CN103055771A - Magnetic MFe2O4/C/AOX composite material using phenol organic molecules as carbon source and preparation method thereof - Google Patents
Magnetic MFe2O4/C/AOX composite material using phenol organic molecules as carbon source and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnetic MFe2O4/C/AOX composite using phenol organic molecules as a carbon source and a preparation method thereof. The preparation method is characterized by comprising the following steps: 1. preparing magnetic nanoparticle MFe2O4; 2. preparing a magnetic MFe2O4/C composite; and 3. preparing a crystalline magnetic MFe2O4/C/AOX composite nano material, wherein in the MFe2O4, M is Fe, Co, Mn, Ni, Zn, Cu or a combination of more than two elements, and the metal oxide AOX is TiO2, SnO2, ZrO2, ZnO, CeO2 or a combination of two or more than two metal oxides. The magnetic MFe2O4/C/AOX composite material can enable the surface of the magnetic nanoparticle to be negatively charged, can not be chemically degraded in an actual use environment, is convenient for magnetic resolution and recycling after use, and enhances the catalytic activity of the magnetic metal oxide.
Description
Technical field
The present invention relates to a kind of is the magnetic MFe of carbon source based on benzenediol class organic molecule
2O
4/ C/AO
XComposite and preparation method thereof.
Background technology
The ferrite nano structural material because of its data storage, catalysis, sensor, pollutant process and the numerous areas such as biological medicine in extensive use, and cause that people more and more pay close attention to.Yet the surface functional groups of ferrite nano structural material is fewer, for increase the surface can be handling, avoid magnetic ferric oxide nano particles in application process by chemical degradation or gathering, be necessary very much at its surface coverage one deck organic or inorganic shell.Application number a kind of method of synthetic polymethylacrylic acid magnetic composite microsphere that has been 200910218934.1 patent disclosure.Application number is that 201010207481.5 patent also discloses and a kind ofly realizes magnetic ferrites-dendritic polyamide core-shell nano complex by the chemical coupling method.
Usually using more inorganic shell is SiO
2And C.Application number provides a kind of preparation method of magnetic Nano silicon ball, this patent utilization SiO for 200610116026.8 patent
2Coat Fe
3O
4Nano particle, and load TiO
2Photocatalyst material is applied to water purification and processing aspect.Professor Yin Longwei of Shandong University group is with SiO
2Be coated on magnetic nano-particle γ-Fe
2O
3The surface, composite Ti O then
2, prepared the magnetic hybrid nano material, studies show that this material has higher photo-catalysis capability.(Magnetic (γ-Fe
2O
3@SiO
2)
n@TiO
2Functional Hybrid Nanoparticles with Actived Photocatalytic Ability, Chengxiang Wang, Longwei Yin, Luyuan Zhang, Le Kang, Xianfen Wang, Rui Gao, J.Phys.Chem.C 2009,113,4008-4011) in addition, the tri-iron tetroxide that carbon covers also is widely used in preparation inorganic oxide composite nano materials, and for example: many seminar have reported ZrO
2The composite magnetic of shell (Preparation of Fe
3O
4@ZrO
2Core-Shell Microspheres as Affinity Probes for Selective Enrichment and Direct Determination of Phosphopeptides Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry, Yan Li, Taohua Leng, Huaqing Lin, Chunhui Deng, Xiuqing Xu, Ning Yao, Pengyuan Yang, Xiangmin Zhang, J.Proteome Res.2007,6,4498-4510), TiO
2(Novel Approach for the Synthesis of Fe
3O
4@TiO
2Core-Shell Microspheres and Their Application to the Highly Specific Capture of Phosphopeptides for MALDI-TOF MS Analysis, Yan Li, Jinsong Wu, Dawei Qi, Xiuqing Xu, Chunhui Deng, Pengyuan Yang, Xiangmin Zhang, Chem.Commun.2008,564-566), SnO
2(Magnetically Responsive Fe
3O
4@C@SnO
2Core-Shell Microspheres:Synthesis, Characterization and Application in Phosphoproteomics, Dawei Qi, Jin Lu, Chunhui Deng, Xiangmin Zhang, J.Phys.Chem.C 2009,113,15854-15861).
Graphene is a kind of carbonaceous new material that monolayer carbon atom close-packed arrays becomes two-dimentional hexagonal structure, to make up other dimension carbonaceous material, elementary cell (Electric Field Effect in Atomically Thin Carbon Films such as zero dimension fullerene, one dimension CNT, three-dimensional graphite, K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov, Science 2004,306,666-669).Because the two-dimensional structure of Graphene uniqueness, it has excellent electricity, calorifics and mechanical property, makes it become rapidly material science and Condensed Matter Physics field study hotspot in recent years.There are some researches show that the composite of metal oxide and Graphene has good photocatalytic activity (Hierarchically Ordered Macro-Mesoporous TiO
2-Graphene Composite Films:Improved Mass Transfer, Reduced Charge Recombination, and Their Enhanced Photocatalytic Activities, Jiang Du, Xiaoyong Lai, Nailiang Yang, Jin Zhai, David Kisailus, Fabing Su, Dan Wang, Lei Jiang, ACS Nano 2011,5,590-596).Aspect lithium battery applications, TiO
2@TiO
xN
y/ TiN-GS hybrid material is compared with independent titanic oxide material, has promoted the electronics transportation, has high capacity and cycle performance (Synthesis of Size-Tunable Anatase TiO
2Nanospindles and Their Assembly into Anatase@Titanium Oxynitride/Titanium Nitride-Graphene Nanocomposites for Rechargeable Lithium Ion Batteries with High Cycling Performance, Yongcai Qiu, Keyou Yan, Shihe Yang, Limin Jin, Hong Deng, Weishan Li, ACS Nano 2010,4,6515-6526).2008, professor Zhu Yongfa utilized glucose for carbon source has prepared the titanium dioxide nano material that graphene-like carbon coats, and studies show that this material has than the better catalytic capability of business-like P25 (Efficient TiO
2Photocatalysts from Surface Hybridization of TiO
2Particles with Graphite-like Carbon, Li-Wu Zhang, Hong-Bo Fu, Yong-Fa Zhu, Adv.Funct.Mater.2008,18,2180-2189).If use the carbon source material of graphene-like structure to be coated on the magnetic nano particle sub-surface, carry out the modification of metal nanoparticle, be expected to greatly improve the catalytic activity of carbon source clad composite material.Generally everybody used carbon source material is glucose, and this patent proposes a kind of phenol organic molecule that utilizes and is carbon source material, carries out the method that magnetic nano-particle coats.Utilizing this material to carry out carbonization coats: 1) can make hydroxyl, the carbonyl of negative electrical charge on the surface band of magnetic nano-particle, be convenient to the absorption of metal cation, depositing metal oxide; 2) can effectively protect magnetic nano-particle not oxidized; 3) after the carbon-coating protection, material can be kept good magnetic; 4) the six-membered cyclic class graphene-structured of carbon-coating can promote the electronics transportation, improves the catalytic activity of magnetic metal oxide.In addition, magnetic nano-particle has very high specific area, this magnetic inorganic metal oxide materials for synthetic high catalytic activity provides platform, has important using value at aspects such as Magnetic Isolation, water treatment, medical imaging and drug delivery, biology sensor, solar cells.
