetic composite of obtained ferriferrous oxide nano-particle enveloped carbon nanometer tube has a higher saturation magnetization, and performance is preferable.
Description
Technical field
The invention belongs to nano composite material technical field, and in particular to a kind of magnetic of Fe 3 O 4 coating carbon nanotube
Property composite and preparation method thereof.
Background technology
Since CNT (CNTs) is found, its unique structure and physicochemical properties, such as excellent mechanics, heat
The performances such as, electricity and high-specific surface area get more and more people's extensive concerning.The high surface area that CNTs possesses, low-resistivity, and
Good chemical stability so that CNT is in catalyst, ultracapacitor, lithium ion battery material and biological field
Etc. application aspect, all there is huge potential.In recent years, the modification to CNT is increasingly becoming focus, because after modification
CNT, can not only overcome some defects of itself to be such as not easy scattered but also its new performance can be assigned, such as magnetics, electricity, light
Etc. performance.Magnetic material is shown because it has unique physical and chemical performance in physics, chemistry, biology, medicine and other fields
Huge application potential, thus often by magnetic-particle with CNT is compound obtains magnetic carbon nano-tube.Magnetic ferroferric oxide
(Fe3O4) convieniently synthesized, better heat stability, magnetic property be excellent, compatibility is good, is widely used for being coated on carbon nano tube surface.
Use magnetic Fe3O4CNT after particles coat, the characteristics such as outstanding magnetic, electromagnetic wave absorption can be shown, it is in electricity
Chemical field, catalytic field, suction ripple field and Material reinforcement body field have wide practical use.
At present, the magnetic carbon nano-tube of ferroso-ferric oxide cladding is prepared into typically by coprecipitation or solvent-thermal method etc.
Arrive.Such as：By CoCl2·6H2O、FeCl3·6H2O、CrCl3·6H2O、ZnCl2Deionization is dissolved in surface-modified carbon nanotubes
In water, precursor solution is obtained, using the NaOH aqueous solution as precipitating reagent, magnetic carbon nano-tube is obtained by coprecipitation.It is this
Method adds excessive heavy metal salt, and cost is high, there is pollution, and ferriferrous oxide particles size and size distribution ranges to environment
Control be extremely limited.Using organic solvent as medium, the magnetic carbon of ferroso-ferric oxide load is obtained by solvent-thermal method
Nanotube.But this method and step is cumbersome, temperature is high, time length, and uses organic solvent, and obtained product is impure, security
It is relatively low.
The content of the invention
For the above-mentioned problems in the prior art, the present invention provides a kind of magnetic of Fe 3 O 4 coating carbon nanotube
Property composite and preparation method thereof, can effectively solve that existing preparation technology is cumbersome, and severe reaction conditions, cost is high, to ring
The problem of border pollutes.
To achieve the above object, the technical solution adopted for the present invention to solve the technical problems is：
A kind of magnetic composite of Fe 3 O 4 coating carbon nanotube, its preparation method comprise the following steps：
(1) CNTs after acidifying is added in deionized water and carries out ultrasonic disperse, CNTs dispersion liquids are made；CNTs is acidified
After processing, its purity is higher, and is more favorable for the attachment of follow-up nano ferriferrous oxide；
(2) by soluble ferrite/iron salt dissolved in deionized water, ferrous salt/iron salt solutions are made；
(3) CNTs dispersion liquids are mixed with ferrous salt/iron salt solutions, hydrazine hydrate and surface-active is added after stirring and evenly mixing
Agent, after stirring and evenly mixing, it is placed at 100-180 DEG C and reacts 8-16h；
The hydrazine hydrate added can carry out redox reaction with molysite/ferrous salt, generate ferriferrous oxide nano-particle,
Surfactant can control the pattern of the ferriferrous oxide nano-particle of generation as template；
(4) reaction end, which is cooled to after room temperature, filters and washing reaction product is to neutrality, finally dry ferroso-ferric oxide
The magnetic composite of enveloped carbon nanometer tube.
Further, the CNTs after being acidified in step (1) is prepared by the following method to obtain：
1) it is 3 by volume by the concentrated sulfuric acid and concentrated nitric acid:1 mixing, is made nitration mixture；
2) CNTs is added in nitration mixture to the solution for being configured to that concentration is 6-9g/L, added after being ultrasonically treated 1-4h then at 120 DEG C
Heat backflow 1-3h；
3) it is 7 step 2) products therefrom to be filtered and washed to filtrate pH, and vacuum drying 12-14h is made.
