CN102807254A - Amino functionalized superparamagnetism carbon nanosphere and preparation method thereof - Google Patents
Amino functionalized superparamagnetism carbon nanosphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an amino functionalized superparamagnetism carbon nanosphere and a preparation method of the amino functionalized superparamagnetism carbon nanosphere. The nanosphere comprises a core and an outer layer, wherein the core is wrapped by the outer layer; the nanosphere is characterized in that the core is a ferroferric oxide nano particle, the outer layer is a carbon shell layer, and an amino is connected onto the carbon shell layer. Compared with the prior art, dicyclopentadienyl iron and ferric acetylacetonate are taken as aniron source, a cane sugar or glucose is taken as a carbon source, then the iron source and the carbon source react in a polyethylene glycol or tetraglycol solution, so that the superparamagnetism carbon nanosphere with rich amines on the surface and a core-shell structure is obtained, and the prepared magnetism carbon nanosphere is widely applied to the fields of biology, catalysis, analysis, energy sources, and information storage. Equipment needed in the preparation process is cheap, the reaction raw materials and the solvent are safe and free from toxic, the prepared nanosphere is economical and environment-friendly, is wide in practicality and has wide application prospect.
Description
Technical field
The present invention relates to the magnetic Nano carbon balls of amino functional, particularly relate to a kind of method for preparing the paramagnetism Nano carbon balls of amino functional.
Background technology
Ferroferric oxide magnetic nano-particles is with a wide range of applications and receives much concern in fields such as biomedicines because of its special performances.Yet there is a following difficult problem in ferriferrous oxide nano-particle in practical application: under the magneto-dipole graviational interaction, ferriferrous oxide nano-particle is very easy to reunite; Contain Fe in the ferriferrous oxide nano-particle
2+, chemicalstability is low, is prone to oxidized.In order to address the above problem, the ferriferrous oxide nano-particle surface of being everlasting superscribes resists such as polymer, biomacromolecule or silicon-dioxide, to improve the stability and the biological safety of ferroferric oxide magnetic nano-material.
The chemicalstability of carbon material is high; Use the carbon coated ferriferrous oxide magnetic nano-particle; Can protect ferriferrous oxide nano-particle in use not oxidized; Can improve the conductivity and the biocompatibility of magnetic Nano material again, help expanding the Application Areas of ferroferric oxide magnetic nano-particles.The preparation method of the carbon material of nucleocapsid structure mainly contains arc discharge method, ion beam sputtering, electron beam irradiation method, laser evaporation method, vapour deposition process, pyrogenic silica etc.The complex equipments that these methods are used, power consumption is big, cost is high, processing parameter is wayward, often with carbide impurity; And be difficult to control size, carbon-coating thickness, the composite particles size of magnetic kernel; Thereby be difficult to realize extensive synthesizing, cause its application and development to relatively lag behind.Simultaneously, because carbon material surface is a high hydrophobicity, restricted this type of material in Application for Field such as biological medicines.In order to solve carbon material hydrophobicity problem, people utilize traditional Hydrothermal Preparation to go out magnetic carbon material [J. Biomed. Mater. Res. A, 2007,80, the 333-341 of carboxyl-functional; Talanta, 2012,89,189-194], the magnetic carbon micron tube [Adv. Funct. Mater., 2008,18,1809-1823] of amino functional.In view of the limitation of traditional hydrothermal method, still there is not the report of the superparamagnetism Nano carbon balls of preparation amino functional at present.Therefore, a kind of method for preparing the magnetic Nano carbon balls of amino functional of development has important theory and realistic meaning.
Summary of the invention
The 1st purpose of the present invention provides the superparamagnetism Nano carbon balls of amino functional.
The 2nd purpose of the present invention is its preparation method of above-mentioned nanometer ball.
The superparamagnetism Nano carbon balls of amino functional according to the invention comprises core and skin, outer parcel core, and core is a ferriferrous oxide nano-particle, skin is the carbon shell, is connected with amino on the carbon shell.
Core according to the invention is the ferriferrous oxide nano-particle of 8 nm ~ 20 nm; Said superparamagnetism Nano carbon balls particle diameter is the particle of 10 nm ~ 30 nm; The specific surface area of said superparamagnetism Nano carbon balls is 50 ~ 150 m
2/ g; The quality percentage composition of carbon is 6% ~ 94% in the said superparamagnetism Nano carbon balls.
