CN106311248B - A kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation - Google Patents
A kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation Download PDFInfo
- Publication number
- CN106311248B CN106311248B CN201610670201.1A CN201610670201A CN106311248B CN 106311248 B CN106311248 B CN 106311248B CN 201610670201 A CN201610670201 A CN 201610670201A CN 106311248 B CN106311248 B CN 106311248B
- Authority
- CN
- China
- Prior art keywords
- zinc
- carbon
- composite material
- znfe
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 64
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910002090 carbon oxide Inorganic materials 0.000 title claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002077 nanosphere Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims description 31
- 239000011701 zinc Substances 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011258 core-shell material Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229940031098 ethanolamine Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002114 nanocomposite Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 230000000877 morphologic effect Effects 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 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 description 9
- 239000008103 glucose Substances 0.000 description 9
- 230000005415 magnetization Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000004627 transmission electron microscopy Methods 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 210000001742 aqueous humor Anatomy 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/40—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation, which is a kind of zinc ferrite/carbon/zinc oxide nanometer composite material with hollow structure, chemical expression ZnFe2O4/C/ZnO；The preparation method of the material is to utilize Fe3O4@C sky ball is template, under conditions of solvent heating, obtains the ZnFe of size uniformity, morphological rules by reaction in-situ2O4/ C/ZnO composite hollow nanometer, wherein size is about 350nm, and pattern is hollow ball-shape structure.Present invention firstly provides with Fe3O4@C hollow nano-sphere is template, synthesizes the ZnFe2O4@C@ZnO compound nano-hollow sphere；Technique is advanced, and the product prepared has excellent properties；Preparation process is simple, easy to operate.
Description
Technical field
The present invention relates to field of nano material preparation, are related to the preparation of oxidate nano hollow sphere, and especially one kind has both
Magnetic, photocatalysis and glucose detection performance ZnFe2O4The preparation of/C/ZnO composite hollow nanosphere.
Background technique
ZnO has been widely used in the fields such as gas sensor, photocatalysis as a kind of important wide band gap semiconducter.
However, the band gap due to ZnO is up to 3.2eV, only the ultraviolet light of short wavelength can just make it generate light induced electron in sunlight
The hole and.But in sunlight, the content of ultraviolet light only accounts for 5%, and most visible light (50%) can not but excite ZnO, this
Limit its extensive use.In order to solve this problem, by the ZnO of broad-band gap together with the semiconductors coupling of narrow band gap,
It is a kind of raising sun light utilization efficiency, promotes its electronics to separate with hole and improve the effective way of its photocatalysis efficiency.
ZnFe2O4It is a kind of semiconductor material of narrow band gap (1.9eV), can use most visible light.In addition, ZnFe2O4Also have
There are good chemical stability and higher ferromagnetism.But semiconductor ZnFe2O4Under excited by visible light, light induced electron and
The recombination rate in hole is very fast, and overall utilization efficiency is not high.If by ZnO and ZnFe2O4It is combined with each other to form heterojunction structure,
The structure will promote the light induced electron of two kinds of semiconductors and the separation in hole simultaneously, to greatly improve photocatalysis efficiency.Closely
Nian Lai, document report are some about ZnO/ZnFe2O4The synthetic method of composite material, specific as follows:
Holland's " alloy and compound magazine " (Journal of Alloys and Compounds, 2013, the 564th
Volume, page 55-62) it reports under the conditions of hydro-thermal method, zinc source and source of iron, one-step synthesis ZnFe is added2O4/ ZnO composite Nano
Grain.The nano particle that the method obtains does not have regular shape, and agglomeration is serious.
Switzerland's " chemical engineering journal " (Chemical Engineering Journal, 2013, volume 217, the 185th-
Page 191) it reports with ZnFe2O4For template, the ZnFe with core-shell structure is synthesized2O4/ ZnO composite nanometer particle.Due to
ZnFe2O4The pattern of itself is irregular and size is inhomogenous, causes the pattern of the composite nanometer particle of synthesis also irregular.
