CN105148837A - Composite material by using carbon nano-tube as core and ferriferrous oxide as shell and preparation method thereof - Google Patents
Composite material by using carbon nano-tube as core and ferriferrous oxide as shell and preparation method thereof Download PDFInfo
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- CN105148837A CN105148837A CN201510452953.6A CN201510452953A CN105148837A CN 105148837 A CN105148837 A CN 105148837A CN 201510452953 A CN201510452953 A CN 201510452953A CN 105148837 A CN105148837 A CN 105148837A
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Abstract
The invention relates to a composite material by using a carbon nano-tube as a core and ferriferrous oxide as a shell and a preparation method thereof. The composite material is characterized in that a Fenton reagent comprising FeCl2/H2O2, reductant iron powder, a carbon nano-tube and precipitant urea or hexamethylenetetramine are used as raw materials. The preparation method comprises the following steps of, firstly, performing surface hydroxylation modification on the carbon nano-tube with the Fenton reagent; then, adding a proper amount of the iron powder to regulate the concentration of Fe<2+> ions, further precipitating the iron ions with urea or hexamethylenetetramine by adopting a homogeneous precipitation method under a proper condition; and finally, conducting separating, washing, drying and other processes on the precipitate to obtain a final product. The carbon nano-tube/ferriferrous oxide composite material with a 'core-shell' structure is characterized by having a special structure by using the carbon nano-tube as the core and the ferriferrous oxide as the shell; and ferriferrous oxide having a continuous thin-layer structure uniformly covers the outer surface of the carbon nano-tube, and the interface between the core and the shell is weak. The preparation method is simple in process, and the product has a wide application prospect in chemical catalysis, sensors, new energy materials, electromagnetic shielding materials, high-performance polymer-based composite materials and other fields.
Description
Technical field
The invention belongs to carbon nanomaterial processing and applied technical field, be specifically related to a kind of take CNT as core, the tri-iron tetroxide composite that is shell and preparation method thereof.
Background technology
CNT has very excellent mechanical performance and electric heating magnetic functional characteristic, is a kind of desirable nano-carbon material.Through the basic and applied research of more than two decades, CNT research field achieves lot of research and technological progress, enter into the industrial applications stage at present, purposes is very extensive, as for improving the performance improving metal, nonmetal, polymer-based composite, be also usually used in inhaling the fields such as ripple, catalyst, electrochemistry, new forms of energy.Although CNT has many excellent properties, in some field, only have and carry out suitable surface modification or process playing its outstanding characteristic better to CNT, thus the application of CNT can be expanded, have great importance.
A common class carbon nano tube surface processing method is at carbon nano tube surface coated magnetic nano particle, as tri-iron tetroxide (Fe
3o
4) nano particle.Patent [Li Kezhi, Cheng Sanxu, Qi Lehua, Li Hejun, Tong Yonghuang. tri-iron tetroxide (Fe
3o
4the preparation method of)/carbon nano tube compound material: China, CN102583315A] disclose a kind of method preparing ferroferric oxide/carbon nanotube, the clad nanometer Fe of ferroferric oxide/carbon nano tube composite material prepared by the method
3o
4uniform particle sizes, nano particle average grain diameter is less than 10nm.Patent [Deng Jingheng, Xiao Guoguang, Yu Kanping, Yang Guochao, Zeng Juan, Tian Jianli. carbon nanotube loaded multi-stage nano ferroferric oxide adsorbent and preparation method thereof and application: China, CN103007887A] disclose a kind of preparation method preparing carbon nanotube loaded tri-iron tetroxide, preparation method's condition controls comparatively strict.Document [ZhanY, ZhaoR, LeiY, etal.Anovelcarbonnanotubes/Fe
3o
4inorganichybridmaterial.JournalofMagnetismandMagneticMat erials, 2011,323 (7): 1006-1010.] make Fe by solvent-thermal method
3o
4nano-particles self assemble in carbon nano tube surface, CNT/Fe
3o
4composite has good absorbing property.
The tri-iron tetroxide that prior art relates to is substantially all graininess, and some other special appearance structure is more rare.
Summary of the invention
The object of this invention is to provide a kind of take CNT as core, the tri-iron tetroxide composite that is shell and preparation method thereof.Employing sluggish precipitation has prepared a kind of CNT/Fe of " core-shell " structure
3o
4composite, Fe
3o
4in continuous print flake nano structure, preparation method has that technique is simple, environmental protection, coated uniform and stable, absorbing property is better and cost is low feature, have a good application prospect in fields such as catalysis, sensor, electromagnetic shielding material, new energy materials, biotechnology and high-performance composite materials.