Summary of the invention
The first technical problem to be solved by this invention is that to provide a kind of for above-mentioned present situation be the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
xComposite, it has middle carbon-coating, can protect magnetic nano-particle, thereby has good performance.
The second technical problem to be solved by this invention is that to provide a kind of for above-mentioned present situation be the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
xThe composite manufacture method.
The technical scheme that the present invention solves the first technical problem is: a kind of is the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
XComposite, it is characterized in that core is MFe
2O
4Magnetic nano-particle, the intermediate layer is based on the carbon-coating that the carbonization of phenol organic molecule produces, thickness is 1-30nm, skin is AO
X, thickness is 10-100nm; Wherein, magnetic nano-particle MFe
2O
4Middle M is the combination of a kind of or above two kinds of elements in Fe, Co, Mn, Ni, Zn, the Cu element; Metal oxide AO wherein
XTiO
2, SnO
2, ZrO
2, ZnO or CeO
2In a kind of, or the combination of above two or more metal oxide, X is positive integer.
The technical scheme that the present invention solves the second technical problem is: a kind of is the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
xThe composite manufacture method, it is characterized in that step is followed successively by:
The first step takes by weighing 0.3-1.0g two hydration trisodium citrates and is scattered in 25～35mL ethylene glycol, stirs 8～10 hours until dissolve, and then adds the 1.5-3.0g sodium acetate trihydrate, 2.5～3.5mmol MCl
y, wherein, M is Fe, Co, and Mn, Ni, Zn, one or more among the Cu, Y is positive integer, is stirred to dissolving, then mixed liquor is transferred in the reactor 200-230 ℃ of reaction 10-20h, preparation magnetic nano-particle;
Second step, with the ultrasonic 10～30min of magnetic nano-particle that obtains, be dispersed in water, add a certain amount of phenol organic molecule aqueous solution, at this moment, the mass concentration of magnetic nano-particle is 0.1～5mg/mL, and the mass ratio of magnetic nano-particle and phenol organic molecule is 1: 1～1: 20; Then, stirred for several minute shifts mixed solution to reactor, 160～200 ℃, reaction 10～36h naturally cools to room temperature, perhaps mixed solution is stirred 0.5-5h, Magnetic Isolation, ultra-pure water cleans, then vacuum drying is transferred to sample in the Muffle furnace, calcines under the inert gas, inert gas comprises nitrogen, argon gas, one or both mists in the helium, calcination temperature range is at 500～1000 ℃, and keeps 3～5h under this temperature, prepares magnetic MFe
2O
4/ C compound;
The 3rd step, ethanol or the aqueous solution 7～9mL of preparation 0.5～3mmol slaine, slaine comprises the ester salt of titanium, zirconium, tin, cerium or hydrochloride is a kind of or more than one, adds the MFe of 9～1lmg
2O
4/ C nano particle, ultrasonic dispersion 8～12min, then stirring at room 0.8～1.2h places under ice-water bath or the room temperature, 1) or 1.8～2.2M NaOH aqueous solution (the ethanol/water volume ratio is 4～6:, stir 2-24h dropwise to add the mixed solution of the ethanol/water of 2mL 0-0.5mM nitric acid.At last, the compound that obtains is utilized Magnetic Isolation, ethanol cleans, the ethanol/water mixed solution cleans or ultra-pure water cleans, and is scattered in 25～35mL volume ratio and is in 0.8～1.2: 1 the ethanol/water solution, is transferred to reactor, 160～230 ℃ of reaction 3～10h, drop to room temperature, water cleans, and obtains crystallinity magnetic MFe
2O
4/ C/AO
XComposite nano materials.
In the such scheme,
Magnetic nano-particle also comprises γ-Fe
2O
3The source of described metallic element can be one or more in its oxide, chloride, bromide, nitrate, sulfate, the carbonate.
In the described magnetic nano-particle synthetic method, be not limited to the hydrothermal/solvent by the use of thermal means, also comprise chemical coprecipitation method or oxidation-precipitation method.Wherein:
Chemical coprecipitation method: take by weighing 0.5～2mmol MCl
2(wherein M comprises Co, Mn, Cu, Zn, Ni more than one) and 1～4mmol FeCl
36H
2O is scattered in the 2M HCl aqueous solution of 25mL, stirs 8～15min under the nitrogen atmosphere, then adds 30～50mL, 28% ammoniacal liquor, stirs 0.5～1.5h, Magnetic Isolation, and water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains MFe
2O
4Nano particle.