U.S.'s " physical chemistry magazine " (Journal of Physical Chemistry C, 2010, volume 114,
Page 17455-17459) one kind is reported using carbon ball as template, the zinc source source of iron that molar ratio is 1:2 is added, under alkaline condition,
It forms metal hydroxides and the ZnFe of hollow structure is obtained by high annealing2O4/ ZnO nano composite material.The method obtains
Particle size it is larger, the specific surface area of material is small, is unfavorable for the progress of light-catalyzed reaction.In addition, removing carbon elimination template in high temperature
When, easily cause the collapsing of sky spherical structure.
German " advanced material " (Advanced Materials, 2014, volume 26, page 6622-6628) is reported
With metal-organic framework materials (MOFs) for presoma, by annealing process, ZnFe is synthesized2O4/ ZnO/C nanocomposite.This
Kind method synthesis process is comparatively laborious, and equipment and technical conditions are more demanding.
The U.S. " ACS application material and interface " (ACS Applied Materials&Interfaces, 2015, the 7th
Volume, the 17811-17818 pages) it reports using ZnO sky ball as template, source of iron is added, by high-temperature annealing process, having synthesized has
The ZnFe of the double-deck sky spherical structure2O4/ ZnO composite nano materials.The size of ZnO template in the micron-scale, leads to compound receive in the method
Rice grain is oversized.Particle size is excessive, reduces its specific surface area, is unfavorable for light-catalyzed reaction.
In conclusion currently in synthesis morphological rules, size uniformity, with the ZnFe of hollow structure2O4/ ZnO composite Nano
Challenge is still remained on material, we have proposed a kind of low costs, easy synthesis ZnFe in the present invention2O4/ ZnO compound air
The method of heart nanosphere.The ZnFe synthesized by this method2O4/ ZnO composite hollow nanosphere has morphological rules, size equal
One (about 400nm) and good dispersibility.Meanwhile the particle of this method preparation, there is preferable ferromagnetism, the composition of product
It is controllable with performance, photocatalytic degradation of dye and in terms of show good application prospect.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of new preparation ZnFe2O4/ C/ZnO compound nano-hollow sphere
Method, to overcome disadvantages mentioned above of the existing technology.
The present invention solves its technical problem, and the following technical solution is employed:
Zinc ferrite/carbon/zinc oxide nanometer composite material provided by the invention, be a kind of zinc ferrite with hollow structure/
Carbon/zinc oxide nanometer composite material, chemical expression ZnFe2O4/C/ZnO。
Zinc ferrite/carbon/the zinc oxide nanometer composite material, having a size of 320-370nm, pattern is hollow ball-shape
Structure.
Zinc ferrite provided by the invention/carbon/zinc oxide nanometer composite material preparation method, specifically: utilizing Fe3O4@C
Empty ball is template, under conditions of solvent heating, obtains the ZnFe of size uniformity, morphological rules by reaction in-situ2O4/C/ZnO
Composite hollow nanometer, wherein pattern is hollow ball-shape structure having a size of 320-370nm.
