CN102489252A - Ferroferric oxide nano crystal loaded on acid-modified carbon nano tube and preparation method thereof - Google Patents
Ferroferric oxide nano crystal loaded on acid-modified carbon nano tube and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 41
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- 238000006396 nitration reaction Methods 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims 3
- 230000009514 concussion Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000003287 bathing Methods 0.000 abstract 1
- 229910001448 ferrous ion Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
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- 230000005540 biological transmission Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Abstract
The invention discloses a magnetic ferroferric oxide nano crystal loaded on an acid-modified carbon nano tube and a preparation method thereof and belongs to the field of nano crystals. The preparation method comprises the following steps of: carrying out ultrasonic modification treatment on the carbon nano tube in mixed acid composed of nitric acid and sulfuric acid; then dispersing the modified carbon nano tube in aqueous solution; under the condition of introducing inert gas and stirring, adding ferrous ions; and under the condition of hot-water bathing, adding a strongly-alkaline solution of nitrate, and growing the magnetic ferroferric oxide nano crystal with a regular structure directly on the carbon nano tube. The preparation method is simple and practicable, the conditions are easily controlled, roasting is not needed, the energy consumption is lower and industrial production can be achieved. The combination of the loaded ferroferric oxide crystal and the carrier carbon nano tube is compact, and the structure is stable. The prepared magnetic nano composite material is an excellent out-phase Fenton catalyst which has a function of absorbing organic pollutants and is convenient in separation, and simultaneously can be used for manufacturing chemical sensors and electromagnetic material devices.
Description
Technical field
The present invention relates to the modification and the modification field of carbon nanomaterial, what be specifically related to is sour modified carbon nano-tube supported magnetic ferroferric oxide nanocrystal and preparation method thereof.
Background technology
The special construction of CNT (CNTs) has determined it to have special electricity, engineering properties and good absorption property.The electric conductivity of CNT can be metal, semimetal property and semiconductive.CNT particular structural and mechanics, calorifics and electric property have caused scientist's extensive interest, and various fields such as emission on the scene, molecular electronic device, composite reinforcing material, hydrogen storage material, catalyst have obtained certain application.Compare the hollow nano structure that CNT is unique, high heat endurance with the conventional carriers material; High intensity and hardness; Corrosion resistance, suitable pore-size distribution, bigger specific area; And the surperficial characteristics that can carry out the distinct methods modification according to needs of people, make it that good application prospects also arranged aspect novel catalyst carrier.The Application Research of relevant CNT becomes the research focus.In recent years, a lot of patents (CN200510123481.6, the CN200510030919.6 of domestic applications; CN200710049525.4; CN200710046709.5, CN200810035150.0 is CN200910045160.7) with the modification of CNT and use relevant.
At present, the method for carbon nanotube loaded nano-metal-oxide has liquid-phase chemistry deposition technique, impregnation-calcination method, sol-gal process, hydrothermal synthesis method and gas chemistry sedimentation etc.Liquid-phase chemistry deposition technique is simple, can prepare metal oxide at the equally distributed composite nanoparticle of carbon nano tube surface.The impregnation-calcination method can be come the control load amount through the length of control soak time.But, the combining of the oxide of liquid-phase chemistry deposition technique and the load of impregnation-calcination method and CNT is not very tight, in use comes off easily.This makes the result of use of product reduce even can not bring into play due effect.In addition, above method carrying method is in essence all through the process of a deposition-roasting, except that loaded article combine with carrier not firm, also relatively power consumption.
Nano ferriferrous oxide (Fe
3O
4) have certain magnetic, and can directedly move under the outside magnetic field, its stable chemical performance, thereby purposes is quite extensive.Magnetic Nano material is widely used as the carrier of various medicines, the separation of immunocyte, magnetic resonance imaging imaging, magnetic recording material, high gradient magnetic separator, microwave absorbing material, sapecial coating and electrophotography developing agent.Also be employed simultaneously and make chemical sensor and ultracapacitor.It also is a kind of good heterophase Fenton catalyst of being convenient to separate simultaneously.