Further, CNTs dispersion liquid concentrations are 3-8g/L in step (1).
Further, CNTs is multi-walled carbon nanotube, a diameter of 10-100nm, and length is 10-50 μm.
Further, soluble ferrite is iron ammonium sulfate, frerrous chloride or ferrous sulfate in step (2)；It is soluble
Molysite is iron chloride, ferric sulfate or ferric nitrate.
Further, the concentration of ferrous salt/iron salt solutions is 0.2-0.8mol/L in step (2).
Further, the volume ratio of CNTs dispersion liquids and ferrous salt/iron salt solutions is 1-1.5 in step (3):1.
Further, the volume ratio of hydrazine hydrate and ferrous salt/iron salt solutions is 3-4 in step (3):10.
Further, surfactant is sodium citrate, sodium acetate, cetyl trimethylammonium bromide and polyethylene glycol
At least one of 2000, the mol ratio of its addition and added ferrous salt/molysite is 0.01-0.8:1.
Magnetic composite of a kind of Fe 3 O 4 coating carbon nanotube provided by the invention and preparation method thereof, has
Following beneficial effect：
(1) preparation technology of the invention is simple, and preparation condition is gentle, and reaction temperature is relatively low, and cost is cheap, using water as molten
Agent, heavy metal salt is not added, it is environmentally friendly.
(2) ferroso-ferric oxide produced by the present invention is nano-particle, and is evenly distributed on CNTs surface.
(3) magnetic composite of ferriferrous oxide nano-particle enveloped carbon nanometer tube produced by the present invention has relatively low
Coercivity and higher saturation magnetization, performance are preferable.
Brief description of the drawings
Fig. 1 is CNTs/Fe prepared by the embodiment of the present invention 13O4The scanning electron microscope (SEM) photograph of magnetic composite.
Fig. 2 is CNTs/Fe prepared by the embodiment of the present invention 23O4The scanning electron microscope (SEM) photograph of magnetic composite.
Fig. 3 is CNTs/Fe prepared by the embodiment of the present invention 13O4The X-ray diffractogram of magnetic composite.
Fig. 4 is CNTs/Fe prepared by the embodiment of the present invention 13O4The infrared spectrogram of magnetic composite.
Fig. 5 is CNTs/Fe prepared by the embodiment of the present invention 13O4The hysteresis curve figure of magnetic composite.
Embodiment
Embodiment 1
A kind of magnetic composite of Fe 3 O 4 coating carbon nanotube, its preparation method comprise the following steps：
(1) CNTs after 0.1g is acidified is added to ultrasonic disperse 30min in 20ml deionized waters, and it is 5g/L to obtain concentration
CNTs dispersion liquids；
Wherein, the CNTs after acidifying is prepared by the following method to obtain：
1) 3 are pressed:1 volume ratio measures the 60ml concentrated sulfuric acids and 20ml concentrated nitric acids prepare nitration mixture；
2) 0.6g CNTs and the nitration mixture prepared are mixed, being placed in 120 DEG C after supersound process 4h is heated to reflux 3h；
3) it is 7 product to be filtered and washed to filtrate pH, is subsequently placed in 60 DEG C of vacuum drying 12h and produces acidifying CNTs.
(2) by 0.005mol (NH4)2Fe(SO4)2·6H2O is completely dissolved in 15ml deionized waters, is obtained concentration and is
0.33mol/L ferrous salt solution；
(3) by CNTs dispersion liquids and (NH4)2Fe(SO4)2Solution is mixed, and 5ml N are added after being sufficiently stirred2H4·H2O, stir
0.003mol sodium acetates and 0.000068mol cetyl trimethylammonium bromides are added after mixing uniformly as surfactant,
It is transferred to after well mixed in reactor, reacts 10h at 120 DEG C；
(4) reaction end, which is cooled to after room temperature, filters and washing reaction product is to neutrality, is finally placed in 60 DEG C dry four
The magnetic composite of Fe 3 O enveloped carbon nanometer tube is CNTs/Fe3O4Magnetic composite.
Fig. 1 is CNTs/Fe3O4The scanning electron microscope (SEM) photograph of magnetic composite, as seen from the figure, nanometer Fe3O4For block polyhedron
Particle and uniformly it is attached on CNTs.