Above-mentioned zinc ferrite/carbon/zinc oxide nanometer composite material preparation method provided by the invention, including following step
It is rapid:
A, it utilizesMethod synthesizes SiO2Particle:
(1) by ethyl alcohol, deionized water, ammonium hydroxide, 25:2:1 is mixed by volume, is quickly stirred 30min, is divided ammonium hydroxide sufficiently
It dissipates in reaction system；
(2) 3mL TEOS is added rapidly in above-mentioned solution, is quickly stirred, milky occurred to solution, reduce stirring
Speed continues to stir 4h, after products therefrom is centrifuged, is washed with deionized repeatedly, is finally scattered in deionized water, is made into
Concentration is the solution for standby of 0.6M；
B, synthesis core shell structure SiO2@Fe3O4@C nano particle:
(1) the above-mentioned silicon ball of 2~6mL is taken, is centrifuged, it is multiple with acetone washing, it is finally scattered in 30mL acetone；
(2) 0.6g ferrocene is added in above-mentioned suspension, ultrasonic 30min, addition 3mL mass fraction is 30%H2O2, stir
30min is mixed, being sealed in liner is polytetrafluoroethylene (PTFE), and shell is in the reaction vessel of steel material, in 200 DEG C of 24~48h of reaction；
After the reaction was completed, cooled to room temperature is centrifuged, and washing obtains the SiO with core-shell structure2@Fe3O4@C nano particle；
C, the Fe of synthesis bivalve layer3O4@C sky ball nano particle:
By resulting SiO2@Fe3O4@C nano particle, is scattered in the mixed solution of 10mL deionized water and 5mL ammonium hydroxide,
3min is stirred, being enclosed in liner is polytetrafluoroethylene (PTFE), and shell is to react 4 in 140 DEG C~160 DEG C in the reaction vessel of steel material
~8h；Cooled to room temperature is washed with deionized and obtains the Fe with the double-deck empty spherical structure three times3O4@C nano particle；
D, ZnFe is synthesized2O4/ C@/ZnO composite hollow nanosphere:
Using solvent-thermal method, specifically: by Fe3O4@C nano particle is scattered in the mixed solution of acetone, ethanol amine, is surpassed
Sound 30min, is added a certain amount of zinc source, and the molar ratio in Fe and zinc source is (6~1): (0~1), stirs 10min, being enclosed in liner is
Polytetrafluoroethylene (PTFE), shell are in the reaction vessel of steel material, in 200 DEG C of 12~36h of reaction；Again after Magneto separate and washing,
Obtain ZnFe2O4/ C/ZnO composite hollow nanosphere.
In above-mentioned steps D, the acetone: ethanol amine volume ratio is 1:1.
In above-mentioned steps D, the zinc source uses one of zinc nitrate, zinc acetate, zinc chloride.
In above-mentioned steps D, the zinc source uses zinc acetate.
In above-mentioned steps D, the molar ratio in the Fe and zinc source is 3:2.
The present invention has major advantage below compared with prior art:
1. being put forward for the first time with Fe3O4@C hollow nano-sphere is template, synthesizes the ZnFe2O4@C@ZnO compound nano-hollow sphere.
2. technique is advanced, the product prepared has excellent properties.
Using Fe3O4@C hollow nano-sphere prepares composite nanometer particle as template, by reaction in-situ, after reaction
It is not required to remove template, effectively avoids destruction of the high-temperature annealing process to hollow structure, the composite Nano that such method is prepared
Grain structure is stablized, and its composition and performance easy-regulating.The compound nano-hollow sphere have uniform size, rule structure,
Composition and performance easy-regulating and good dispersibility.In photocatalytic degradation of organic matter and the experiment of colorimetric determination glucose
Show excellent performance.
3. preparation method simple process, easy to operate.
Due to using solvent structure, so easy to operate, at low cost, the requirement to equipment is low.
Detailed description of the invention
Fig. 1 is ferroferric oxide/carbon (Fe3O4@C) hollow Nano particle and zinc ferrite/carbon/zinc oxide (ZnFe2O4/C/
ZnO) the X-ray diffractogram of composite hollow nano particle, wherein@indicates cladding.The standard card of ferroso-ferric oxide is JCPDS
No.19-0629；The standard card of zinc ferrite is JCPDS No.89-1011；The standard card of zinc oxide is JCPDS No.79-
0704。
Fig. 2 isThe SiO of method preparation2The transmission electron microscopy figure of nano particle.
Fig. 3 is SiO2@Fe3O4The transmission electron microscopy figure of@C nano particle.
Fig. 4 is Fe3O4The transmission electron microscopy figure of@C sky ball nano particle.
When Fig. 5 is Fe:Zn=6:1, the transmission electron microscopy figure of the sample of preparation.
When Fig. 6 is Fe:Zn=3:1, the transmission electron microscopy figure of the sample of preparation.
When Fig. 7 is Fe:Zn=3:2, the transmission electron microscopy figure of the sample of preparation.
When Fig. 8 is Fe:Zn=1:1, the transmission electron microscopy figure of the sample of preparation.
When Fig. 9 is Fe:Zn=3:2, the scanning electron microscopy of the sample of preparation.