The technical scheme realizing the object of the invention is:
Take CNT as core, a preparation method for the tri-iron tetroxide composite that is shell, comprise the steps:
(1) by a certain percentage, by carbon nanotube dispersed in deionized water, add watery hydrochloric acid adjustment 1.0≤PH≤3.5, Fenton reagent is dripped under ultrasonic agitation condition, excessive reduced iron powder is added after 1-12h dropwises, continue ultrasonic agitation 0.5-4h, by magnet adsorption method removing excess iron powder;
(2) suspension obtained in step (1) is got, according to Fe
2+concentration, adds the OH of 0.5-2 times of equivalent
-1type precipitating reagent, under the mechanical agitation and 75-95 DEG C of temperature conditions of 200-2500rmp, react 1-12h, after terminating further across being separated, washing, the 80-200 DEG C technique such as drying, pulverizing obtains having with CNT is core, tri-iron tetroxide is shell special construction.
Described CNT is at least one in multi-walled carbon nano-tubes, SWCN.
Described CNT and the mass ratio of deionized water are 1:(50-500).
Described Fenton reagent is by Fe
2+and H
2o
2assembly forms, Fe
2+the sediment tri-iron tetroxide generated and the mass ratio of CNT are 1:(0.5-2).
Described OH
-1type precipitating reagent is at least one in urea, hexamethylenetetramine.
The general principle that the present invention prepares composite is: through Fenton reagent process, and carbon nano tube surface hangs the oh group of upper some, thus enables CNT at Fe
2+keeping fine dispersion and stability in Solution Dispersion system, add precipitating reagent urea or hexamethylenetetramine, when being warming up to proper temperature, starting slowly to dissociate OH
-1with Fe
2+react, and preferentially separate out precipitation in carbon nano tube surface, under suitable mixing speed condition, velocity gradient field induced precipitation thing, along the growth of CNT top layer, forms continuous print laminate structure.
Substantial advantage of the present invention is:
(1) features such as in the preparation technology of tri-iron tetroxide in the composite, directly make use of Fe source in Fenton reagent, have that technique is simple, environmental protection and energy saving, cost are low.
(2) CNT prepared by/ferriferrous oxide composite material novel structure, the special construction that to have with CNT be core, tri-iron tetroxide is shell, tri-iron tetroxide is continuous print laminate structure, covers CNT outer surface equably, and core-shell interface is weak.
Accompanying drawing explanation
CNT (CNTs)/tri-iron tetroxide (Fe of Fig. 1 prepared by embodiment 1
3o
4) the typical XRD diffraction pattern of composite.Fe is respectively at 30.45 °, 35.78 °, 43.39 °, 53.74 °, 57.27 ° and 62.81 ° of corresponding diffraction maximums
3o
4(220), (311), (400), (422), (511) and (440) crystal face;
Fig. 2 is CNTs/Fe prepared by embodiment 1
3o
4the typical scan Electronic Speculum figure of composite.As can be seen from the figure, the composite of arrow indication makes CNT expose because of bending failure, shows typical " core-shell " structure, Fe
3o
4in continuous print laminate structure, cover CNT outer surface equably.
Fig. 3 is CNTs/Fe prepared by embodiment 1
3o
4the hysteresis curve figure of composite.CNTs/Fe
3o
4the remanent magnetization of composite is 4.22emu/g, and saturated magnetic saturation intensity is 16.68emu/g, and coercivity is 24.73Oe, shows soft magnetism.
Fig. 4 is CNTs/Fe prepared by embodiment 1
3o
4the absorbing property figure of composite.CNTs/Fe
3o
4the suction wavestrip of composite is wide is 6-18GHz, and have larger suction wavestrip wide, maximum reflectivity decays to-8.3dB.
Detailed description of the invention
Below in conjunction with specific embodiment the present invention done and further elaborate.
embodiment 1
(1) take 1g multi-walled carbon nano-tubes, be dispersed in 200mL deionized water, add watery hydrochloric acid, adjustment pH=3.5.Dripping by 100ml mass concentration under ultrasonic agitation condition is the hydrogen peroxide of 30%, 100ml concentration is the Fenton reagent that the solution of ferrous chloride of 0.1mol/L obtains, add excessive reduced iron powder after dropwising in 6h, continue ultrasonic agitation 0.5h, by magnet adsorption method removing excess iron powder;
(2) suspension obtained in step (1) is got, according to Fe
2+concentration, adds equivalent OH
-1urea, be warming up to 95 DEG C, at the mechanic whirl-nett reaction 1h of 200rmp, after terminating further across separation, washing, 200 DEG C of techniques such as drying, pulverizing obtain end product.
embodiment 2
(1) take 1g multi-walled carbon nano-tubes, be dispersed in 50ml deionized water, add watery hydrochloric acid, adjustment pH=3.5.Dripping by 100ml mass concentration under ultrasonic agitation condition is the hydrogen peroxide of 30%, 20ml concentration is the Fenton reagent () that the solution of ferrous chloride of 0.1mol/L obtains, after 1h dropwises, add excessive reduced iron powder, continue ultrasonic agitation 0.5h, by magnet adsorption method removing excess iron powder.