Fig. 3 is CNTs/Fe3O4The X-ray diffractogram of magnetic composite, as can be seen from Figure, the diffraction maximum of sample with
Fe3O4PDF cards JCPDs19-0629 it is consistent, indicate the Fe in products therefrom3O4It is inverse spinel structure, thing is mutually single,
Exist without other impurities, crystallinity is higher.
Fig. 4 is CNTs/Fe3O4The infrared spectrogram of magnetic composite, 1634cm in figure-1The carbon skeleton of the corresponding graphite in place
Peak, in 590cm-1There is Fe in place3O4Fe-O stretching vibration characteristic peaks.
Fig. 5 is CNTs/Fe3O4The hysteresis curve figure of magnetic composite, as seen from the figure, CNTs/Fe3O4Magnetic coupling material
The saturation magnetization of material has reached 65emu/g, and saturation magnetization is higher.
Embodiment 2
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：Added surfactant is
0.001mol sodium citrates and 0.000068mol cetyl trimethylammonium bromides.
Fig. 2 is CNTs/Fe3O4The scanning electron microscope (SEM) photograph of magnetic composite, as seen from the figure, nanometer Fe3O4For spherical particle and
Uniformly it is attached on CNTs.
Embodiment 3
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：(NH4)2Fe(SO4)2Solution
Concentration be 0.5mol/L.
Embodiment 4
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：Ferrous salt solution used is
0.33mol/L solution of ferrous chloride.
Embodiment 5
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：Iron salt solutions used are
0.33mol/L ferrum sulfuricum oxydatum solutum.
Embodiment 6
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：Add N2H4·H2O volume
For 6ml.
Embodiment 7
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：Reaction temperature in step (3)
For 160 DEG C.
Embodiment 8
The method of the method for the present embodiment and embodiment 1 is essentially identical, and difference is：Reaction time in step (3)
For 12h.
According to embodiment 1-8 preparation method, nanometer Fe can obtain3O4The magnetic that particle is uniformly attached on CNTs is answered
Condensation material, and nanometer Fe can control by surfactant3O4The pattern of particle, such as spherical, block, each embodiment is made
The saturation magnetization of standby magnetic composite is higher, the nanometer Fe being coated on CNTs3O4Purity is higher, crystallinity compared with
It is good.
Claims (10)
1. a kind of preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube, it is characterised in that including following
Step：
(1) CNTs after acidifying is added in deionized water and carries out ultrasonic disperse, CNTs dispersion liquids are made；
(2) by soluble ferrite/iron salt dissolved in deionized water, ferrous salt/iron salt solutions are made；
(3) the CNTs dispersion liquids are mixed with the ferrous salt/iron salt solutions, hydrazine hydrate is added after stirring and evenly mixing and surface is lived
Property agent, after being again stirring for mixing, is placed at 100-180 DEG C and reacts 8-16h；
(4) reaction end filters after being cooled to room temperature and washing reaction product is to neutrality, finally dry that ferroso-ferric oxide coats
The magnetic composite of CNT.
2. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that the CNTs after being acidified in step (1) is prepared by the following method to obtain：
1) it is 3 by volume by the concentrated sulfuric acid and concentrated nitric acid:1 mixing, is made nitration mixture；
2) CNTs is added in nitration mixture to the solution for being configured to that concentration is 6-9g/L, heated back after being ultrasonically treated 1-4h then at 120 DEG C
Flow 1-3h；
3) it is 7 step 2) products therefrom to be filtered and washed to filtrate pH, and vacuum drying 12-14h is made.
3. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that CNTs dispersion liquid concentrations are 3-8g/L in step (1).
4. the preparation side of the magnetic composite of the Fe 3 O 4 coating carbon nanotube according to claim any one of 1-3
Method, it is characterised in that CNTs is multi-walled carbon nanotube, a diameter of 10-100nm, and length is 10-50 μm.
5. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that soluble ferrite is iron ammonium sulfate, frerrous chloride or ferrous sulfate in step (2)；Soluble ferric iron salt is chlorination
Iron, ferric sulfate or ferric nitrate.
6. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that the concentration of ferrous salt/iron salt solutions is 0.2-0.8mol/L in step (2).
7. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that the volume ratio of CNTs dispersion liquids and ferrous salt/iron salt solutions is 1-1.5 in step (3):1.
8. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that the volume ratio of hydrazine hydrate and ferrous salt/iron salt solutions is 3-4 in step (3):10.
