CN105148837B - A kind of by core, ferroso-ferric oxide of CNT is composite of shell and preparation method thereof - Google Patents
A kind of by core, ferroso-ferric oxide of CNT is composite of shell and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to it is a kind of by core, ferroso-ferric oxide of CNT be composite of shell and preparation method thereof.It is characterised by with FeCl2/H2O2Fenton reagent, reducing agent iron powder, CNT and the precipitating reagent urea or hexamethylenetetramine of composition are raw material, carry out surface hydroxylation modification to CNT with Fenton reagent first, then add appropriate iron powder regulation Fe2+The concentration of ion, further with urea or hexamethylenetetramine, precipitation of iron ions is come out under suitable condition using sluggish precipitation, sediment is finally obtained into final product by the technique such as separation, washing, dry.CNT/the ferriferrous oxide composite material of gained " core shell " structure is characterized in that with using special construction of the CNT as core, ferroso-ferric oxide for shell, ferroso-ferric oxide is equably covered in CNT outer surface in continuous laminate structure, and the interface between core shell is weak.The preparation method technique is simple, and products therefrom will have broad application prospects in fields such as chemical catalysis, sensor, new energy materialses, electromagnetic shielding material and high performance polymer base composite materials.
Description
Technical field
The invention belongs to carbon nanomaterial processing and applied technical field, and in particular to one kind is using CNT as core, four
Fe 3 O is composite of shell and preparation method thereof.
Background technology
CNT has very excellent mechanical performance and electric heating magnetic functional characteristic, is a kind of preferable nano carbon material
Material.By the basic and applied research of more than two decades, CNT research field achieves lot of research and technological progress,
The industrial applications stage is had been introduced at present, purposes is quite varied, is such as used to improve and improves metal, nonmetallic, macromolecule
The performance of based composites, it is also commonly used for inhaling the fields such as ripple, catalyst, electrochemistry, new energy.Although CNT has many excellent
It is different in nature can, but in some fields, only carry out that suitable surface is modified or processing could preferably play it to CNT
Prominent characteristic, so as to expand the application field of CNT, have great importance.
Common a kind of carbon nano tube surface processing method is in carbon nano tube surface coated magnetic nano-particle, such as four oxygen
Change three-iron（Fe3O4）Nano-particle.Patent [Li Kezhi, Cheng Sanxu, Qi Lehua, Li Hejun, virgin forever bright ferroso-ferric oxides
(Fe3O4The preparation method of)/carbon nano tube compound material：China, CN102583315A] disclose one kind and prepare four oxidations three
The method of iron/CNT, the clad nanometer Fe of ferroferric oxide/carbon nano tube composite material prepared by this method3O4Particle diameter
Uniformly, nano particle average grain diameter is less than 10nm.Patent [Deng Jingheng, Xiao Guoguang, Yu Kanping, Yang Guochao, Zeng Juan, Tian Jian
Sharp carbon nanotube loaded multi-stage nano ferroferric oxide adsorbents of and preparation method and application：China, CN103007887A]
A kind of preparation method for preparing carbon nanotube loaded ferroso-ferric oxide is disclosed, the control of preparation method condition is more strict.Document
[ Zhan Y, Zhao R, Lei Y, et al. A novel carbon nanotubes/Fe3O4 inorganic
hybrid material. Journal of Magnetism and Magnetic Materials, 2011, 323(7):
1006-1010.] Fe made by solvent-thermal method3O4Nano-particles self assemble is in carbon nano tube surface, CNT/Fe3O4It is multiple
Condensation material has good absorbing property.
The ferroso-ferric oxide that prior art is related to all is in granular form substantially, and some other special appearance structure is more rare.
The content of the invention
It is an object of the invention to provide a kind of using CNT as the composite of core, ferroso-ferric oxide for shell and its preparation
Method.A kind of CNT/Fe of " core-shell " structure has been prepared using sluggish precipitation3O4Composite, Fe3O4In continuous
Flake nano structure, preparation method have technique it is simple, it is green, be evenly coated stabilization, absorbing property preferably and into
The characteristics of this is low, in catalysis, sensor, electromagnetic shielding material, new energy materialses, biotechnology and high-performance composite materials etc.
Field has a good application prospect.