Oxidation-precipitation method: compound concentration is the FeCl of 0.6～1.4g/L respectively
24H
2The NaOH aqueous solution of O and 1.2～2.8M.FeCl with 8～12mL
24H
2The O aqueous solution joins in 52～48mL ultra-pure water, stirs the NaOH aqueous solution of the lower 1.6～2.4M of adding, regulates the pH value about 10, continues under the room temperature to stir until solution becomes black.Adopt Magnetic Isolation, and clean for several times with ultra-pure water, in 50 ℃ of vacuum drying chamber dryings, obtain Fe
3O
4Nano particle.
Described phenol organic molecule can be phenol, catechol, hydroquinones, resorcinol, '-biphenyl diphenol and derive hexatomic ring or other heterocyclic organic molecules with hydroxyl, carboxyl, ketone group.
Described magnetic MFe
2O
4In/C compound the synthetic method, can be method for calcinating under the inert gas, also can adopt hydro-thermal treatment method.When adopting the inert gas method for calcinating, inert gas comprises nitrogen, argon gas, one or both mists in the helium.Calcination temperature range is at 500～1000 ℃, and keeps 3～5h under this temperature.In hydrothermal treatment consists carbonization experimental technique, adjusting phenol organic molecule is preferably 10 times with the quality of magnetic nano-particle than scope; Temperature is preferably 180 ℃, and keeps 10～36h under this temperature.
Described metal oxide AO
XCan be TiO
2, SnO
2, ZrO
2, ZnO, CeO
2, or the combination of above two or more metal oxide.The precursor of described metal oxide is its fluoride, chloride, bromide, sulfate, nitrate, acetate, oxide, one or more in isopropoxide and the ester salt thereof.
The preparation method of metal oxide is not limited to sol-gel process, also comprises hydrothermal/solvent by the use of thermal means or collosol and gel-hydrothermal method.Wherein:
Sol-gel process: ethanol or the aqueous solution 5～40mL of preparation 0.5～3mmol slaine, slaine comprises the ester salt of titanium, zirconium, tin, cerium or hydrochloride is a kind of or more than one, adds the MFe of 9～15mg
2O
4/ C nano particle, ultrasonic dispersion 8～12min, stirring at room 0.8～1.2h dropwise adds the NaOH aqueous solution of 0.1～20mL, 0.1～0.5M, stirs 2～24h.At last, the compound that obtains is utilized Magnetic Isolation, ethanol cleans, and the ethanol/water mixed solution cleans or ultra-pure water cleans, and 40～150 ℃ of vacuum drying obtain magnetic MFe
2O
4/ C/AO
XComposite nano materials.
Hydrothermal/solvent by the use of thermal means: ethanol and water (the ethanol/water volume ratio is 5: 0.01～0.01: the 5) mixed solution 30～50mL of preparation 0.5～3mmol slaine, the MFe of adding 9～15mg
2O
4/ C nano particle, ultrasonic 8～12min is transferred in the reactor, and 160～200 ℃ of reaction 10～20h obtain MFe
2O
4/ C/AO
XComposite nano materials.
Compared with prior art, the invention has the advantages that:
1, can make negative electrical charge on the surface band of magnetic nano-particle, as: hydroxyl, carbonyl, be convenient to the absorption of metal cation, depositing metal oxide;
2, can effectively protect magnetic nano-particle, not oxidized in the pyroprocess of coated metal oxide; Under the practical service environment not by chemical degradation;
3, after the carbon-coating protection, material can be kept good magnetic, is convenient to carry out Magnetic Isolation behind the materials'use, recycles;
4, the six-membered cyclic class graphene-structured of carbon-coating can promote the electronics transportation, and this material has potential using value aspect environmental improvement.
Description of drawings
Among Fig. 1 a) and b) be respectively Fe
3O
4The SEM figure of/C composite nano materials and EDS energy spectrogram;
Fig. 2 is Fe
3O
4The hysteresis curve of/C composite nano materials;
Fig. 3 is Fe
3O
4/ C/TiO
2The XRD diffraction of composite nano materials.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the specific embodiment of the present invention is described further, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played any restriction effect.
Embodiment 1:
(1) Fe
3O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.3g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.819g FeCl
36H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 10h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Fe
3O
4Microballoon.
(2) Fe
3O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the Fe of experiment (1) preparation
3O
420mmg is scattered in the 35mL water, and then ultrasonic dispersion 10min adds the 5mL catechol aqueous solution, and stirred for several minute is transferred in the reactor, 180 ℃ of reaction 16h.Be cooled to room temperature, water cleans for several times, in 60 ℃ of vacuum drying chamber dryings, obtains Fe
3O
4/ C microballoon.
(3) Fe
3O
4/ C/TiO
2The preparation of composite nano materials
The butyl titanate of 1mmol is scattered in the 8mL ethanol, adds the Fe of 10mg
3O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 2h.At last, the compound that obtains is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 180 ℃ of reaction 4h drop to room temperature, and water cleans, and obtains magnetic Fe
3O
4/ C/TiO
2Composite nano materials.
Embodiment 2:
(1) Fe
3O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 1.0g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.819g FeCl
36H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 230 ℃ of reaction 12h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Fe
3O
4Microballoon.
(2) Fe
3O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the Fe of experiment (1) preparation
3O
48mg is scattered in the 37mL water, and then ultrasonic dispersion 10min adds the 3mL catechol aqueous solution, and stirred for several minute is transferred in the reactor, 200 ℃ of reaction 16h.Be cooled to room temperature, water cleans for several times, in 60 ℃ of vacuum drying chamber dryings, obtains Fe
3O
4/ C microballoon.
(3) Fe
3O
4/ C/ZrO
2The preparation of composite nano materials
The ZrOCl of 2mmol
28H
2O is scattered in the 8mL ethanol, adds the Fe of 10mg
3O
4/ C nano particle, ultrasonic dispersion 10min, stirring at room 1h then at room temperature, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of 2mL ethanol/water, stirs 16h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 230 ℃ of reaction 10h drop to room temperature, and water cleans, and obtains magnetic Fe
3O
4/ C/ZrO
2Composite nano materials.