9. the preparation method of the magnetic composite of Fe 3 O 4 coating carbon nanotube according to claim 1, it is special
Sign is that the surfactant is in sodium citrate, sodium acetate, cetyl trimethylammonium bromide and polyethylene glycol 2000
At least one, the mol ratio of its addition and added ferrous salt/molysite is 0.01-0.8:1.
10. the magnetic for the Fe 3 O 4 coating carbon nanotube that the method as described in claim any one of 1-9 is prepared is answered
Condensation material.
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| CN108598440A (en) * | 2018-05-15 | 2018-09-28 | 浙江南都电源动力股份有限公司 | A kind of preparation method of composite material |
| CN108659660A (en) * | 2018-06-12 | 2018-10-16 | 阜南县猛发工艺品有限公司 | A kind of preparation method of the water-fast heat-resisting aqueous woodware paint of wood artwork |
| CN109119625A (en) * | 2018-09-28 | 2019-01-01 | 国网山东省电力公司电力科学研究院 | A kind of preparation method of ferroso-ferric oxide-carbon nanotube lithium cell cathode material |
| CN109535122A (en) * | 2019-01-14 | 2019-03-29 | 浙江昊唐实业有限公司 | A method of preparing glycerol formal |
| CN110559935A (en) * | 2019-10-25 | 2019-12-13 | 青岛科技大学 | Preparation method of one-dimensional nano magnetons with stable solution dispersibility |
| CN110868818A (en) * | 2019-11-28 | 2020-03-06 | 安徽实友电力金具有限公司 | Smart home devices's protecting sheathing with moisture resistance |
| CN113339509A (en) * | 2021-06-26 | 2021-09-03 | 北京建筑大学 | Application method of magnetic carbon nano tube for sealing technology |
| CN113388374A (en) * | 2021-06-16 | 2021-09-14 | 北京建筑大学 | Application method of magnetic carbon nano tube |
| CN113999432A (en) * | 2021-11-18 | 2022-02-01 | 彗晶新材料科技(杭州)有限公司 | Fe3O4Preparation method of @ MWCNTs nano composite material and electronic equipment |
| CN114524463A (en) * | 2022-03-18 | 2022-05-24 | 中南大学 | Super-large-size high-length-diameter-ratio ferroferric oxide two-dimensional nanosheet and preparation method thereof |
-
2017
- 2017-10-30 CN CN201711035583.1A patent/CN107601461A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 吴涛: "纳米碳基磁性复合材料的制备及在磷酸钙骨水泥中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (11)
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| CN108598440A (en) * | 2018-05-15 | 2018-09-28 | 浙江南都电源动力股份有限公司 | A kind of preparation method of composite material |
| CN108659660A (en) * | 2018-06-12 | 2018-10-16 | 阜南县猛发工艺品有限公司 | A kind of preparation method of the water-fast heat-resisting aqueous woodware paint of wood artwork |
| CN109119625A (en) * | 2018-09-28 | 2019-01-01 | 国网山东省电力公司电力科学研究院 | A kind of preparation method of ferroso-ferric oxide-carbon nanotube lithium cell cathode material |
| CN109535122A (en) * | 2019-01-14 | 2019-03-29 | 浙江昊唐实业有限公司 | A method of preparing glycerol formal |
| CN110559935A (en) * | 2019-10-25 | 2019-12-13 | 青岛科技大学 | Preparation method of one-dimensional nano magnetons with stable solution dispersibility |
| CN110868818A (en) * | 2019-11-28 | 2020-03-06 | 安徽实友电力金具有限公司 | Smart home devices's protecting sheathing with moisture resistance |
| CN113388374A (en) * | 2021-06-16 | 2021-09-14 | 北京建筑大学 | Application method of magnetic carbon nano tube |
| CN113339509A (en) * | 2021-06-26 | 2021-09-03 | 北京建筑大学 | Application method of magnetic carbon nano tube for sealing technology |
| CN113999432A (en) * | 2021-11-18 | 2022-02-01 | 彗晶新材料科技(杭州)有限公司 | Fe3O4Preparation method of @ MWCNTs nano composite material and electronic equipment |
| CN114524463A (en) * | 2022-03-18 | 2022-05-24 | 中南大学 | Super-large-size high-length-diameter-ratio ferroferric oxide two-dimensional nanosheet and preparation method thereof |
| CN114524463B (en) * | 2022-03-18 | 2023-05-26 | 中南大学 | Super-large-size high-length-diameter-ratio ferroferric oxide two-dimensional nano sheet and preparation method thereof |
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Application publication date: 20180119 |