Utilize the carbon nanotube loaded nano ferriferrous oxide crystal potentiality that are widely used.As chemical catalyst, it has absorption and two kinds of functions of catalysis concurrently, can effectively be applied to the absorption and the Fenton degraded of micro quantity organic pollutant.Therefore, utilize the method exploitation of easy low energy consumption and produce tri-iron tetroxide to combine with CNT closely, the composite that the tri-iron tetroxide crystalline structure is good has very important realistic meaning.
Summary of the invention
1, invents the technical problem that will solve
Need in high temperature furnace, handle in the method for load ferroferric oxide nano crystal on CNT to existing; Relatively consume energy and time-consuming technology; The present invention provides sour modified carbon nano-tube supported magnetic ferroferric oxide nanocrystal and preparation method thereof; Can be in the aqueous solution of heat the direct tight ferriferrous oxide nano-particle of grown crystal tactical rule on the nitration mixture carbon nano tube modified, and need not high-temperature roasting, cut down the consumption of energy.
2, technical scheme
The preparation method of loaded with nano tri-iron tetroxide crystal the steps include: on a kind of sour modified carbon nano-tube
(1) in the nitration mixture that the concentrated sulfuric acid and nitric acid are formed, adds CNT, stir, 30~70 ℃ of heating, sonicated;
(2) mixed liquor filtration and washing after handling in the top step are obtained sour modified carbon nanotube;
(3) above-mentioned modified carbon nano-tube is scattered in the water, adds green vitriol, place logical nitrogen (or argon gas) heating of 90 ℃ of water-baths;
(4) in above-mentioned hot solution, add the solution that contains sodium nitrate (or potassium nitrate) and NaOH (or potassium hydroxide) mixture, keep logical nitrogen, stir;
(5) mixed liquor after step finishes above was warm 1~5 hour of 90 ℃ of water-bath relaying continuations of insurance.
(6) above-mentioned mixed liquor is filtered, washing, oven dry is ground to such an extent that the black solid powder promptly is carbon nanotube loaded ferroferric oxide nano crystal.
The ratio of nitric acid and sulfuric acid is 1:1~1:4 in the described nitration mixture.
Described CNT is SWCN or multi-walled carbon nano-tubes.
Described water is deionized water, any in distilled water or the pure water.
The described molar concentration that contains green vitriol solution is 0.05~1mol/L.
The described molar concentration that contains the solution of sodium nitrate (or potassium nitrate) and NaOH (or potassium hydroxide) mixture is every milliliter of 0.06~0.4 gram.
Utilize the carbon nanotube loaded ferroferric oxide nano crystal compound of the inventive method preparation; Its transmission electron microscope (TEM) shows; The fairly regular ferriferrous oxide nano-particle of crystal structure of on CNT, closely growing, its average grain diameter is 40~80nm, because ferroferric oxide nano crystal is to locate to grow out with functional group at the fault location on nitration mixture carbon nano tube modified surface; Thereby combine closely in vigorous stirring and ultrasonic cleaning process, not come off; Simultaneously, ferriferrous oxide nano-particle is regular crystal structure basically.Its X ray crystal diffraction result shows that all diffraction maximums are all corresponding one by one with tri-iron tetroxide crystal standard diffraction maximum, does not have other oxide crystal diffraction maximums, explains that the tri-iron tetroxide crystal purity of growing on the CNT is very high.
3, beneficial effect
Compared with present technology, advantage applies of the present invention exists:
(1) carrying method that is adopted among the present invention is simple, and energy consumption is lower;
(2) magnetic ferroferric oxide nano-particles among the present invention combines closely with CNT, and load is firm;
(3) ferriferrous oxide nano-particle among the present invention is regular crystal structure growth, Stability Analysis of Structures;
(4) compound of being developed among the present invention can be used for the association area of adsoption catalysis and nano magnetic material aspect.
Description of drawings
Fig. 1 is nitration mixture modified carbon nanotube transmission electron microscope (TEM) figure of the inventive method preparation;
Fig. 2 is carbon nanotube loaded ferroferric oxide nano crystal transmission electron microscope (TEM) figure of the inventive method preparation, and sample is in advance through repeatedly supersound washing and vigorous stirring;
Fig. 3 is X ray crystal diffraction (XRD) figure of the carbon nanotube loaded ferroferric oxide nano crystal compound of the inventive method preparation.
The specific embodiment
Below further specify the present invention through instantiation.