Embodiment 3:
(1) Fe
3O
4The preparation of nano particle
The preparation of employing chemical coprecipitation method takes by weighing 1.5mmol FeCl
2With 3mmol FeCl
36H
2O is scattered in the 2M HCl aqueous solution of 25mL, stirs 10min under the nitrogen atmosphere, then adds 40mL 28% ammoniacal liquor, stirs 1h, Magnetic Isolation, and water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains Fe
3O
4Nano particle.
(2) Fe
3O
4The preparation of/C composite nano materials
The hydroquinones aqueous solution of preparation 0.04g/mL.Take by weighing the Fe of experiment (1) preparation
3O
410mg is scattered in the 36mL water, and then ultrasonic dispersion 10min adds the 4mL hydroquinones aqueous solution, and stirred for several minute is transferred in the reactor, 200 ℃ of reaction 26h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains Fe
3O
4/ C microballoon.
(3) Fe
3O
4/ C/Zr
X 'Ti
Y 'O
2The preparation of composite nano materials
0.2 the ZrOCl of～1.8mmol
28H
2O and 1.8～0.2mmol butyl titanate are scattered in the 8mL ethanol, add the Fe of 10mg
3O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 2h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 220 ℃ of reaction 6h drop to room temperature, and water cleans, and obtains magnetic Fe
3O
4/ C/Zr
X 'Ti
Y 'O
2Composite nano materials, x ', y ' they are positive mark or natural number, the proportioning that is put to the test determines.
Embodiment 4:
(1) Fe
3O
4The preparation of nano particle
The preparation of employing oxidation-precipitation method, compound concentration is the FeCl of 1g/L respectively
24H
2The NaOH aqueous solution of O and 2M.FeCl with 10mL
24H
2The O aqueous solution joins in the 50mL ultra-pure water, stirs the NaOH aqueous solution of the lower 2M of adding, regulates the pH value about 10, continues under the room temperature to stir until solution becomes black.Adopt Magnetic Isolation, and clean for several times with ultra-pure water, in 50 ℃ of vacuum drying chamber dryings, obtain Fe
3O
4Nano particle.
(2) Fe
3O
4The preparation of/C composite nano materials
Take by weighing the Fe that experiment (1) obtains
3O
420mg, the ultrasonic 0.02g/mL resorcinol aqueous solution that is scattered in 10mL stirs 1h, filters, and cleans three times 50 ℃ of vacuum drying with ethanol.Then, sample is transferred in the Muffle furnace, under the nitrogen atmosphere, 800 ℃ of heat treatment 3h obtain Fe
3O
4/ C microballoon.
(3) Fe
3O
4/ C/SnO
2The preparation of composite nano materials
Preparation 2mmol SnCl
4Ethanolic solution 40mL, the Fe of adding 15mg
3O
4/ C nano particle, ultrasonic 10min is transferred in the reactor, and 200 ℃ of reaction 18h obtain Fe
3O
4/ C/SnO
2Composite nano materials.
Embodiment 5:
(1) Fe
3O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 1.0g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 1.5g sodium acetate trihydrate, 0.819g FeCl
36H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 220 ℃ of reaction 12h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Fe
3O
4Microballoon.
(2) Fe
3O
4The preparation of/C composite nano materials
Take by weighing the Fe that experiment (1) obtains
3O
420mg is scattered in the 30mL water, and ultrasonic 15min adds the 0.02g/mL '-biphenyl diphenol aqueous solution of 10mL, stirs 1h, Magnetic Isolation, and clean 50 ℃ of vacuum drying three times with ultra-pure water.Then, sample is transferred in the Muffle furnace, under the nitrogen atmosphere, 500 ℃ of heat treatment 5h obtain Fe
3O
4/ C microballoon.
(3) Fe
3O
4/ C/CeO
2The preparation of composite nano materials
With 1mmol Ce (NO
3)
46H
2O is dissolved in the 30mL ultra-pure water, adds the sample of preparation in the 10mg experiment (2), and ultrasonic 10min stirs 1h.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature continues to stir 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains Fe
3O
4/ C/Ce (OH)
4Composite nano materials, last, sample is dry in 100 ℃ of baking ovens, obtain Fe
3O
4/ C/CeO
2Composite nano materials.
Embodiment 6:
(1) CoFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.6g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmol CoCl
2, be stirred to dissolving, then mixed liquor is transferred in the reactor 220 ℃ of reaction 15h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain CoFe
2O
4Microballoon.
(2) CoFe
2O
4The preparation of/C composite nano materials
The '-biphenyl diphenol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL '-biphenyl diphenol aqueous solution, and stirred for several minute is transferred in the reactor, and 160 ℃ are reacted 36h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains CoFe
2O
4/ C microballoon.
(3) CoFe
2O
4/ C/TiO
2The preparation of composite nano materials
The butyl titanate of 2mmol is scattered in the 8mL ethanol, adds the CoFe of 10mg
2O
4/ C nano particle, ultrasonic dispersion 10min, stirring at room 1h then at room temperature, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, stirs 20h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice, 50 ℃ of vacuum drying chamber drying, obtains magnetic CoFe
2O
4/ C/TiO
2Composite nano materials.
Embodiment 7:
(1) NiFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmolNiCl
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 230 ℃ of reaction 16h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain NiFe
2O
4Microballoon.
(2) NiFe
2O
4The preparation of/C composite nano materials
The hydroquinones aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersion 10min adds the 5mL hydroquinones aqueous solution, stir 3h, Magnetic Isolation, and with the ultra-pure water cleaning, in 50 ℃ of vacuum drying chambers oven dry, be transferred in the Muffle furnace, under the nitrogen atmosphere, 1000 ℃ of heat treatment 3h obtain NiFe
2O
4/ C microballoon.