Realizing the technical scheme of the object of the invention is：
A kind of preparation method using CNT as core, ferroso-ferric oxide for the composite of shell, comprise the following steps：
（1）By a certain percentage, CNT is distributed in deionized water, adds watery hydrochloric acid to adjust 1.0≤PH≤3.5,
Fenton reagent is added dropwise under the conditions of ultrasonic agitation, excessive reduced iron powder is added after 1-12h is added dropwise, continues to be stirred by ultrasonic
0.5-4h, excess iron powder is removed with magnet adsorption method；
（2）Take step（1）In obtained suspension, according to Fe2+Concentration, add the OH of 0.5-2 times of equivalent-1Type precipitating reagent,
1-12h is reacted under 200-2500rmp mechanical agitation and 75-95 DEG C of temperature conditionss, further across separating, wash after terminating
Wash, 80-200 DEG C of drying, the technique such as crushing obtain having using special construction of the CNT as core, ferroso-ferric oxide for shell.
Described CNT is at least one of multi-walled carbon nanotube, single-walled carbon nanotube.
Described CNT and the mass ratio of deionized water are 1：（50-500）.
Described Fenton reagent is by Fe2+And H2O2Assemble and form, Fe2+The sediment ferroso-ferric oxide of generation and carbon nanometer
The mass ratio of pipe is 1：（0.5-2）.
Described OH-1Type precipitating reagent is at least one of urea, hexamethylenetetramine.
The general principle that the present invention prepares composite is：Handled by Fenton reagent, in carbon nano tube surface suspension
A number of oh group, so that CNT can be in Fe2+Fine dispersion and stability are kept in solution decentralized system,
Precipitating reagent urea or hexamethylenetetramine are added, when being warming up to proper temperature, starts the slow OH that dissociates-1With Fe2+Occur anti-
Should, and preferentially separate out and precipitate in carbon nano tube surface, under the conditions of suitable mixing speed, velocity gradient field induced precipitation thing is along carbon
Nanotube top layer grows, and forms continuous laminate structure.
The substantial advantage of the present invention is：
（1）In the preparation technology of ferroso-ferric oxide in the composite, Fe sources in Fenton reagent are directly make use of, are had
There is the features such as simple and environmentally-friendly energy-conservation of technique, cost is low.
（2）Prepared CNT/ferriferrous oxide composite material structure is novel, has using CNT as core, four
Fe 3 O is the special construction of shell, and ferroso-ferric oxide is in continuous laminate structure, is equably covered in CNT outer surface,
Core-shell interface is weak.
Brief description of the drawings
Fig. 1 is the CNT prepared by embodiment 1（CNTs）/ ferroso-ferric oxide（Fe3O4）The typical XRD of composite
Diffraction pattern.It is respectively Fe in diffraction maximum corresponding to 30.45 °, 35.78 °, 43.39 °, 53.74 °, 57.27 ° and 62.81 °3O4
（220）、（311）、（400）、（422）、（511）With（440）Crystal face；
Fig. 2 is CNTs/Fe prepared by embodiment 13O4The typical scan electron microscope of composite.It can be seen that
The signified composite of arrow shows typical " core-shell " structure, Fe because bending failure makes CNT exposed3O4In continuous thin
Rotating fields, equably it is covered in CNT outer surface.
Fig. 3 is CNTs/Fe prepared by embodiment 13O4The hysteresis curve figure of composite.CNTs/Fe3O4Composite
Remanent magnetization is 4.22emu/g, and saturation magnetic saturation intensity is 16.68emu/g, coercivity 24.73Oe, shows soft magnetism
Property.
Fig. 4 is CNTs/Fe prepared by embodiment 13O4The absorbing property figure of composite.CNTs/Fe3O4Composite
The a width of 6-18GHz of wavestrip is inhaled, wide with larger suction wavestrip, maximum reflectivity decays to -8.3dB.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment.
Embodiment 1
（1）1g multi-walled carbon nanotubes are weighed, are dispersed in 200mL deionized waters, add watery hydrochloric acid, adjust pH=3.5.
It is added dropwise under the conditions of ultrasonic agitation by the hydrogen peroxide that 100ml mass concentrations are 30%, 100ml concentration is 0.1mol/L protochloride
Fenton reagent made from ferrous solution, excessive reduced iron powder is added after being added dropwise in 6h, continue that 0.5h is stirred by ultrasonic, use magnetic
Iron adsorption method removes excess iron powder；
（2）Take step（1）In obtained suspension, according to Fe2+Concentration, add equivalent OH-1Urea, be warming up to 95
DEG C, in 200rmp mechanic whirl-nett reaction 1h, obtained after terminating further across the technique such as separation, washing, 200 DEG C of dryings, crushing
To final product.
Embodiment 2
（1）1g multi-walled carbon nanotubes are weighed, are dispersed in 50ml deionized waters, add watery hydrochloric acid, adjust pH=3.5.
It is added dropwise under the conditions of ultrasonic agitation by the hydrogen peroxide that 100ml mass concentrations are 30%, 20ml concentration is that 0.1mol/L frerrous chloride is molten
Fenton reagent made from liquid（）, excessive reduced iron powder is added after 1h is added dropwise, continues that 0.5h is stirred by ultrasonic, is inhaled with magnet
Subsidiary formula method removes excess iron powder.