Figure 10 is the magnetization curve of sample prepared by different Fe/Zn ratios.
Figure 11 is the sample prepared according to embodiment 3, and the activity figure of catalytic degradation methylene blue is (in figure under visible light
Blue curve, i.e. c curve).In figure as a comparison be no catalyst (black curve in figure, i.e. blank), pure ZnO respectively
(red curve in figure, i.e. a curve), pure ZnFe2O4(green curve in figure, i.e. b curve).
Figure 12 is under fluorescent light, sample prepared with embodiment 3 to be made to detect aqueous humor glucose, dense in different glucose
Under degree, the UV-visible absorption spectrum of solution.
Specific embodiment
Below in conjunction with examples and drawings, the invention will be further described, but does not limit the present invention.
Embodiment 1:
The present invention proposes that a kind of new synthesis has zinc ferrite/carbon/zinc oxide nanometer composite material of hollow structure, changes
Expression formula is ZnFe2O4/C/ZnO。
This preparation ZnFe2O4The method of/C/ZnO composite hollow nano particle, mainly comprises the steps that
1. utilizingMethod synthesizes SiO2Particle:
It (1) is by volume that 25:2:1 is mixed by the ammonium hydroxide that dehydrated alcohol, deionized water, mass fraction are 30%, quickly
30min is stirred, is well-dispersed in ammonium hydroxide in reaction system；
(2) 3mL TEOS (tetraethyl orthosilicate) is added rapidly in above-mentioned solution, is quickly stirred, occurred to solution milky white
Color reduces mixing speed, continues stirring 4h and products therefrom rapid centrifugation (8000rpm, 3min) is washed with deionized more
It is secondary, it is finally scattered in deionized water, is made into the silicon ball solution for standby that concentration is 0.6M.The SiO of this method synthesis2Nanometer
The size of grain is in 250nm or so.
2. synthesis core shell structure SiO2@Fe3O4@C nano particle:
(1) the above-mentioned silicon ball solution of 4mL is taken, is centrifuged, it is multiple with acetone washing, finally it is scattered in 30mL acetone (analysis is pure)
In, obtain suspension；
(2) 0.6g ferrocene is added in above-mentioned suspension, ultrasonic 30min, and the H that 3mL mass fraction is 30% is added2O2, stir
30min is mixed, being sealed in liner is polytetrafluoroethylene (PTFE), and shell is in the reaction vessel of steel material, for 24 hours in 200 DEG C of reactions.Reaction
After the completion, cooled to room temperature is centrifuged, and washing obtains the SiO with core-shell structure2@Fe3O4@C nano particle.
3. synthesizing bivalve layer Fe3O4@C sky ball nano particle:
By above-mentioned resulting SiO2@Fe3O4@C nano particle is scattered in mixed solution (the water 10mL, ammonium hydroxide of water and ammonium hydroxide
5mL total volume 15mL) in, stir 3min, be enclosed in liner be polytetrafluoroethylene (PTFE), shell be steel material reaction vessel in, in
150 DEG C of reaction 6h.Cooled to room temperature is washed with deionized and obtains the Fe with the double-deck empty spherical structure three times3O4@C receives
Rice grain.
4. synthesizing ZnFe2O4/ C/ZnO composite hollow nano particle:
By Fe3O4@C nano particle is scattered in the mixed solution (volume ratio 1:1) of acetone, ethanol amine, ultrasonic 30min,
It is added Zn (AC)2As zinc source, it is that zinc source is added in 6:1 according to the molar ratio in Fe and zinc source, stirs 10min, it is poly- for being enclosed in liner
Tetrafluoroethene, shell are in the reaction vessel of steel material, for 24 hours in 200 DEG C of reactions.Separation, washing.Obtain ZnFe2O4@C@
ZnO composite hollow nanosphere.
Embodiment 2:
On the basis of embodiment 1, the molar ratio in Fe and zinc source is only adjusted to 3:1, other reaction conditions are constant.
Embodiment 3:
On the basis of embodiment 1, the molar ratio in Fe and zinc source is only adjusted to 3:2, other reaction conditions are constant.