(3) NiFe
2O
4/ C/ZrO
2The preparation of composite nano materials
The ZrOCl of 2mmol
28H
2O is scattered in the 8mL water, adds the NiFe of 10mg
2O
4/ C nano particle, ultrasonic dispersion 10min, stirring at room 1h dropwise adds the 0.2mL 2M NaOH aqueous solution, stirs 20h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 200 ℃ of reaction 10h drop to room temperature, and water cleans, and obtains magnetic NiFe
2O
4/ C/ZrO
2Composite nano materials.
Embodiment 8:
(1) CuFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mmL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, lmmol CuCl
2, be stirred to dissolving, then mixed liquor is transferred in the reactor 210 ℃ of reaction 16h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain CuFe
2O
4Microballoon.
(2) CuFe
2O
4The preparation of/C composite nano materials
The resorcinol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL resorcinol aqueous solution, and stirred for several minute is transferred in the reactor, and 160 ℃ are reacted 36h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains CuFe
2O
4/ C microballoon.
3) CuFe
2O
4/ C/Zr
X 'Ti
Y 'O
2The preparation of composite nano materials
0.1 the ZrOCl of～2.9mmol
28H
2O and 2.9～0.1mmol butyl titanate are scattered in the 8mL ethanol, add the CuFe of 10mg
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.2mM nitric acid, and ice-water bath stirs 2h.At last, the compound that obtains is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 220 ℃ of reaction 7h drop to room temperature, and water cleans, and obtains magnetic CuFe
2O
4/ C/Zr
X 'Ti
Y 'O
2Composite nano materials, x ', y ' they are positive mark or natural number, the proportioning that is put to the test determines.
Embodiment 9:
(1) CoFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmol CoCl
2, be stirred to dissolving, then mixed liquor is transferred in the reactor 230 ℃ of reaction 13h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain CoFe
2O
4Microballoon.
(2) CoFe
2O
4The preparation of/C composite nano materials
The '-biphenyl diphenol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL '-biphenyl diphenol aqueous solution, and stirred for several minute is transferred in the reactor, and 180 ℃ are reacted 24h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains CoFe
2O
4/ C microballoon.
(3) CoFe
2O
4/ C/SnO
2The preparation of composite nano materials
Preparation 2.5mmol SnCl
4Ethanolic solution 40mL, the CoFe of adding 12mg
2O
4/ C nano particle, ultrasonic 10min is transferred in the reactor, and 180 ℃ of reaction 16h obtain CoFe
2O
4/ C/SnO
2Composite nano materials.
Embodiment 10:
(1) CuFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmol CuCl
2, be stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 10h.Be cooled to room temperature, clean for several times with ethanol, water, dry in the 50C vacuum drying chamber, obtain CuFe
2O
4Microballoon.
(2) CuFe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL catechol aqueous solution, and stirred for several minute is transferred in the reactor, and 180 ℃ are reacted 36h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains CuFe
2O
4/ C microballoon.
(3) CuFe
2O
4/ C/CeO
2The preparation of composite nano materials
With 1mmol Ce (NO
3)
46H
2O is dissolved in the 30mL ultra-pure water, adds the sample of preparation in the 10mg experiment (2), and ultrasonic 10min stirs 1h.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature continues to stir 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains CuFe
2O
4/ C/Ce (OH)
4Composite nano materials, last, sample is dry in 100 ℃ of baking ovens, obtain CuFe
2O
4/ C/CeO
2Composite nano materials.
Embodiment 11:
(1) NiFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmol NiCl
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 15h.Be cooled to room temperature, clean for several times with ethanol, water, in 70 ℃ of vacuum drying chamber dryings, obtain NiFe
2O
4Microballoon.
(2) NiFe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL catechol aqueous solution, and stirred for several minute is transferred in the reactor, and 160 ℃ are reacted 36h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains NiFe
2O
4/ C microballoon.
(3) NiFe
2O
4/ C/TiO
2The preparation of composite nano materials
The butyl titanate of 2mmol is scattered in the 7.9mL ethanol, adds the NiFe of 10mg
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 10h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 230 ℃ of reaction 6h are down to room temperature, and water cleans, and obtains magnetic NiFe
2O
4/ C/TiO
2Composite nano materials.
Embodiment 12:
(1) ZnFe
2O
4The preparation of microballoon
Take by weighing 1.5mmol ZnCl
2With 3mmol FeCl
36H
2O is scattered in the 2M HCl aqueous solution of 25mL, stirs 10min under the nitrogen atmosphere, then adds 40mL 28% ammoniacal liquor, stirs 1h, Magnetic Isolation, and water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains ZnFe
2O
4Microballoon.
(2) ZnFe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water ultrasonic dispersion 10min, then add the 5mL catechol aqueous solution, stir 3h, Magnetic Isolation, and clean with ultra-pure water, in 50 ℃ of vacuum drying chamber oven dry, be transferred in the Muffle furnace, under the nitrogen atmosphere, 600 ℃ of heat treatment 5h, in 50 ℃ of vacuum drying chamber dryings, obtain ZnFe
2O
4/ C microballoon.
(3) ZnFe
2O
4/ C/ZrO
2The preparation of composite nano materials
The ZrOCl of 2mmol
28H
2O is scattered in the 8mL water, adds the ZnFe of 10mg
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the 0.2mL 2M NaOH aqueous solution, and ice-water bath stirs 4h.At last, the gained compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 230 ℃ of reaction 6h drop to room temperature, and water cleans, and obtains magnetic ZnFe
2O
4/ C/ZrO
2Composite nano materials.
Embodiment 13:
(1) ZnFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmolZn (NO
3)
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 220 ℃ of reaction 13h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain ZnFe
2O
4Microballoon.
(2) ZnFe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersion 10min adds the 5mL catechol aqueous solution, stirs 3h, Magnetic Isolation, and with the ultra-pure water cleaning, in 50 ℃ of vacuum drying chambers oven dry, be transferred in the Muffle furnace, the lower 800 ℃ of heat treatment 3h of nitrogen atmosphere obtain ZnFe
2O
4/ C microballoon.