Embodiment 1
Take by weighing 5 milligrams of multi-walled carbon nano-tubes, add 3 milliliters of red fuming nitric acid (RFNA)s, 9 milliliters of concentrated sulfuric acids, 50 ℃ of following sonicated 2 hours, cooling, the deionized water dilution is filtered, washing.This modified carbon nano-tube is scattered in 80 ml waters, adds green vitriol 4 grams, place 90 ℃ of water-baths, logical nitrogen flooding oxygen.Preparation contains 40 milliliters of the mixed solutions of 0.093 every milliliter of NaOH of gram and every milliliter of sodium nitrate of 0.045 gram, is keeping logical nitrogen to stir down, and this mixed solution is added drop-wise in the ferrous mixed liquor with CNT of above-mentioned sulfur acid, dropwises, and continues to be incubated 2 hours.With supersound washing 8 times after black magnetic solid that generates and the fluid separation applications, be drying to obtain the carbon nanotube loaded ferroferric oxide nano crystal of product.
Embodiment 2
Take by weighing 5 milligrams of multi-walled carbon nano-tubes, add 3 milliliters of red fuming nitric acid (RFNA)s, 9 milliliters of concentrated sulfuric acids, 60 ℃ of following sonicated 1 hour, cooling, the deionized water dilution is filtered, washing.This modified carbon nano-tube is scattered in 50 ml waters, adds green vitriol 2 grams, place 90 ℃ of water-baths, logical nitrogen flooding oxygen.Preparation contains 40 milliliters of the mixed solutions of 0.047 every milliliter of NaOH of gram and every milliliter of sodium nitrate of 0.023 gram, is keeping logical nitrogen to stir down, and this mixed solution is added drop-wise in the ferrous mixed liquor with CNT of above-mentioned sulfur acid, dropwises, and continues to be incubated 3 hours.With supersound washing 8 times after black magnetic solid that generates and the fluid separation applications, be drying to obtain the carbon nanotube loaded ferroferric oxide nano crystal of product.
Embodiment 3
Take by weighing 10 milligrams of multi-walled carbon nano-tubes, add 10 milliliters of red fuming nitric acid (RFNA)s, 20 milliliters of concentrated sulfuric acids, 70 ℃ of following sonicated 1 hour, cooling, the deionized water dilution is filtered, washing.This modified carbon nano-tube is scattered in 100 ml waters, adds green vitriol 4 grams, place 90 ℃ of water-baths, logical nitrogen flooding oxygen.Preparation contains 20 milliliters of the mixed solutions of 0.20 every milliliter of potassium hydroxide of gram and every milliliter of sodium nitrate of 0.045 gram, is keeping logical nitrogen to stir down, and this mixed solution is added drop-wise in the ferrous mixed liquor with CNT of above-mentioned sulfur acid, dropwises, and continues to be incubated 3 hours.With supersound washing 8 times after black magnetic solid that generates and the fluid separation applications, be drying to obtain the carbon nanotube loaded ferroferric oxide nano crystal of product.
Embodiment 4
Take by weighing 200 milligrams of multi-walled carbon nano-tubes, add 60 milliliters of red fuming nitric acid (RFNA)s, 180 milliliters of concentrated sulfuric acids, 50 ℃ of following sonicated 3 hours, cooling, the deionized water dilution is filtered, washing.This modified carbon nano-tube is scattered in 1000 ml waters.Get 40 milliliters of above dispersion liquids, add green vitriol 6 grams, place 90 ℃ of water-baths, logical nitrogen flooding oxygen.Preparation contains 20 milliliters of the mixed solutions of 0.30 every milliliter of NaOH of gram and every milliliter of sodium nitrate of 0.06 gram, is keeping logical nitrogen to stir down, and this mixed solution is added drop-wise in the ferrous mixed liquor with CNT of above-mentioned sulfur acid, dropwises, and continues to be incubated 4 hours.With supersound washing 8 times repeatedly after black magnetic solid that generates and the fluid separation applications, be drying to obtain the carbon nanotube loaded ferroferric oxide nano crystal of product.