（2）Take step（1）In obtained suspension, according to Fe2+Concentration, add 0.5 times of equivalent OH-1Six methines four
Amine, 75 DEG C are warming up to, in 1000rmp mechanic whirl-nett reaction 4h, further across separation, washing, 80 DEG C of dryings, powder after terminating
The technique such as broken obtains final product.
Embodiment 3
（1）1g single-walled carbon nanotubes are weighed, are dispersed in 500ml deionized waters, add watery hydrochloric acid, adjust pH=3.
It is added dropwise under the conditions of ultrasonic agitation by the hydrogen peroxide that 400ml mass concentrations are 30%, 50ml concentration is that 0.2mol/L ferrous sulfate is molten
Fenton reagent made from liquid, excessive reduced iron powder is added after 12h is added dropwise, continue that 4h is stirred by ultrasonic, use magnet adsorption
Method removes excess iron powder.
（2）Take step（1）In obtained suspension, according to Fe2+Concentration, add 0.5 times of equivalent OH-1Six methines four
Amine, be warming up to 85 DEG C, in 2500rmp mechanic whirl-nett reaction 12h, after terminating further across separation, washing, 120 DEG C of dryings,
The techniques such as crushing obtain final product.
Embodiment 4
（1）1g single-walled carbon nanotubes are weighed, are dispersed in 200ml deionized waters, add watery hydrochloric acid, adjust pH=3.
It is added dropwise under the conditions of ultrasonic agitation by the hydrogen peroxide that 100ml mass concentrations are 30%, 50ml concentration is that 0.2mol/L ferrous sulfate is molten
Fenton reagent made from liquid, excessive reduced iron powder is added after 6h is added dropwise, continue that 4h is stirred by ultrasonic, with magnet adsorption side
Method removes excess iron powder.
（2）Take step（1）In obtained suspension, according to Fe2+Concentration, add 2 times of equivalent OH-1Urea, be warming up to 85
DEG C, in 1000rmp mechanic whirl-nett reaction 2h, obtained after terminating further across the technique such as separation, washing, 120 DEG C of dryings, crushing
To final product.
Claims (4)
- A kind of 1. composite using CNT as core, ferroso-ferric oxide for shell, it is characterised in that：The composite is one kind CNT/the Fe of " core-shell " structure3O4Composite, Fe3O4In continuous flake nano structure, carbon is equably covered in Nanometer tube outer surface, core-shell interface are weak；Its preparation method includes the steps：（1）By a certain percentage, CNT is distributed in deionized water, adds watery hydrochloric acid to adjust 1.0≤PH≤3.5, in ultrasound Fenton reagent is added dropwise under stirring condition, excessive reduced iron powder is added after 1-12h is added dropwise, continues that 0.5- is stirred by ultrasonic 4h, excess iron powder is removed with magnet adsorption method；（2）Take step（1）In obtained suspension, according to Fe2+Concentration, add the OH of 0.5-2 times of equivalent-1Type precipitating reagent, React 1-12h under 200-2500rmp mechanical agitation and 75-95 DEG C of temperature conditionss, after terminating further across separation, washing, 80-200 DEG C of drying, crushing are obtained using composite of the CNT as core, ferroso-ferric oxide for shell；Step（2）Described OH-1Type precipitating reagent is at least one of urea, hexamethylenetetramine.
- 2. composite according to claim 1, it is characterized in that：Step（1）Described CNT is multi-wall carbon nano-tube At least one of pipe, single-walled carbon nanotube.
- 3. composite according to claim 1 or claim 2, it is characterized in that：Step（1）Described CNT and deionized water Mass ratio is 1：（50-500）.
- 4. composite according to claim 1, it is characterized in that：Step（1）Described Fenton reagent is by Fe2+And H2O2Group With into Fe2+The sediment ferroso-ferric oxide of generation and the mass ratio of CNT are 1：（0.5-2）.
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| CN111036184A (en) * | 2020-01-03 | 2020-04-21 | 福州大学 | Preparation of hydroxylated magnetic nitrogen-doped carbon nano-tube based on MOF and application of hydroxylated magnetic nitrogen-doped carbon nano-tube in detection of auxin content in tea |
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| CN102489252A (en) * | 2011-12-19 | 2012-06-13 | 南京大学 | Ferroferric oxide nano crystal loaded on acid-modified carbon nano tube and preparation method thereof |
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| 多壁碳纳米管表面均匀沉淀包覆四氧化三铁及其磁性能的研究;孙健明等;《材料科学与工艺》;20140630;第22卷(第3期);102-107 * |
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