(3) ZnFe
2O
4/ C/Zr
X 'Ti
Y 'O
2The preparation of composite nano materials
0.2 the ZrOCl of～1.8mmol
28H
2O and 1.8～0.2mmol butyl titanate are scattered in the 8mL ethanol, add the ZnFe of 10mg
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.1mM nitric acid, and ice-water bath stirs 2h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 200 ℃ of reaction 6h are down to room temperature, and water cleans, and obtains magnetic ZnFe
2O
4/ C/Zr
X 'Ti
Y 'O
2Composite nano materials, x ', y ' they are positive mark or natural number, the proportioning that is put to the test determines.
Embodiment 14:
(1) MnFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmol MnCl
24H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 12h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain MnFe
2O
4Microballoon.
(2) MnFe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL catechol aqueous solution, and stirred for several minute is transferred in the reactor, and 200 ℃ are reacted 16h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains MnFe
2O
4/ C microballoon.
(3) MnFe
2O
4/ C/SnO
2The preparation of composite nano materials
The SnCl of 1mmol
4Be scattered in 40mL ethanol, add the compound of 10mg experiment (2) preparation, ultrasonic 10min is transferred in the reactor, and 200 ℃ of reaction 20h are down to room temperature, clean with ethanol, and 50 ℃ of vacuum drying obtain MnFe
2O
4/ C/SnO
2Composite nano materials.
Embodiment 15:
(1) MnFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmolMnCl
24H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 17h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain MnFe
2O
4Microballoon.
(2) MnFe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersion 10min adds the 5mL catechol aqueous solution, stir 3h, Magnetic Isolation, and with the ultra-pure water cleaning, in 50 ℃ of vacuum drying chambers oven dry, be transferred in the Muffle furnace, the lower 700 ℃ of heat treatment 4h of nitrogen atmosphere are down to room temperature, obtain MnFe
2O
4/ C microballoon.
(3) MnFe
2O
4/ C/CeO
2The preparation of composite nano materials
With 1mmol Ce (NO
3)
46H
2O is dissolved in the 30mL ultra-pure water, adds the sample of preparation in the 10mg experiment (2), and ultrasonic 10min stirs 30min.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature continues to stir 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains MnFe
2O
4/ C/Ce (OH)
4Composite nano materials, last, sample is dry in 100 ℃ of baking ovens, obtain MnFe
2O
4/ C/CeO
2Composite nano materials.
Embodiment 16:
(1) Zn
X 'Co
1-x 'Fe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.2mmol FeCl
36H
2O, 0.01～0.09mmolCoCl
2, 0.09～0.01mmol Zn (NO
3)
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 230 ℃ of reaction 18h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Zn
X 'Co
1-x 'Fe
2O
4Microballoon.X ' is the positive number less than 1, and the proportioning that is put to the test determines.
(2) Zn
X 'Co
1-x 'Fe
2O
4The preparation of/C composite nano materials
The '-biphenyl diphenol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL '-biphenyl diphenol aqueous solution, and stirred for several minute is transferred in the reactor, and 160 ℃ are reacted 30h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains Zn
X 'Co
1-x 'Fe
2O
4/ C microballoon.
(3) Zn
X 'Co
1-x 'Fe
2O
4/ C/TiO
2The preparation of composite nano materials
1.5mmol butyl titanate be scattered in the 8mL ethanol, add the Zn of 10mg
xCo
1-xFe
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 5h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 220 ℃ of reaction 6h are down to room temperature, and water cleans, and obtains magnetic Zn
X 'Co
1-x 'Fe
2O
4/ C/TiO
2Composite nano materials.
Embodiment 17:
(1) Zn
X 'Co
1-x 'Fe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.2mmol FeCl
36H
2O, 0.01～0.09mmolCoCl
2, 0.09～0.01mmolZn (NO
3)
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 180 ℃ of reaction 16h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Zn
X 'Co
1-x 'Fe
2O
4Microballoon.X ' is the positive number less than 1, and the proportioning that is put to the test determines.
(2) Zn
X 'Co
1-x 'Fe
2O
4The preparation of/C composite nano materials
The hydroquinones aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL hydroquinones aqueous solution, and stirred for several minute is transferred in the reactor, and 160 ℃ are reacted 20h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains Zn
X 'Co
1-x 'Fe
2O
4/ C microballoon.
(3) Zn
X 'Co
1-x 'Fe
2O
4/ C/ZrO
2The preparation of composite nano materials
The ZrOCl of 2mmol
28H
2O is scattered in the 8mL water, adds the Zn of 10mg
xCo
1-xFe
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds 0.2mL 2M NaOH solution, and ice-water bath stirs 4h.At last, the gained compound is utilized Magnetic Isolation, the ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 180 ℃ of reaction 4h drop to room temperature, and water cleans, and obtains magnetic Zn
X 'Co
1-x 'Fe
2O
4/ C/ZrO
2Composite nano materials.
Embodiment 18:
(1) Zn
X 'Co
1-x 'Fe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.2mmol FeCl
36H
2O, 0.01～0.09mmolCoCl
2, 0.09～0.01mmolZn (NO
3)
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 220 ℃ of reaction 12h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Zn
X 'Co
1-x 'Fe
2O
4Microballoon.X ' is the positive number less than 1, and the proportioning that is put to the test determines.
(2) Zn
X 'Co
1-x 'Fe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 1mL catechol aqueous solution, and stirred for several minute is transferred in the reactor, and 180 ℃ are reacted 20h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains Zn
X 'Co
1-x 'Fe
2O
4/ C microballoon.