Embodiment 4:
On the basis of embodiment 1, the molar ratio in Fe and zinc source is only adjusted to 1:1, other reaction conditions are constant.
Fig. 1 shows template Fe3O4The X ray diffracting spectrum of@C sky ball nano particle and the composite nanometer particle finally synthesized,
That diamond indicia mark is Fe in the figure3O4Diffraction maximum；Circular mark mark is ZnFe2O4Diffraction maximum, triangle mark
What note marked is the diffraction maximum of ZnO.The curve of lower section is Fe in figure3O4The diffraction curve of@C, by comparison, it was found that, in figure line
Diffraction maximum position and Fe3O4(cubic phase) standard card JCPDS No.19-0629 is consistent, illustrates that we use during the experiment
Fe3O4It is pure phase, without impurity.The curve of top is ZnFe in figure2O4The diffraction curve of/C/ZnO is found by comparison, is schemed
Diffraction maximum position and ZnFe in line2O4(cubic phase) standard card JCPDS No.89-1011 and ZnO (hexagonal phase) standard card
JCPDS No.79-0704 is consistent, in addition to this without the appearance of other miscellaneous peaks, illustrates in final product really by ZnFe2O4
With two phase composition of ZnO, and free from admixture mutually exists.
The sample in sample and synthesis process that Fig. 2-is synthesized Fig. 8 shows best synthetic schemes is in transmission electron microscope
The data obtained is characterized under (abbreviation TEM).Fig. 2 indicates to utilizeThe SiO of method synthesis2The TEM of particle characterizes picture, shows
The SiO synthesized in experiment2Particle has well-regulated pattern, and uniform size and good monodispersity, size about exist
250nm or so.Fig. 3 indicates SiO2@Fe3O4The TEM of@C nano particle characterizes picture, shows Fe3O4It is coated on completely with C shell
SiO2The surface of particle, in addition, particle still keeps good dispersibility.Fig. 4 indicates Fe3O4The TEM table of@C sky ball nano particle
Picture is levied, as can be seen that synthesized particle has empty spherical structure, sample topography rule really from data, size uniformity divides
It is good to dissipate property.Fig. 5 is the TEM characterization picture of the resulting sample of embodiment 1.Fig. 6 is the TEM characterization of the resulting sample of embodiment 2
Picture.Fig. 5, Fig. 6 and Fig. 4 it was found that, significant change does not occur for the pattern of sample, illustrate under both ratios, and
There is no the generation of ZnO.Fig. 7 is the TEM characterization picture of the resulting sample of embodiment 3, as can be seen from the figure in Fe3O4@C sky ball
The surface of nano particle has coated ZnO.Fig. 8 is the TEM characterization picture of the resulting sample of specific embodiment 4, can from figure
Out, start a small amount of ZnO nanorod occur in the surrounding of particle, illustrate Zn2+Additional amount should control within this range.
Fig. 9 is that sample prepared by best synthesis technology characterizes the data obtained at scanning electron microscope (abbreviation SEM).
It can be seen from the figure that sample has well-regulated spherical shape, and there is substance attachment on surface；In addition, passing through particle damaged in Fig. 9
As can be seen that sample really has hollow structure.
Figure 10 indicates the sample of best synthetic schemes synthesis and the magnetization curve figure of the sample in synthesis process, can from figure
To find out, reaction front and back, the coercivity of sample is zero, illustrates that sample all has superparamagnetism.S1 indicates Fe in figure3O4@C is empty
The magnetization curve of ball nano particle, S2 indicate the magnetization curve of the sample as prepared by embodiment 1, and S3 is indicated by 2 institute of embodiment
The magnetization curve of the sample of preparation, S4 indicate the magnetization curve of the sample as prepared by embodiment 3, and S5 is indicated by 4 institute of embodiment
The magnetization curve of the sample of preparation.By comparing it can be found that when Fe/Zn molar ratio increases to 3:1 (from S1-S3), sample from 6:0
The magnetism of product gradually increases, and illustrates ZnFe2O4Content is increasing；When Fe/Zn molar ratio continues growing (S4-S5), the magnetic of sample
Property gradually weakens, and illustrates that the content of ZnO is increasing.