(2) suspension obtained in step (1) is got, according to Fe
2+concentration, adds 0.5 times of equivalent OH
-1hexamethylenetetramine, be warming up to 75 DEG C, at the mechanic whirl-nett reaction 4h of 1000rmp, after terminating further across separation, washing, 80 DEG C of techniques such as drying, pulverizing obtain end product.
embodiment 3
(1) take 1g SWCN, be dispersed in 500ml deionized water, add watery hydrochloric acid, adjustment pH=3.Dripping by 400ml mass concentration under ultrasonic agitation condition is the hydrogen peroxide of 30%, 50ml concentration is the Fenton reagent that the copperas solution of 0.2mol/L obtains, after 12h dropwises, add excessive reduced iron powder, continue ultrasonic agitation 4h, by magnet adsorption method removing excess iron powder.
(2) suspension obtained in step (1) is got, according to Fe
2+concentration, adds 0.5 times of equivalent OH
-1hexamethylenetetramine, be warming up to 85 DEG C, at the mechanic whirl-nett reaction 12h of 2500rmp, after terminating further across separation, washing, 120 DEG C of techniques such as drying, pulverizing obtain end product.
embodiment 4
(1) take 1g SWCN, be dispersed in 200ml deionized water, add watery hydrochloric acid, adjustment pH=3.Dripping by 100ml mass concentration under ultrasonic agitation condition is the hydrogen peroxide of 30%, 50ml concentration is the Fenton reagent that the copperas solution of 0.2mol/L obtains, after 6h dropwises, add excessive reduced iron powder, continue ultrasonic agitation 4h, by magnet adsorption method removing excess iron powder.
(2) suspension obtained in step (1) is got, according to Fe
2+concentration, adds 2 times of equivalent OH
-1urea, be warming up to 85 DEG C, at the mechanic whirl-nett reaction 2h of 1000rmp, after terminating further across separation, washing, 120 DEG C of techniques such as drying, pulverizing obtain end product.
Claims (6)
1. one kind be core with CNT, the tri-iron tetroxide composite that is shell, it is characterized in that: the special construction that it take CNT as core, tri-iron tetroxide is shell, tri-iron tetroxide is continuous print laminate structure, covers CNT outer surface equably, and core-shell interface is weak.
2. composite material and preparation method thereof according to claim 1, is characterized in that, prepares according to following step:
(1) by a certain percentage, by carbon nanotube dispersed in deionized water, add watery hydrochloric acid adjustment 1.0≤PH≤3.5, Fenton reagent is dripped under ultrasonic agitation condition, excessive reduced iron powder is added after 1-12h dropwises, continue ultrasonic agitation 0.5-4h, by magnet adsorption method removing excess iron powder;
(2) suspension obtained in step (1) is got, according to Fe
2+concentration, adds the OH of 0.5-2 times of equivalent
-1type precipitating reagent, reacts 1-12h under the mechanical agitation and 75-95 DEG C of temperature conditions of 200-2500rmp, after terminating further across separation, washing, 80-200 DEG C drying, pulverize the composite that to obtain take CNT as core, tri-iron tetroxide is shell.
3. preparation method according to claim 2, is characterized in that: the CNT described in step (1) is at least one in multi-walled carbon nano-tubes, SWCN.
4. preparation method according to claim 2, is characterized in that: the CNT described in step (1) and the mass ratio of deionized water are 1:(50-500).
5. preparation method according to claim 2, is characterized in that: the Fenton reagent described in step (1) is by Fe
2+and H
2o
2assembly forms, Fe
2+the sediment tri-iron tetroxide generated and the mass ratio of CNT are 1:(0.5-2).
6. preparation method according to claim 2, is characterized in that: the OH described in step (2)
-1type precipitating reagent is at least one in urea, hexamethylenetetramine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106925325A (en) * | 2015-12-31 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925328A (en) * | 2015-12-31 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925324A (en) * | 2015-12-31 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| 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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| 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 |
Non-Patent Citations (1)
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925325A (en) * | 2015-12-31 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925328A (en) * | 2015-12-31 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925324A (en) * | 2015-12-31 | 2017-07-07 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925325B (en) * | 2015-12-31 | 2019-03-22 | 中国石油化工股份有限公司 | One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925324B (en) * | 2015-12-31 | 2019-08-16 | 中国石油化工股份有限公司 | One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN106925328B (en) * | 2015-12-31 | 2019-09-24 | 中国石油化工股份有限公司 | One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| 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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