Take by weighing 100 milligrams of multi-walled carbon nano-tubes, add 30 milliliters of red fuming nitric acid (RFNA)s, 90 milliliters of concentrated sulfuric acids, 70 ℃ of following sonicated 2 hours, cooling, the deionized water dilution is filtered, washing.This modified carbon nano-tube is scattered in 500 ml waters.Get 30 milliliters of above dispersion liquids, add green vitriol 4 grams, place 90 ℃ of water-baths, logical nitrogen flooding oxygen.Preparation contains 20 milliliters of the mixed solutions of 0.30 every milliliter of potassium hydroxide of gram and every milliliter of potassium nitrate of 0.06 gram, is keeping logical nitrogen to stir down, and this mixed solution is added drop-wise in the ferrous mixed liquor with CNT of above-mentioned sulfur acid, dropwises, and continues to be incubated 2.5 hours.With supersound washing 6 times repeatedly after black magnetic solid that generates and the fluid separation applications, be drying to obtain the carbon nanotube loaded ferroferric oxide nano crystal of product.
Embodiment 6
Take by weighing 10 milligrams of SWCNs, add 10 milliliters of red fuming nitric acid (RFNA)s, 10 milliliters of concentrated sulfuric acids, 30 ℃ of following sonicated 1 hour, cooling, the deionized water dilution is filtered, washing.This modified carbon nano-tube is scattered in 100 ml waters, adds green vitriol 15 grams, place 90 ℃ of water-baths, logical nitrogen flooding oxygen.Preparation contains 20 milliliters of the mixed solutions of 0.20 every milliliter of potassium hydroxide of gram and every milliliter of sodium nitrate of 0.045 gram, is keeping logical nitrogen to stir down, and this mixed solution is added drop-wise in the ferrous mixed liquor with CNT of above-mentioned sulfur acid, dropwises, and continues to be incubated 1 hour.With supersound washing 8 times after black magnetic solid that generates and the fluid separation applications, be drying to obtain the carbon nanotube loaded ferroferric oxide nano crystal of product.
The present invention is not limited to above specific embodiment.
Claims (7)
1. a sour modified carbon nano-tube load ferroferric oxide nano crystal preparation method the steps include:
(1) CNT is scattered in the ultrasonic concussion processing of heating in the nitration mixture;
(2) mixed liquor filtration and washing after step (1) processing are obtained sour modified carbon nanotube;
(3) above-mentioned modified carbon nano-tube is scattered in the water, adds green vitriol, place the logical inert gas heating of 90~100 ℃ of water-baths;
(4) in the hot solution that step (3) obtains, add the solution that contains sodium nitrate or potassium nitrate and NaOH or potassium hydroxide mixture, keep logical nitrogen, stir;
(5) mixed liquor after step (4) finishes was warm 1~5 hour of 90 ℃ of water-bath relaying continuations of insurance;
(6) mixed liquor after step (5) is finished carries out Separation of Solid and Liquid with above-mentioned mixed liquor, washing, and oven dry is ground and is obtained carbon nanotube loaded ferroferric oxide nano crystal.
2. the preparation method at sour modified carbon nano-tube load ferroferric oxide nano crystal according to claim 1 is characterized in that: the nitration mixture in the step (1) is that nitric acid and sulfuric acid volume ratio are the mixture of 1:1~1:4.
3. the preparation method at sour modified carbon nano-tube load ferroferric oxide nano crystal according to claim 1 and 2 is characterized in that: CNT is multi-walled carbon nano-tubes or SWCN in the step (1).
4. the preparation method at sour modified carbon nano-tube load ferroferric oxide nano crystal according to claim 1 and 2 is characterized in that: heating-up temperature is 30~70 ℃ in the step (1).
5. the preparation method at sour modified carbon nano-tube load ferroferric oxide nano crystal according to claim 1 is characterized in that: the molar concentration of green vitriol solution is 0.05~1mol/L in the step (3).
6. the preparation method at sour modified carbon nano-tube load ferroferric oxide nano crystal according to claim 1; It is characterized in that: the mass concentration that contains the solution of sodium nitrate or potassium nitrate and NaOH or potassium hydroxide mixture in the step (4) is every milliliter of 0.06~0.4 gram, and the mass concentration of NaOH or potassium hydroxide and sodium nitrate or potassium nitrate is 2:1~5:1.
7. the carbon nanotube supported magnetic ferroferric oxide nanocrystal for preparing of the said preparation method of claim 1.
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