Figure 11 is prepared by the best synthesis technology of light irradiation of the visible wavelength (being obtained using filter plate) issued with 50W xenon lamp
ZnFe2O4@C@ZnO sample carries out the activity curve of photocatalytic degradation to methylene blue solution, the difference in Figure 11 as a comparison
It is no catalyst (the blank curve in Figure 11), pure ZnO (a curve in Figure 11), pure ZnFe2O4(the b curve in Figure 11).It is logical
Cross comparison discovery, the ZnFe of best synthesis technology synthesis2O4The activity of@C@ZnO sample degradation methylene blue be higher than pure phase ZnO and
Pure phase ZnFe2O4。
Figure 12 is the glucose in sample detection aqueous solution prepared using best synthesis technology, not under fluorescent light
With under concentration of glucose, the UV-visible absorption spectrum of solution.In figure 12 it can be seen that with the increasing of concentration of glucose
Add, the absorbance of solution also becomes larger.Illustrate sample synthesized in experiment, has to the detection of aqueous humor glucose very high
Activity.
By evaluation result it is found that the sample synthesized using the method for the present invention, catalytic degradation organic dyestuff under visible light,
And there is good activity in terms of detection aqueous humor glucose.In four kinds of embodiments, the performance for the sample that embodiment 3 is prepared
Most preferably.
Claims (8)
1. a kind of zinc ferrite/carbon/zinc oxide nanometer composite material, it is characterized in that a kind of zinc ferrite/carbon/oxygen with hollow structure
Change zinc nanocomposite, chemical expression ZnFe2O4/C/ZnO；The material is to utilize Fe3O4@C sky ball is template,
It under conditions of solvent heating, is obtained by reaction in-situ, wherein the molar ratio in Fe and zinc source is 3:2~1:1.
2. zinc ferrite/carbon/zinc oxide nanometer composite material according to claim 1, it is characterised in that the zinc ferrite/
Carbon/zinc oxide nanometer composite material, having a size of 350nm, pattern is hollow ball-shape structure.
3. a kind of zinc ferrite/carbon/zinc oxide nanometer composite material preparation method, it is characterized in that utilizing Fe3O4@C sky ball is mould
Plate obtains size uniformity, shape by reaction in-situ under conditions of the molar ratio in solvent heating and Fe and zinc source is 3:2~1:1
The ZnFe of looks rule2O4/ C/ZnO composite hollow nano particle, having a size of 350nm, pattern is hollow ball-shape structure.
4. zinc ferrite according to claim 3/carbon/zinc oxide nanometer composite material preparation method, it is characterized in that including
Following steps:
A, SiO is synthesized using St ber method2Particle:
(1) by ethyl alcohol, deionized water, ammonium hydroxide, 25:2:1 is mixed by volume, is quickly stirred 30 min, is well-dispersed in ammonium hydroxide
In reaction system；
(2) 3 mL TEOS are added rapidly in above-mentioned solution, are quickly stirred, milky occur to solution, reduce stirring speed
Degree continues to stir 4h, after products therefrom is centrifuged, is washed with deionized repeatedly, is finally scattered in deionized water, is made into dense
Degree is the solution for standby of 0.6 M；
B, synthesis core shell structure SiO2@Fe3O4@C nano particle:
(1) SiO for taking 2 ~ 6 mL step A to obtain2The solution of particle, centrifugation is multiple with acetone washing, is finally scattered in 30 mL third
In ketone；
(2) 0.6 g ferrocene is added in above-mentioned suspension, 30 min of ultrasound, 3 mL mass fractions of addition are 30%H2O2, stir
30 min are mixed, being sealed in liner is polytetrafluoroethylene (PTFE), and shell is to react 24 ~ 48 in 200 DEG C in the reaction vessel of steel material
h；After the reaction was completed, cooled to room temperature is centrifuged, and washing obtains the SiO with core-shell structure2@Fe3O4@C nano particle；
C, the Fe of synthesis bivalve layer3O4@C sky ball nano particle:
By resulting SiO2@Fe3O4@C nano particle is scattered in the mixed solution of 10 mL deionized waters and 5 mL ammonium hydroxide, stirs
Mix 3 min, be enclosed in liner be polytetrafluoroethylene (PTFE), shell be steel material reaction vessel in, in 140 DEG C ~ 160 DEG C react 4 ~
8h；Cooled to room temperature is washed with deionized and obtains the Fe with the double-deck empty spherical structure three times3O4@C nano particle；
D, ZnFe is synthesized2O4/ C/ZnO composite hollow nanosphere:
Using solvent-thermal method, specifically: by Fe3O4@C nano particle is scattered in the mixed solution of acetone, ethanol amine, ultrasound 30
A certain amount of zinc source is added in min, and the ratio between Fe and the amount of substance in zinc source are 3:2~1:1, stirs 10 min, it is poly- for being enclosed in liner
Tetrafluoroethene, shell are in the reaction vessel of steel material, in 200 DEG C of 12 ~ 36 h of reaction；Again after Magneto separate and washing, obtain
To ZnFe2O4/ C/ZnO composite hollow nanosphere.