Amidized superparamagnetism Nano carbon balls (single stage method) may further comprise the steps:
Molysite is distributed in the solvent, under ultransonic condition, mixes, add carbohydrate again, under ultransonic condition, mix, above-mentioned mixing solutions is transferred in the autoclave, behind the adding ammoniacal liquor, in 160-270 ℃ of reaction 3-24 h; Cool to room temperature, the gained deposition gets final product after magnetic separation, washing, drying;
Said carbohydrate is 1 with the amount of substance ratio of molysite: (0.5 ~ 2.0); Said ammoniacal liquor is 1 with the amount of substance ratio of molysite: (0.07 ~ 0.18).
Described molysite is ferrocene or ferric acetyl acetonade; Said solvent is Tetraglycol 99 or polyoxyethylene glycol, and the molecular weight of said polyoxyethylene glycol is 200 ~ 600.
Said carbohydrate is sucrose or glucose;
Amidized superparamagnetism Nano carbon balls (method of fractional steps) may further comprise the steps:
Molysite is distributed in the solvent, under ultransonic condition, mixes, reflux in nitrogen atmosphere, reflux temperature is 230 ~ 260 ℃, refluxes to be no less than 3 hours, prepares monodispersed ferriferrous oxide nano-particle;
Magnetic is isolated ferriferrous oxide nano-particle, and with the ferriferrous oxide nano-particle ultra-sonic dispersion that is obtained in solvent, obtain the suspension liquid of ferriferrous oxide nano-particle; Add carbohydrate again, under ultransonic condition, mix, above-mentioned mixing solutions is transferred in the autoclave, behind the adding ammoniacal liquor, in 180-270 ℃ of reaction 8-24 h; Cool to room temperature, the gained deposition gets final product after magnetic separation, washing, drying;
Said carbohydrate is 1 with the amount of substance ratio of molysite: (1.0 ~ 2.0); Said ammoniacal liquor is 1 with the amount of substance ratio of molysite: (0.13 ~ 0.27).
Described molysite is ferrocene or ferric acetyl acetonade; Said solvent is Tetraglycol 99 or polyoxyethylene glycol, and the molecular weight of said polyoxyethylene glycol is 200 ~ 600.
Said carbohydrate is sucrose or glucose.
Product characterizes through sem, confirms that the diameter of the amidized superparamagnetism Nano carbon balls of gained is 10 ~ 30 nm; Characterize through X-ray diffraction, confirm that product is the Z 250 that carbon coats; Characterize through high resolution transmission electron microscopy, confirm that the internal core of magnetic Nano carbon balls is a Z 250, skin is the nucleocapsid structure of carbon-coating; Characterize through SQID, the confirmation Nano carbon balls is a superparamagnetism; Characterize through specific surface and aperture analyser, confirm that the specific surface area of product is 50 ~ 150 m
2/ g; Characterize through Fourier transformation infrared spectrometer, confirm that carbon shell surface has amino.
The present invention uses for reference the advantage of hydrothermal method; Adopt the single stage method or the method for fractional steps to prepare that specific surface area is big, the surface has the Nano carbon balls that enriches amido functional group; Wherein the ferriferrous oxide nano-particle with superparamagnetism has been filled in Nano carbon balls inside, has formed nucleocapsid structure.
The present invention is a source of iron with ferrocene or ferric acetyl acetonade; Sucrose or glucose are carbon source; In polyoxyethylene glycol or Tetraglycol 99 solution, react; Can obtain the superparamagnetism Nano carbon balls that the surface has abundant amino, nucleocapsid structure, prepared magnetic Nano carbon balls is widely used at biology, catalysis, analysis, the energy and area information storage.Preparation process required equipment of the present invention is cheap, and reaction raw materials and solvent safety are nontoxic, and economic environmental protection, and practicality is wide, is with a wide range of applications.
Description of drawings
Fig. 1 is that the sem of the prepared product of embodiment 1 detects figure.
Fig. 2 is that the transmission electron microscope of the prepared product of embodiment 1 detects figure, and figure (a) be an original graph, and scheming (b) is partial enlarged drawing.