(3) Zn
X 'Co
1-x 'Fe
2O
4/ C/Zr
aTi
bO
2The preparation of composite nano materials
0.2 the ZrOCl of～1.8mmol
28H
2O and 1.8～0.2mmol butyl titanate are scattered in the 8mL ethanol, add the Zn of 10mg
X 'Co
1-x 'Fe
2O
4/ C nano particle, ultrasonic dispersion 10min, then stirring at room 1h places ice-water bath, dropwise adds the mixed solution (the ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.1mM nitric acid, and ice-water bath stirs 6h.At last, resulting compound is utilized Magnetic Isolation, ethanol cleans twice.The ethanol/water mixed solution cleans, and is scattered in the 30mL volume ratio and is in 1: 1 the ethanol/water solution, is transferred to reactor, and 200 ℃ of reaction 5h drop to room temperature, and water cleans, and obtains magnetic Zn
X 'Co
1-x 'Fe
2O
4/ C/Zr
aTi
bO
2Composite nano materials.A, b are positive mark or natural number, and the proportioning that is put to the test determines.
Embodiment 19:
(1) Zn
X 'Co
1-x 'Fe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.2mmol FeCl
36H
2O, 0.01～0.09mmolCoCl
2, 0.09～0.01mmol Zn (NO
3)
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 10h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Zn
X 'Co
1-x 'Fe
2O
4Microballoon.X ' is the positive number less than 1, and the proportioning that is put to the test determines.
(2) Zn
X 'Co
1-x 'Fe
2O
4The preparation of/C composite nano materials
The catechol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersion 10min adds the 10mL catechol aqueous solution, stir 3h, Magnetic Isolation, and with the ultra-pure water cleaning, in 50 ℃ of vacuum drying chambers oven dry, be transferred in the Muffle furnace, under the nitrogen atmosphere, 1000.℃ heat treatment 3h obtains Zn
X 'Co
1-x 'Fe
2O
4/ C microballoon.X ' is the positive number less than 1, and the proportioning that is put to the test determines.
(3) Zn
X 'Co
1-x 'Fe
2O
4/ C/SnO
2The preparation of composite nano materials
The SnCl of 2mmol
4Be scattered in 40mL ethanol, add the compound of 10mg experiment (2) preparation, ultrasonic 10min is transferred in the reactor, and 200 ℃ of reaction 12h are down to room temperature, clean with ethanol, and 50 ℃ of vacuum drying obtain Zn
xCo
1-xFe
2O
4/ C/SnO
2Composite nano materials.
Embodiment 20:
(1) Zn
X 'Co
1-x 'Fe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 0.2mmol FeCl
36H
2O, 0.01～0.09mmolCoCl
2, 0.09～0.01mmol Zn (NO
3)
26H
2O is stirred to dissolving, then mixed liquor is transferred in the reactor 200 ℃ of reaction 10h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain Zn
X 'Co
1-x 'Fe
2O
4Microballoon.X ' is the positive number less than 1, and the proportioning that is put to the test determines.
(2) Zn
X 'Co
1-x 'Fe
2O
4The preparation of/C composite nano materials
The resorcinol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL resorcinol aqueous solution, and stirred for several minute is transferred in the reactor, and 180 ℃ are reacted 36h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains Zn
X 'Co
1-x 'Fe
2O
4/ C microballoon.
(3) Zn
X 'Co
1-x 'Fe
2O
4/ C/CeO
2The preparation of composite nano materials
With 1mmol Ce (NO
3)
46H
2O is dissolved in the 30mL ultra-pure water, adds the sample of preparation in the 10mg experiment (2), and ultrasonic 10min stirs 1h.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature continues to stir 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains Zn
xCo
1-xFe
2O
4/ C/Ce (OH)
4Composite nano materials, last, sample is dry in 100 ℃ of baking ovens, obtain Zn
X 'Co
1-x 'Fe
2O
4/ C/CeO
2Composite nano materials.
Embodiment 21:
(1) Fe
3O
4The preparation of nano particle
The preparation of employing oxidation-precipitation method, compound concentration is the FeCl of 1g/L respectively
24H
2The NaOH aqueous solution of O and 2M.FeCl with 10mL
24H
2The O aqueous solution joins in the 50mL ultra-pure water, stirs the NaOH aqueous solution of the lower 2M of adding, regulates the pH value about 10, continues under the room temperature to stir until solution becomes black.Adopt Magnetic Isolation, and clean for several times with ultra-pure water, in 50 ℃ of vacuum drying chamber dryings, obtain Fe
3O
4Nano particle.
(2) Fe
3O
4The preparation of/C composite nano materials
Take by weighing the Fe that experiment (1) obtains
3O
420mg, the ultrasonic 0.02g/mL resorcinol aqueous solution that is scattered in 10mL stirs 1h, filters, and cleans three times 50 ℃ of vacuum drying with ethanol.Then, sample is transferred in the Muffle furnace, under the nitrogen atmosphere, 800 ℃ of heat treatment 3h obtain Fe
3O
4/ C microballoon.
(3) Fe
3O
4The preparation of/C/ZnO composite nano materials
Preparation 2mmol Zn (NO
3)
26H
2O aqueous solution 40mL, the Fe of adding 15mg
3O
4/ C nano particle, ultrasonic 10min is transferred in the reactor, and 200 ℃ of reaction 12h obtain Fe
3O
4/ C/ZnO composite nano materials.
Embodiment 22:
(1) CoFe
2O
4The preparation of microballoon
Employing solvent thermal process preparation takes by weighing 0.318g two hydration trisodium citrates and is scattered in the 30mL ethylene glycol, stirs 9 hours until dissolve, and then adds the 3.0g sodium acetate trihydrate, 2mmol FeCl
36H
2O, 1mmol CoCl
2, be stirred to dissolving, then mixed liquor is transferred in the reactor 230 ℃ of reaction 13h.Be cooled to room temperature, clean for several times with ethanol, water, in 50 ℃ of vacuum drying chamber dryings, obtain CoFe
2O
4Microballoon.
