CN108745217A - The preparation method of more shell hollow magnetic microballoons - Google Patents
The preparation method of more shell hollow magnetic microballoons Download PDFInfo
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- CN108745217A CN108745217A CN201810445695.2A CN201810445695A CN108745217A CN 108745217 A CN108745217 A CN 108745217A CN 201810445695 A CN201810445695 A CN 201810445695A CN 108745217 A CN108745217 A CN 108745217A
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 24
- 239000004793 Polystyrene Substances 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000006249 magnetic particle Substances 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000011806 microball Substances 0.000 claims 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 10
- 238000010792 warming Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present invention discloses a kind of preparation method of more shell hollow magnetic microballoons, and it is reaming materials synthesis macropore carbosphere as template to use polystyrene, then with Fe2+And Fe3+For source of iron, the Fe generated under alkaline environment3O4It is enriched in the surface and inside of carbosphere, form composite magnetic carbosphere, through calcination process, carbonization time and rate is set also accordingly to change by heating rate difference, cause the separating step for occurring repeatedly hollow shell and carbon core until template is decomposed completely, to form more shell magnetic hollow microspheres, the hollow Fe of more shells has effectively been synthesized3O4Microballoon.
Description
Technical field
The present invention relates to field of nanometer technology more particularly to a kind of preparation methods of more shell hollow magnetic microballoons.
Background technology
Prepare single layer hollow Fe at present3O4With superparamagnetism Fe3O4Nano-particle it is more, but it is hollow for more shells
Fe3O4The document of report is less, and 201710653700.4 disclose a kind of preparation side of the hollow ferroso-ferric oxide microballoon of superparamagnetic
Method, but microballoon is still limited only to the preparation of monoshell layer hollow microsphere.201510982022.7 disclosing one kind hollow four
Fe 3 O absorbing material elaborates that multiple reflections and absorption can occur inside hollow structure, to realize the absorption to sound wave
And shielding, however this material only has single layer hollow structure, and more shell hollow magnetic materials can be increased with the reflection of sound wave
Number and repeatedly absorption are to be expected to become the absorbing material of the following rationality.
Invention content
In view of this, present invention aim to address above-mentioned the deficiencies in the prior art, provide it is a kind of use polystyrene for
Reaming material prepares the preparation method of more shell hollow magnetic microballoons of macropore carbon ball.
Technical solution is used by the present invention solves above-mentioned the deficiencies in the prior art：A kind of more shell hollow magnetic microballoons
Preparation method, preparation method includes the following steps：
Step（1）：Using hydro-thermal method, with glucose, sucrose is the sources C, and sodium nitrite is dissolved in deionized water, is turned after being completely dissolved
Enter in high-pressure hydrothermal reaction kettle, 180 DEG C of isothermal reaction a few hours, centrifuge, ethyl alcohol is washed 3 times, is washed 3 times, and freeze-drying is situated between
Hole carbosphere；
Step（2）：By step（1）Obtained monodisperse mesoporous carbosphere surpasses in the mixed liquor of styrene and azodiisobutyronitrile
Sound is swollen, and adds SDS and deionized water ultrasonic disperse, leads to N2, 70 DEG C of polymerisations obtain PS@C complex microspheres；
Step（3）：By step（2）In obtained PS@C complex microspheres be dissolved in 72h in tetrahydrofuran solution, remove polystyrene,
Through 3 removal tetrahydrofuran solutions of washing, freeze-drying obtains macropore carbosphere；
Step（4）：Take step（3）Obtained macropore carbosphere is template, with FeCl3And FeCl2For source of iron, in sodium hydroxide
Under effect, using the method being co-precipitated in situ on the surface of macropore carbosphere and internal enrichment Fe3O4Magnetic particle centrifuges, washing
Freeze-drying obtains magnetic carbon complex microsphere；
Step（5）：Take step（4）Obtained magnetic carbon complex microsphere is put in 600 DEG C of calcining 3h in crucible, and it is hollow to obtain more shells
Magnetic microsphere.
Particularly, the mesoporous carbosphere is prepared by freeze-drying.
Particularly, the macropore carbosphere is freeze-dried through polystyrene swelling reaming.
Compared to the prior art, the present invention is swollen reaming principle using polystyrene, and a large amount of macropores are manufactured on carbon ball surface
Defect makes the Fe of generation3O4A large amount of surfaces externally and internallies for being enriched in carbon ball, increase the amount of iron load of carbon, contribute to for the carbon that subsequently heats up
Change forms Fe3O4Complete shell, the generation for phenomena such as avoiding shell from caving in.
Description of the drawings
Fig. 1 is the PS@C complex microspheres prepared in the embodiment of the present invention 1, scanning nuclear microprobe result；
Fig. 2 is that the PS@C complex microspheres prepared in the embodiment of the present invention 1 load Fe3O4Afterwards, transmission electron microscope results；
Fig. 3 is transmission electron microscope results when being warming up to 500 DEG C in the embodiment of the present invention 1；
Fig. 4 is transmission electron microscope results when being warming up to 600 DEG C in the embodiment of the present invention 1；
Fig. 5 is transmission electron microscope results after being warming up to 600 DEG C of constant temperature 1h in the embodiment of the present invention 1；
Fig. 6 is transmission electron microscope results after being warming up to 600 DEG C of constant temperature 3h in the embodiment of the present invention 1；
Fig. 7 is transmission electron microscope results after being warming up to 600 DEG C of constant temperature 3h in the embodiment of the present invention 2；
Fig. 8 is transmission electron microscope results after being warming up to 600 DEG C of constant temperature 3h in the embodiment of the present invention 3.
Specific implementation mode
It is described below for disclosing the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
The present invention basic principle can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
Embodiment 1
The present embodiment prepares a kind of preparation method of more shell hollow magnetic microballoons：
Glucose 7g, sucrose 5g, sodium nitrite 0.2g are dissolved in 100ml deionized waters, and it is anti-that high pressure hydro-thermal is transferred to after being completely dissolved
It answers in kettle, 140 DEG C of isothermal reactions 12 hours, centrifugation, ethyl alcohol is washed 3 times, is washed 3 times, and freeze-drying obtains mesoporous carbosphere；
The ultrasound swelling in the mixed liquor of 0.3g styrene and 0.02g azodiisobutyronitriles of 0.5g carbospheres is taken, 0.6g is added
SDS and 100ml deionized water ultrasonic disperse 15min, form uniform brown emulsion, lead to N230min, 70 DEG C of polymerisations, obtains
To PS@C complex microspheres, obtained PS@C complex microspheres are dissolved in 72h in 50ml tetrahydrofuran solutions, remove polystyrene, warp
3 removal tetrahydrofuran solutions of washing, freeze-drying obtain macropore carbosphere, and it is template to take 0.2g macropore carbospheres, with
FeCl3And FeCl2For source of iron, under the action of sodium hydroxide, using the method being co-precipitated in situ on the surface of macropore carbosphere and
Inside enrichment Fe3O4Magnetic particle, centrifugation, washing freeze-drying obtain magnetic carbon complex microsphere, finally answer obtained magnetic carbon
It closes microballoon and is put in 550 DEG C of calcining 3h in crucible, obtain more shell hollow magnetic microballoons.
Please refer to the transmission picture of Fig. 1 to Fig. 6, wherein the pattern of the compound carbosphere of polystyrene is complete in Fig. 1
Whole, sphericity is high, and a large amount of Fe of macropore carbosphere surface enrichment is can see in Fig. 23O4Particle is warming up to 500 DEG C in Fig. 3
After see that microsphere surface shell has been formed, kernel has been detached with shell；It will be detached through 600 DEG C of nucleocapsids in Fig. 4；In Fig. 5
Nucleocapsid separating distance gradually increases after 600 DEG C of nucleocapsid 1h, and carbosphere is tapered into the extension carbon core of time；Fig. 6 is through 600
Second layer shell and third layer shell have occurred after DEG C 3h.
Embodiment 2
The present embodiment prepares a kind of preparation method of more shell hollow magnetic microballoons：
Glucose 7g, sucrose 5g, sodium nitrite 0.4g are dissolved in 100ml deionized waters, and it is anti-that high pressure hydro-thermal is transferred to after being completely dissolved
It answers in kettle, 140 DEG C of isothermal reactions 12 hours, centrifugation, ethyl alcohol is washed 3 times, is washed 3 times, and freeze-drying obtains mesoporous carbosphere；
The ultrasound swelling in the mixed liquor of 0.5g styrene and 0.025g azodiisobutyronitriles of 0.5g carbospheres is taken, 0.8g is added
SDS and 100ml deionized water ultrasonic disperse 15min, form uniform brown emulsion, lead to N230min, 70 DEG C of polymerisations, obtains
To PS@C complex microspheres, obtained PS@C complex microspheres are dissolved in 72h in 50ml tetrahydrofuran solutions, remove polystyrene, warp
3 removal tetrahydrofuran solutions of washing, freeze-drying obtain macropore carbosphere, and it is template to take 0.2g macropore carbospheres, with
FeCl3And FeCl2For source of iron, under the action of sodium hydroxide, using the method being co-precipitated in situ on the surface of macropore carbosphere and
Inside enrichment Fe3O4Magnetic particle, centrifugation, washing freeze-drying obtain magnetic carbon complex microsphere, finally answer obtained magnetic carbon
It closes microballoon and is put in 550 DEG C of calcining 3h in crucible, please refer to transmission electron microscope results shown in Fig. 7, it is micro- to obtain more shell hollow magnetics
Ball.
Embodiment 3
The present embodiment prepares a kind of preparation method of more shell hollow magnetic microballoons：
Glucose 7g, sucrose 5g, sodium nitrite 0.6g are dissolved in 100ml deionized waters, and it is anti-that high pressure hydro-thermal is transferred to after being completely dissolved
It answers in kettle, 140 DEG C of isothermal reactions 12 hours, centrifugation, ethyl alcohol is washed 3 times, is washed 3 times, and freeze-drying obtains mesoporous carbosphere；
The ultrasound swelling in the mixed liquor of 0.7g styrene and 0.03g azodiisobutyronitriles of 0.5g carbospheres is taken, 1.0 g are added
SDS and 100ml deionized water ultrasonic disperse 15min, form uniform brown emulsion, lead to N230min, 70 DEG C of polymerisations, obtains
To PS@C complex microspheres, obtained PS@C complex microspheres are dissolved in 72h in 50ml tetrahydrofuran solutions, remove polystyrene, warp
3 removal tetrahydrofuran solutions of washing, freeze-drying obtain macropore carbosphere, and it is template to take 0.2g macropore carbospheres, with
FeCl3And FeCl2For source of iron, under the action of sodium hydroxide, using the method being co-precipitated in situ on the surface of macropore carbosphere and
Inside enrichment Fe3O4Magnetic particle, centrifugation, washing freeze-drying obtain magnetic carbon complex microsphere, finally answer obtained magnetic carbon
It closes microballoon and is put in 550 DEG C of calcining 3h in crucible, please refer to transmission electron microscope results shown in Fig. 8, it is micro- to obtain more shell hollow magnetics
Ball.
It should be understood by those skilled in the art that the embodiment of the present invention shown in foregoing description and attached drawing is only used as illustrating
And it is not intended to limit the present invention.The purpose of the present invention has been fully and effectively achieved.The function and structural principle of the present invention exists
It shows and illustrates in embodiment, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (3)
1. a kind of preparation method of more shell hollow magnetic microballoons, which is characterized in that include the following steps：
Step（1）：Using hydro-thermal method, with glucose, sucrose is the sources C, and sodium nitrite is dissolved in deionized water, and stirring is completely dissolved
After be transferred in high-pressure hydrothermal reaction kettle, 140 DEG C of isothermal reaction a few hours, centrifugation, ethyl alcohol washes 3 times, washes 3 times, is freeze-dried
To mesoporous carbosphere；
Step（2）：By step（1）Obtained monodisperse mesoporous carbosphere surpasses in the mixed liquor of styrene and azodiisobutyronitrile
Sound is swollen, and adds SDS and deionized water ultrasonic disperse, leads to N2, 70 DEG C of polymerisations obtain PS@C complex microspheres；
Step（3）：By step（2）In obtained PS@C complex microspheres be dissolved in 72h in tetrahydrofuran solution, remove polystyrene,
Through 3 removal tetrahydrofuran solutions of washing, freeze-drying obtains macropore carbosphere；
Step（4）：Take step（3）Obtained macropore carbosphere is template, with FeCl3·6H2O and FeCl2·4H2O is source of iron,
Under the action of sodium hydroxide, using the method being co-precipitated in situ on the surface of macropore carbosphere and internal enrichment Fe3O4Magnetic particles
Son, centrifugation, washing freeze-drying obtain magnetic carbon complex microsphere；
Step（5）：Take step（4）Obtained magnetic carbon complex microsphere is put in 600 DEG C of calcining 3h in crucible, and it is hollow to obtain more shells
Magnetic microsphere.
2. the preparation method of more shell hollow magnetic microballoons according to claim 1, which is characterized in that the mesoporous carbon is micro-
Ball is prepared by freeze-drying.
3. the preparation method of more shell hollow magnetic microballoons according to claim 1, which is characterized in that the macropore carbon is micro-
Ball is freeze-dried through polystyrene swelling reaming.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961162A (en) * | 2019-12-09 | 2020-04-07 | 北京化工大学 | Catalyst carrier, precious metal catalyst, and preparation method and application thereof |
| CN111233048A (en) * | 2020-01-17 | 2020-06-05 | 曲靖师范学院 | Double-shell MnCo2O4Hollow nanosphere material and synthesis method thereof |
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