Fig. 3 is that the X-ray powder diffraction of the prepared product of embodiment 1 detects figure.X-coordinate is diffraction angle 2-Theta (degree), and ordinate zou is intensity I ntensity (a.u.).
Fig. 4 is the infrared spectrogram of the prepared product of embodiment 1, and X-coordinate is wave number Wavelength/cm
-1, ordinate zou is transmittance % Transmittance.
Fig. 5 is the N of the prepared product of embodiment 1
2Isothermal adsorption desorption graphic representation.
Fig. 6 is the magnetic hysteresis loop figure of the product of embodiment 1 preparation.Figure (a) is an original graph, and figure (b) is a partial enlarged drawing, and X-coordinate is magneticstrength H (Oe), and ordinate zou is saturation magnetization M (emu/g).
Fig. 7 is that the transmission electron microscope of the prepared product of embodiment 9 detects figure.
Fig. 8 is the infrared spectrogram of the prepared product of embodiment 9.X-coordinate is wave number Wavelength/cm
-1, ordinate zou is transmittance % Transmittance.
Fig. 9 is the magnetic hysteresis loop figure of the product of embodiment 9 preparations, and in Fig. 9, X-coordinate is magneticstrength H (Oe), and ordinate zou is saturation magnetization M (emu/g), and figure (a) is an original graph, and figure (b) is a partial enlarged drawing.
Figure 10 is the cyclic voltammetric test result of the product of embodiment 3 preparations; Figure (a) is the cyclic voltammetric test result; Figure (b) be under the different scanning speed than electric capacity figure; Can know that by figure cyclic voltammetry curve all near symmetrical rectangle, can reach 43.8 F/g than electric capacity, show that magnetic carbon sample has good capacitance characteristic.
Embodiment
Take by weighing 706.3 mg ferric acetyl acetonades and join in the 20 mL Macrogol 200s, ultrasonic 5 min obtain 0.1 molL
-1The methyl ethyl diketone ferrous solution; Take by weighing 360.0 mg glucose and join in the above-mentioned methyl ethyl diketone ferrous solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 240 ℃ of reaction 24 h; Question response naturally cools to room temperature after finishing, and the gained deposition is a black powder after magnetic separation, washing, drying.Product characterizes through sem, confirms that the diameter of the amidized superparamagnetism Nano carbon balls of gained is 10 ~ 30 nm; Characterize through X-ray diffraction, confirm that product is the Z 250 that carbon coats; Characterize through high resolution transmission electron microscopy, confirm that the internal core of magnetic Nano carbon balls is the ferriferrous oxide nano-particle of 8 nm ~ 20 nm, skin is the nucleocapsid structure of carbon-coating; Characterize through SQID, the confirmation Nano carbon balls is a superparamagnetism; Characterize through specific surface and aperture analyser, confirm that the specific surface area of magnetic carbon nanomaterial is 105.8 m
2/ g; Levy through the simultaneous thermal analysis instrument, confirm that the quality percentage composition of carbon in the magnetic Nano carbon balls is 15%;
As shown in Figure 3: through contrasting with standard diagram (JCPDS:01-1111), the product diffraction peak corresponds respectively to cube diffraction peak of phase Z 250 (111) in 18.3 °, 30.3 °, 35.6 °, 43.0 °, 53.4 °, 57.1 °, 62.8 °; (220); (311), (400), (422); (511), (440).
Infrared spectrum characterization has been confirmed the amino on product surface, and is as shown in Figure 4: its 3457 cm
-1With 3427 cm
-1Locating two absorption peaks is amino N-H stretching vibration peak, 2927 cm
-1With 3285 cm
-1Place's absorption peak ownership is-CH
2Stretching vibration peak, 1640 cm
-1With 1548 cm
-1Place's absorption peak is N-H flexural vibration peaks, 1386 cm
-1Place's absorption peak is the C-N stretching vibration peak, 1085 cm
-1With 573 cm
-1Place's absorption peak is the Z 250 charateristic avsorption band.
As shown in Figure 5: by N
2Isothermal adsorption desorption graphic representation can know that the magnetic carbon material is a vesicular structure, has bigger specific surface area.