(2) CoFe
2O
4The preparation of/C composite nano materials
The '-biphenyl diphenol aqueous solution of preparation 0.04g/mL.Take by weighing the sample 20mg of experiment (1) preparation, be scattered in the 35mL water, then ultrasonic dispersions 10min adds the 5mL '-biphenyl diphenol aqueous solution, and stirred for several minute is transferred in the reactor, and 180 ℃ are reacted 30h.Be cooled to room temperature, water cleans for several times, in 50 ℃ of vacuum drying chamber dryings, obtains CoFe
2O
4/ C microballoon.
(3) CoFe
2O
4The preparation of/C/ZnO composite nano materials
Preparation 2.5mmol Zn (NO
3)
26H
2O aqueous solution 40mL, the CoFe of adding 12mg
2O
4/ C nano particle, ultrasonic 10min is transferred in the reactor, and 180 ℃ of reaction 16h obtain CoFe
2O
4/ C/ZnO composite nano materials.
More than all examples of implementation show through test, be the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
XComposite, core is MFe
2O
4Magnetic nano-particle, the intermediate layer is based on the carbon-coating that the carbonization of phenol organic molecule produces, thickness is 1～30nm, skin is metal oxide AO
X, thickness is 10～100nm.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that the above only is specific embodiments of the invention; be not limited to the present invention; all any modifications of making in principle scope of the present invention and improvement etc. all should be included within protection scope of the present invention.
Claims (8)
1. one kind is the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
XComposite, it is characterized in that core is MFe
2O
4Magnetic nano-particle, the intermediate layer is based on the carbon-coating that the carbonization of phenol organic molecule produces, thickness is 1～30nm, skin is metal oxide AO
X, thickness is 10～100nm; Wherein, magnetic nano-particle MFe
2O
4Middle M is the combination of a kind of or above two kinds of elements in Fe, Co, Mn, Ni, Zn, the Cu element; Metal oxide AOX is TiO
2, SnO
2, ZrO
2, ZnO or CeO
2In a kind of, or the combination of above two or more metal oxide, X is positive integer.
2. one kind is the magnetic MFe of carbon source based on the phenol organic molecule
2O
4/ C/AO
xThe preparation method of compound is characterized in that step is followed successively by:
The first step takes by weighing 0.3～1.0g, two hydration trisodium citrates and is scattered in 25～35mL ethylene glycol, stirs 8～10 hours until dissolve, and then adds the 1.5-3.0g sodium acetate trihydrate, 2.5～3.5mmol MCl
Y, wherein, M is Fe, Co, and Mn, Ni, Zn, one or more among the Cu, Y is positive integer, is stirred to dissolving, then mixed liquor is transferred in the reactor 200～230 ℃ of reaction 10～20h, preparation magnetic nano-particle;
Second step, with the ultrasonic 10～30min of magnetic nano-particle that obtains, be dispersed in water, add a certain amount of phenol organic molecule aqueous solution, at this moment, the mass concentration of magnetic nano-particle is 0.1～5mg/mL, and the mass ratio of magnetic nano-particle and phenol organic molecule is 1: 1～1: 20; Then, stirred for several minute shifts mixed solution to reactor, 160～200 ℃, reaction 10～36h naturally cools to room temperature, perhaps with the mixed solution Magnetic Isolation, ultra-pure water cleans, vacuum drying, then sample is transferred in the Muffle furnace, calcines under the inert gas, inert gas comprises nitrogen, argon gas, one or both mists in the helium, calcination temperature range is at 500～1000 ℃, and under this temperature, keep 3-5h, prepare magnetic MFe
2O
4/ C compound;
In the 3rd step, the ethanolic solution 7～9mL of preparation 0.5～3mmol slaine, slaine are the ester salt of titanium, zirconium, tin, cerium or hydrochloride is a kind of or more than one, add the MFe of 9～11mg
2O
4/ C nano particle, ultrasonic dispersion 8～12min, stirring at room 0.8～1.2h, then place under ice-water bath or the room temperature, 1) or 1.8～2.2M NaOH aqueous solution (the ethanol/water volume ratio is 4～6: dropwise to add the mixed solution of the ethanol/water of 2mL 0～0.5mM nitric acid, stir 2～24h, at last, the compound that obtains is utilized Magnetic Isolation, clean, be scattered in 25～35mL volume ratio and be in 0.8～1.2: 1 the ethanol/water solution, be transferred to reactor, 160～230 ℃ of reaction 3～10h drop to room temperature, water cleans, and obtains crystallinity magnetic MFe
2O
4/ C/AO
XComposite nano materials, metal oxide AO
XTiO
2, SnO
2, ZrO
2, ZnO or CeO
2In a kind of, or the combination of above two or more metal oxide, X is positive integer.
3. preparation method according to claim 2 is characterized in that described magnetic nano-particle also comprises γ-Fe
2O
3, the described step first step, the source of metallic element M is one or more in its oxide, chloride, bromide, nitrate, sulfate, the carbonate in the precursor salt.
4. preparation method according to claim 2 is characterized in that the magnetic nano-particle preparation is not limited to the hydrothermal/solvent by the use of thermal means in the described step first step, also comprises chemical coprecipitation method, ball-milling method or oxidation-precipitation method.
5. preparation method according to claim 2 is characterized in that described phenol organic molecule is phenol, catechol, hydroquinones, resorcinol, '-biphenyl diphenol and derive hexatomic ring or other heterocyclic organic molecules with hydroxyl, carboxyl, ketone group.
6. preparation method according to claim 2 is characterized in that described step second step, and in hydrothermal treatment consists carbonization experimental technique, the mass ratio of described magnetic nano-particle and phenol organic molecule is 1: 10, and reaction temperature is 180 ℃.
7. preparation method according to claim 2 is characterized in that described metal oxide AO
XThe metallic element precursor be in its fluoride, chloride, bromide, sulfate, nitrate, acetate, oxide, isopropoxide and the ester salt thereof one or more.
8. preparation method according to claim 2 is characterized in that the preparation method of metal oxide in described the 3rd step is not limited to the hydrothermal/solvent by the use of thermal means, also comprises collosol and gel-hydrothermal method or sol-gel process.
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