5. zinc ferrite according to claim 4/carbon/zinc oxide nanometer composite material preparation method, it is characterized in that in step
In rapid D, the acetone: ethanol amine volume ratio is 1:1.
6. zinc ferrite according to claim 4/carbon/zinc oxide nanometer composite material preparation method, it is characterized in that in step
In rapid D, the zinc source uses one of zinc nitrate, zinc acetate, zinc chloride.
7. zinc ferrite according to claim 4/carbon/zinc oxide nanometer composite material preparation method, it is characterized in that in step
In rapid D, the zinc source uses zinc acetate.
8. zinc ferrite according to claim 4/carbon/zinc oxide nanometer composite material preparation method, it is characterized in that in step
In rapid D, the molar ratio in the Fe and zinc source is 3:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610670201.1A CN106311248B (en) | 2016-08-15 | 2016-08-15 | A kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610670201.1A CN106311248B (en) | 2016-08-15 | 2016-08-15 | A kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106311248A CN106311248A (en) | 2017-01-11 |
| CN106311248B true CN106311248B (en) | 2019-02-22 |
Family
ID=57740513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610670201.1A Active CN106311248B (en) | 2016-08-15 | 2016-08-15 | A kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106311248B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311234A (en) * | 2017-06-28 | 2017-11-03 | 大连理工大学 | A kind of preparation method of zinc oxide/zinc ferrite nano composite material and application |
| CN109390564B (en) * | 2017-08-03 | 2020-08-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ternary metal oxide based on zinc ion doping, preparation method and application thereof |
| CN109399725B (en) * | 2017-08-15 | 2021-04-13 | 中国石油化工股份有限公司 | Preparation method and application of zinc ferrite-containing nano-structure array |
| CN107481827B (en) * | 2017-08-31 | 2019-04-19 | 扬州大学 | The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs |
| CN108012518B (en) * | 2017-12-13 | 2019-12-17 | 横店集团东磁股份有限公司 | Preparation and application method of bell-shaped wave-absorbing material with controllable performance |
| CN108456530B (en) * | 2018-03-26 | 2020-09-25 | 郑州轻工业学院 | Magnetic carboxylated hollow microsphere soil remediation agent, and preparation method and application thereof |
| CN108480393B (en) * | 2018-03-26 | 2020-09-04 | 郑州轻工业学院 | Magnetic aminated hollow microsphere soil remediation agent, and preparation method and application thereof |
| CN108855236A (en) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | A kind of recyclable high temperature resistant photocatalysis film and preparation method for sewage treatment |
| CN111298783A (en) * | 2020-03-06 | 2020-06-19 | 浙江农林大学暨阳学院 | Method for preparing nano microsphere photocatalyst by doping rare earth Ce with ZnO and catalytic degradation method thereof |
| CN111715300B (en) * | 2020-06-22 | 2021-08-24 | 江南大学 | Zinc ferrite/Bi-MOF/tannic acid composite visible light catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104275196A (en) * | 2014-10-24 | 2015-01-14 | 浙江师范大学 | Ferroferric oxide/carbon/cadmium sulfide composite nano material and preparation method thereof |
| CN105126855A (en) * | 2015-07-15 | 2015-12-09 | 浙江大学 | ZnO/ZnFe2O4/C nano-structure hollow spheres and preparation method of same |
-
2016
- 2016-08-15 CN CN201610670201.1A patent/CN106311248B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104275196A (en) * | 2014-10-24 | 2015-01-14 | 浙江师范大学 | Ferroferric oxide/carbon/cadmium sulfide composite nano material and preparation method thereof |