As shown in Figure 6, its saturation magnetization is 81.8 emu/g, and remanent magnetism is 0.7 emu/g, and coercive force is 5.1 Oe, learns that this magnetic carbon material has ultra paramagnetic effect.
Take by weighing 372.1 mg ferrocene and add in the 20 mL Macrogol 200s, ultrasonic 5 min obtain 0.1 molL
-1Ferrocene solution; Take by weighing 684.6 mg sucrose and join in the above-mentioned ferrocene solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 240 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 94% in the product, and the specific surface area of product is 50.0 m
2/ g.
Embodiment 3,
Take by weighing 706.3 mg ferric acetyl acetonades and add in the 20 mL Macrogol 200s, ultrasonic 5 min obtain 0.1 molL
-1The methyl ethyl diketone ferrous solution; Take by weighing 684.6 mg sucrose and join in the above-mentioned methyl ethyl diketone ferrous solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 240 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 39.1% in the product, and the specific surface area of product is 77.8 m
2/ g.
Embodiment 4,
Take by weighing 372.1 mg ferrocene and add in the 20 mL Macrogol 200s, ultrasonic 5 min obtain 0.1 molL
-1Ferrocene solution; Take by weighing 360.0 mg glucose and join in the above-mentioned ferrocene solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 240 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 48.1% in the product, and the specific surface area of product is 150.0 m
2/ g.
Take by weighing 353.2 mg ferric acetyl acetonades and add in the 20 mL PEG 400s, ultrasonic 5 min obtain 0.05 molL
-1The methyl ethyl diketone ferrous solution; Take by weighing 120.0 mg glucose and join in the above-mentioned methyl ethyl diketone ferrous solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 160 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 6% in the product, and the specific surface area of product is 58.4 m
2/ g.
Embodiment 6,
Take by weighing 353.2 mg ferric acetyl acetonades and add in the 20 mL Polyethylene Glycol-600s, ultrasonic 5 min obtain 0.05 molL
-1The methyl ethyl diketone ferrous solution; Take by weighing 360.0 mg glucose and join in the above-mentioned methyl ethyl diketone ferrous solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 270 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 77.5% in the product, and the specific surface area of product is 52.3 m
2/ g.
Embodiment 7,
Take by weighing 744.2 mg ferrocene and add in the 20 mL Tetraglycol 99s, ultrasonic 5 min obtain 0.2 molL
-1Ferrocene solution; Take by weighing 360.0 mg glucose and join in the above-mentioned ferrocene solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1.5 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 270 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 19.7% in the product, and the specific surface area of product is 91.4 m
2/ g.
Embodiment 8,
Take by weighing 353.2 mg ferric acetyl acetonades and add in the 20 mL Macrogol 200s, ultrasonic 5 min obtain 0.05 molL
-1Solution; Take by weighing 360.0 mg glucose and join in the above-mentioned methyl ethyl diketone ferrous solution, ultrasonic 5 min obtain mixing solutions; Above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 270 ℃ of reaction 3 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 36.6% in the product, and the specific surface area of product is 60.2 m
2/ g.
In three-necked flask, with 706.3 mg ferric acetyl acetonade ultra-sonic dispersion in 60 mL Macrogol 200s; In nitrogen atmosphere,, prepare monodispersed ferriferrous oxide nano-particle in 260 ℃ of reflux 3 h; After reaction finished, magnetic was isolated ferriferrous oxide nano-particle, and ultra-sonic dispersion obtains the suspension liquid of ferriferrous oxide nano-particle in 40 mL Macrogol 200s again; Take by weighing 360.0 mg glucose and join in the above-mentioned suspension liquid, ultrasonic 5 min obtain mixing solutions; At last above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 240 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 19.2% in the product, and the specific surface area of product is 75.3 m
2/ g.
As shown in Figure 7: can know that by the high resolution transmission electron microscopy sign internal core of magnetic Nano carbon balls is the ferriferrous oxide nano-particle of 8 nm ~ 20 nm, skin is the nucleocapsid structure of carbon-coating.
As shown in Figure 8, confirmed the surperficial amino of product by infrared spectrum characterization; 3400 cm
-1With 3357 cm
-1Locating two absorption peaks is amino N-H stretching vibration peak, 2944 cm
-1Place's absorption peak ownership is-CH
2Stretching vibration peak, 1640 cm
-1Place's absorption peak is N-H flexural vibration peaks, 1342 cm
-1Place's absorption peak is the C-N stretching vibration peak, 1085 cm
-1With 573 cm
-1Place's absorption peak is the Z 250 charateristic avsorption band.
As shown in Figure 9: its saturation magnetization is 58.7 emu/g, and remanent magnetism is 1.2 emu/g, and coercive force is 14.2 Oe, learns that this magnetic carbon material has ultra paramagnetic effect.
In three-necked flask, with 706.3 mg ferric acetyl acetonade ultra-sonic dispersion in 60 mL PEG 400s; In nitrogen atmosphere,, prepare monodispersed ferriferrous oxide nano-particle in 230 ℃ of reflux 3 h; After reaction finished, magnetic was isolated ferriferrous oxide nano-particle, and ultra-sonic dispersion obtains the suspension liquid of ferriferrous oxide nano-particle in 40 mL PEG 400s again; Take by weighing 684.6 mg sucrose and join in the above-mentioned suspension liquid, ultrasonic 5 min obtain mixing solutions; At last above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 270 ℃ of reaction 8 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 48.6% in the product, and the specific surface area of product is 69.3 m
2/ g.
Embodiment 11,
In three-necked flask, with 744.2 mg ferrocene ultra-sonic dispersion in 60 mL Tetraglycol 99s; In nitrogen atmosphere,, prepare monodispersed ferriferrous oxide nano-particle in 260 ℃ of reflux 3 h; After reaction finished, magnetic was isolated ferriferrous oxide nano-particle, and ultra-sonic dispersion obtains the suspension liquid of ferriferrous oxide nano-particle in 40 mL Tetraglycol 99s again; Take by weighing 360.0 mg glucose and join in the above-mentioned suspension liquid, ultrasonic 5 min obtain mixing solutions; At last above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 180 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 10.5% in the product, and the specific surface area of product is 48.9 m
2/ g.
Embodiment 12,
In three-necked flask, with 744.2 mg ferrocene ultra-sonic dispersion in 60 mL Polyethylene Glycol-600s; In nitrogen atmosphere,, prepare monodispersed ferriferrous oxide nano-particle in 260 ℃ of reflux 3 h; After reaction finished, magnetic was isolated ferriferrous oxide nano-particle, and ultra-sonic dispersion obtains the suspension liquid of ferriferrous oxide nano-particle in 40 mL PEG 400s again; Take by weighing 360.0 mg glucose and join in the above-mentioned suspension liquid, ultrasonic 5 min obtain mixing solutions; At last above-mentioned mixing solutions is transferred in the autoclave, added 1 mL ammoniacal liquor (NH
3Percentage composition, 28%) after, the autoclave of screwing is in 200 ℃ of reaction 24 h.All the other conditions obtain the superparamagnetism carbon nanomaterial of amino functional, nucleocapsid structure with embodiment 1, and the quality percentage composition of carbon is 8.6% in the product, and the specific surface area of product is 66.6 m
2/ g.
Embodiment 13,
Magnetic Nano carbon balls, gac and polytetrafluoroethylene (PTFE) that embodiment 3 is obtained is even according to 80: 15: 5 mixed of mass ratio.Get 5 mg said mixtures, under the pressure of 12 MPa, being pressed in surface-area is 1 cm
2Porous Ni-base at the bottom of on, obtain working electrode.Electro-chemical test uses conventional three-electrode system, and as working electrode, platinized platinum and saturated calomel (SCE) electrode are respectively as auxiliary and reference electrode with the above-mentioned electrode that makes.Electrolytic solution is the KOH solution of 3 %, test forward horizontal stand 6 h.Ultracapacitor character with the Shanghai occasion China CHI660D of company electrochemical workstation test magnetic carbon sample.In-0.4 ~ 0.4 V potential range, with 5 ~ 50 mVs
-1Sweep velocity working electrode is done cyclic voltammetry test.Its result can know that by Figure 10 cyclic voltammetry curve all near symmetrical rectangle, can reach 43.8 F/g than electric capacity, shows that magnetic carbon sample has good capacitance characteristic.
Claims (10)
1. the superparamagnetism Nano carbon balls of amino functional comprises core and skin, outer parcel core, and it is characterized in that: core is a ferriferrous oxide nano-particle, skin is the carbon shell, is connected with amino on the carbon shell.
2. the superparamagnetism Nano carbon balls of amino functional according to claim 1 is characterized in that:
Said core is the ferriferrous oxide nano-particle of 8 nm ~ 20 nm; Said superparamagnetism Nano carbon balls particle diameter is the particle of 10 nm ~ 30 nm.
3. the superparamagnetism Nano carbon balls of amino functional according to claim 2 is characterized in that:
The specific surface area of said superparamagnetism Nano carbon balls is 50 ~ 150 m
2/ g;
The quality percentage composition of carbon is 6% ~ 94% in the said superparamagnetism Nano carbon balls.
4. the preparation method of the described amidized superparamagnetism Nano carbon balls of claim 1 may further comprise the steps:
Molysite is distributed in the solvent, under ultransonic condition, mixes, add carbohydrate again, under ultransonic condition, mix, above-mentioned mixing solutions is transferred in the autoclave, behind the adding ammoniacal liquor, in 160-270 ℃ of reaction 3-24 h; Cool to room temperature, the gained deposition gets final product after magnetic separation, washing, drying;
Said carbohydrate is 1 with the amount of substance ratio of molysite: (0.5 ~ 2.0); Said ammoniacal liquor is 1 with the amount of substance ratio of molysite: (0.07 ~ 0.18).
5. the preparation method of amidized superparamagnetism Nano carbon balls according to claim 4 is characterized in that: described molysite is ferrocene or ferric acetyl acetonade.
6. the preparation method of amidized superparamagnetism Nano carbon balls according to claim 4 is characterized in that:
Said solvent is Tetraglycol 99 or polyoxyethylene glycol;
Said carbohydrate is sucrose or glucose.
7. the preparation method of the described amidized superparamagnetism Nano carbon balls of claim 1 may further comprise the steps:
Molysite is distributed in the solvent, under ultransonic condition, mixes, reflux in nitrogen atmosphere, reflux temperature is 230 ~ 260 ℃, refluxes to be no less than 3 hours, prepares monodispersed ferriferrous oxide nano-particle;
Magnetic is isolated ferriferrous oxide nano-particle, and with the ferriferrous oxide nano-particle ultra-sonic dispersion that is obtained in solvent, obtain the suspension liquid of ferriferrous oxide nano-particle; Add carbohydrate again, under ultransonic condition, mix, above-mentioned mixing solutions is transferred in the autoclave, behind the adding ammoniacal liquor, in 180-270 ℃ of reaction 8-24 h; Cool to room temperature, the gained deposition gets final product after magnetic separation, washing, drying;
Said carbohydrate is 1 with the amount of substance ratio of molysite: (1.0 ~ 2.0); Said ammoniacal liquor is 1 with the amount of substance ratio of molysite: (0.13 ~ 0.27).
8. the preparation method of amidized superparamagnetism Nano carbon balls according to claim 7 is characterized in that: described molysite is ferrocene or ferric acetyl acetonade.
9. the preparation method of amidized superparamagnetism Nano carbon balls according to claim 7 is characterized in that: said solvent is Tetraglycol 99 or polyoxyethylene glycol.
10. the preparation method of amidized superparamagnetism Nano carbon balls according to claim 7 is characterized in that: said carbohydrate is sucrose or glucose.
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| CN108163994A (en) * | 2017-12-25 | 2018-06-15 | 江苏世邦生物工程科技有限公司 | A kind of microorganism formulation for handling trade effluent and its preparation method and application |
| CN109455769A (en) * | 2019-01-08 | 2019-03-12 | 太原理工大学 | A kind of preparation method of magnetism Nano carbon balls |
| CN109455769B (en) * | 2019-01-08 | 2021-06-08 | 太原理工大学 | Preparation method of magnetic carbon nanospheres |
| CN109985604A (en) * | 2019-04-30 | 2019-07-09 | 湘潭大学 | Chelating agent modified magnetic mesoporous carbon adsorbent material and preparation method and application method |
| CN115212860A (en) * | 2022-06-30 | 2022-10-21 | 苏州为度生物技术有限公司 | Carboxylated ferroferric oxide @ carbon magnetic microsphere and preparation method and application thereof |
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