| CN105126855A (en) * | 2015-07-15 | 2015-12-09 | 浙江大学 | ZnO/ZnFe2O4/C nano-structure hollow spheres and preparation method of same |
Non-Patent Citations (1)
| Title |
|---|
| Preparation and photocatalytic application of ZnAFe2O4@ZnO core–shell nanostructures;Rahmatollah Rahimi et al.;《Superlattices and Microstructures》;20150612;第85卷;497-503 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106311248A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106311248B (en) | A kind of zinc ferrite/carbon/zinc oxide nanometer composite material and its method of preparation | |
| Manikandan et al. | Sesamum indicum plant extracted microwave combustion synthesis and opto-magnetic properties of spinel Mn x Co1-x Al2O4 nano-catalysts | |
| Mary Jacintha et al. | Comparative studies of spinel MnFe2O4 nanostructures: structural, morphological, optical, magnetic and catalytic properties | |
| CN105668632B (en) | A kind of tungsten bronze nanometer stub particle of variable valency metal catalysis and doping and preparation method thereof | |
| CN101759146B (en) | Method for preparing ZnO/ZnFe2O4 compound nano hollow sphere | |
| CN106047290B (en) | A kind of method of nanometer Fe 3 O 4 magnetic uniform particle enveloped carbon nanometer tube | |
| CN101289314B (en) | Method for preparing nano hollow microballoons of spinelle type ferrite | |
| CN105148956B (en) | A kind of high efficiency photocatalysis decompose aquatic products hydrogen catalyst and preparation method thereof | |
| CN110534732A (en) | A kind of preparation method of nickel-cobalt-manganese ternary persursor material | |
| CN109317149A (en) | A kind of SiO of nickel-loaded2The preparation method and application of@C core-shell material | |
| CN109603824A (en) | A kind of preparation method and application of silver/zinc oxide composite material | |
| CN108654638A (en) | A kind of hud typed Co based Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN105056926A (en) | Novel TiO2/WO3 coated magnetic nano composite particles and preparation method therefor and use thereof | |
| CN110013880A (en) | A kind of MIL-101 composite photocatalyst material, preparation method and application | |
| CN101219795A (en) | X type zeolite molecular sieve and method for producing the same | |
| CN103789834B (en) | Micrometer/nanometer level gallic acid zinc crystal, Its Preparation Method And Use | |
| CN102660261A (en) | Preparation method of silicon oxynitride fluorescent powder | |
| CN105032457B (en) | Preparation method of Bi2O2CO3/Bi3.84W0.16O6.24 through solvothermal method and application of preparation method | |
| CN100372778C (en) | Method for preparing calcium molybdate self assembling body with hollow structure | |
| CN109158062B (en) | Silicon dioxide colloid composite rare earth core-shell microsphere and preparation method thereof | |
| CN107555467A (en) | A kind of surface exposure being made up of nanoneedle（0001）The preparation method of the Zinc oxide hollow spheres in face | |
| Dewi Elok et al. | Synthesis of Hematite Pigment (ΑFe2O3) from iron lathe waste using precipitation-sonication method as anti-swelling on wood | |
| CN103268801A (en) | FexOy/SiO2 composite material and preparation method thereof | |
| CN113015423B (en) | Fe/Fe with high electromagnetic wave absorption performance4N/Fe3O4-rGO nano material, preparation method and application | |
| CN101914378B (en) | SiO2@ZrO2@Y2O3:Eu3+ fluorescent powder with core-shell structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |