CN103055771B - Be the magnetic MFe of carbon source based on phenol organic molecule 2o 4/ C/AO xcomposite and preparation method thereof - Google Patents

Be the magnetic MFe of carbon source based on phenol organic molecule 2o 4/ C/AO xcomposite and preparation method thereof Download PDF

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CN103055771B
CN103055771B CN201110334606.5A CN201110334606A CN103055771B CN 103055771 B CN103055771 B CN 103055771B CN 201110334606 A CN201110334606 A CN 201110334606A CN 103055771 B CN103055771 B CN 103055771B
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CN103055771A (en
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赵新梅
吴爱国
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

A kind of is the magnetic MFe of carbon source based on phenol organic molecule 2o 4/ C/AO xcompound and preparation method thereof, is characterized in that step is followed successively by: the first step, prepares magnetic nano-particle MFe 2o 4; Second step, prepares magnetic MFe 2o 4/ C compound; 3rd step, preparation crystallinity magnetic MFe 2o 4/ C/AO xcomposite nano materials, MFe 2o 4middle M is Fe, Co, Mn, Ni, Zn, Cu element, or the combination of above two kinds of elements; Described metal oxide AO xtiO 2, SnO 2, ZrO 2, ZnO, CeO 2, or the combination of two or more metal oxide above; Negative electrical charge on the surface band that it can make magnetic nano-particle, not by chemical degradation under practical service environment, carries out Magnetic Isolation after being convenient to materials'use, recycles, and improves the catalytic activity of magnetic metal oxide.

Description

Be the magnetic MFe of carbon source based on phenol organic molecule 2o 4/ C/AO xcomposite and preparation method thereof
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
Ferrite nano structural material because of its extensive use in the numerous areas such as data storage, catalysis, sensor, pollutant process and biological medicine, and causes people more and more to pay close attention to.But the surface functional groups of ferrite nano structural material is fewer, for increase surface can be handling, avoid magnetic ferric oxide nano particles by chemical degradation or gathering in application process, be necessary very much at its surface coverage one deck organic or inorganic shell.Application number be 200910218934.1 patent discloses a kind of method of synthesizing polymethylacrylic acid magnetic composite microsphere.Application number be 201010207481.5 patent also disclose and a kind of realize magnetic ferrites-dendritic polyamide core-shell nano complex by chemical conjugation methods.
The more inorganic shell of usual use is SiO 2and C.Application number be 200610116026.8 patent provide a kind of preparation method of magnetic Nano silicon ball, this patent utilization SiO 2coated Fe 3o 4nano particle, and load TiO 2photocatalyst material is applied to water purification and process aspect.Shandong University's professor's Yin Longwei group is by SiO 2be coated on magnetic nano-particle γ-Fe 2o 3surface, then composite Ti O 2, prepared magnetic hybrid nano material, research shows, 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 prepares inorganic oxide composite nano materials, such as: many seminar report ZrO 2composite magnetic (the Preparation of Fe of shell 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-dimensional hexagonal structure, build other dimension carbonaceous material, as elementary cell (the Electric Field Effect in Atomically Thin Carbon Films of 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).Due to 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, 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).In lithium battery applications, TiO 2@TiO xn y/ TiN-GS hybrid material, compared with independent titanic oxide material, facilitates electronics transport, 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 to prepare the coated titanium dioxide nano material of graphene-like carbon for carbon source, and research shows, this material has catalytic capability (Efficient TiO more better than business-like P25 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 magnetic nano particle sub-surface, carry out the modification of metal nanoparticle, be expected to the catalytic activity greatly improving carbon source clad composite material.Generally everybody carbon source material used is glucose, and this patent proposes one and utilizes phenol organic molecule for carbon source material, carries out the method that magnetic nano-particle is coated.Utilize this material to carry out carbonization coated: hydroxyl, the carbonyl of negative electrical charge on the surface band that 1) can make magnetic nano-particle, be convenient to the absorption of metal cation, depositing metal oxide; 2) can available protecting magnetic nano-particle not oxidized; 3), after carbon-coating protection, material can maintain good magnetic; 4) the six-membered cyclic class graphene-structured of carbon-coating, can promote that electronics transports, and 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 synthesis high catalytic activity provides platform, in Magnetic Isolation, water treatment, medical imaging and drug delivery, biology sensor, solar cell etc., have important using value.
Summary of the invention
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 phenol organic molecule 2o 4/ C/AO xcomposite, it has middle carbon-coating, can protect magnetic nano-particle, thus has good performance.
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 phenol organic molecule 2o 4/ C/AO xthe preparation method of composite.
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 phenol organic molecule 2o 4/ C/AO xcomposite, it is characterized in that core is MFe 2o 4magnetic nano-particle, intermediate layer be based on the carbonization of phenol organic molecule produce carbon-coating, thickness is 1-30nm, and 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, Cu element; Wherein metal oxide AO xtiO 2, SnO 2, ZrO 2, ZnO or CeO 2in one, or the combination of two or more metal oxide above, 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 phenol organic molecule 2o 4/ C/AO xthe preparation method of composite, it is characterized in that step is followed successively by:
The first step, takes 0.3-1.0g bis-citric acid monohydrate trisodium and is scattered in 25 ~ 35mL ethylene glycol, stirs 8 ~ 10 hours until dissolve, then adds 1.5-3.0g sodium acetate trihydrate, 2.5 ~ 3.5mmol MCl y, wherein, M is one or more in Fe, Co, Mn, Ni, Zn, Cu, and Y is positive integer, is stirred to dissolving, then transfers in reactor by mixed liquor, and 200-230 DEG C of reaction 10-20h, prepares magnetic nano-particle;
Second step, by the ultrasonic 10 ~ 30min of magnetic nano-particle obtained, be dispersed in water, add a certain amount of phenol organic molecule aqueous solution, now, 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, transfer mixed solution is in reactor, 160 ~ 200 DEG C, reaction 10 ~ 36h, naturally cools to room temperature, or mixed solution is stirred 0.5-5h, Magnetic Isolation, ultra-pure water cleans, vacuum drying, is then transferred in Muffle furnace by sample, calcines under inert gas, inert gas comprises nitrogen, argon gas, one or both mists in helium, calcination temperature range at 500 ~ 1000 DEG C, and maintains 3 ~ 5h at such a temperature, prepares magnetic MFe 2o 4/ C compound;
3rd step, the ethanol of preparation 0.5 ~ 3mmol slaine or the aqueous solution 7 ~ 9mL, slaine comprises titanium, zirconium, tin, the ester salt of cerium or hydrochloride one or more than one, adds the MFe of 9 ~ 1lmg 2o 4/ C nano particle, ultrasonic disperse 8 ~ 12min, stirring at room temperature 0.8 ~ 1.2h, under being then placed in ice-water bath or room temperature, dropwise add mixed solution (ethanol/water volume ratio is 4 ~ 6: 1) or 1.8 ~ 2.2M NaOH aqueous solution of the ethanol/water of 2mL 0-0.5mM nitric acid, stir 2-24h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge, the cleaning of ethanol/water mixed solution or ultra-pure water cleaning, being scattered in 25 ~ 35mL volume ratio is in the ethanol/water solution of 0.8 ~ 1.2: 1, is transferred to reactor, 160 ~ 230 DEG C of reaction 3 ~ 10h, drop to room temperature, with water cleaning, obtain crystallinity magnetic MFe 2o 4/ C/AO xcomposite nano materials.
In such scheme,
Magnetic nano-particle also comprises γ-Fe 2o 3.The source of described metallic element can be one or more in its oxide, chloride, bromide, nitrate, sulfate, carbonate.
In described magnetic nano-particle synthetic method, be not limited to hydrothermal/solvent by the use of thermal means, also comprise chemical coprecipitation method or oxidation-precipitation method.Wherein:
Chemical coprecipitation method: take 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, then add 30 ~ 50mL 28% ammoniacal liquor under nitrogen atmosphere, stirs 0.5 ~ 1.5h, Magnetic Isolation, with water cleaning several, in 50 DEG C 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.By the FeCl of 8 ~ 12mL 24H 2the O aqueous solution joins in 52 ~ 48mL ultra-pure water, adds the NaOH aqueous solution of 1.6 ~ 2.4M under stirring, and adjust ph is about 10, and room temperature with constant stirs until solution becomes black.Adopt Magnetic Isolation, and with ultra-pure water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Fe 3o 4nano particle.
Described phenol organic molecule can be phenol, catechol, hydroquinones, resorcinol, '-biphenyl diphenol and derivative hexatomic ring thereof or other heterocyclic organic molecules with hydroxyl, carboxyl, ketone group.
Described magnetic MFe 2o 4in/C compound synthetic method, can be method for calcinating under inert gas, also can adopt hydro-thermal treatment method.When adopting inert gas method for calcinating, inert gas comprises nitrogen, argon gas, one or both mists in helium.Calcination temperature range at 500 ~ 1000 DEG C, and maintains 3 ~ 5h at such a temperature.In hydrothermal treatment consists carbonization experimental technique, the mass ratio of phenol organic molecule and magnetic nano-particle is regulated to range preferably from 10 times; Temperature is preferably 180 DEG C, and maintains 10 ~ 36h at such a temperature.
Described metal oxide AO xcan be TiO 2, SnO 2, ZrO 2, ZnO, CeO 2, or the combination of two or more metal oxide above.The precursor of described metal oxide is its fluoride, chloride, bromide, sulfate, nitrate, acetate, oxide, one or more in isopropoxide and 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: the ethanol of preparation 0.5 ~ 3mmol slaine or the aqueous solution 5 ~ 40mL, slaine comprises titanium, zirconium, tin, the ester salt of cerium or hydrochloride one or more than one, adds the MFe of 9 ~ 15mg 2o 4/ C nano particle, ultrasonic disperse 8 ~ 12min, stirring at room temperature 0.8 ~ 1.2h, dropwise add the NaOH aqueous solution of 0.1 ~ 20mL, 0.1 ~ 0.5M, stirs 2 ~ 24h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge, the cleaning of ethanol/water mixed solution or ultra-pure water cleaning, 40 ~ 150 DEG C of vacuum drying, obtain magnetic MFe 2o 4/ C/AO xcomposite nano materials.
Hydrothermal/solvent by the use of thermal means: the ethanol of preparation 0.5 ~ 3mmol slaine and water (ethanol/water volume ratio is 5: 0.01 ~ 0.01: 5) mixed solution 30 ~ 50mL, add the MFe of 9 ~ 15mg 2o 4/ C nano particle, ultrasonic 8 ~ 12min, is transferred in reactor, and 160 ~ 200 DEG C of reaction 10 ~ 20h, obtain MFe 2o 4/ C/AO xcomposite nano materials.
Compared with prior art, the invention has the advantages that:
Negative electrical charge on the surface band that 1, can make magnetic nano-particle, as: hydroxyl, carbonyl, be convenient to the absorption of metal cation, depositing metal oxide;
2, can available protecting magnetic nano-particle, not oxidized in the pyroprocess of coated metal oxide; Not by chemical degradation under practical service environment;
3, after carbon-coating protection, material can maintain good magnetic, carries out Magnetic Isolation after being convenient to materials'use, recycles;
4, the six-membered cyclic class graphene-structured of carbon-coating, can promote that electronics transports, this material has potential using value in environmental improvement.
Accompanying drawing explanation
A) and b) Fe respectively in Fig. 1 3o 4sEM figure and the EDS energy spectrogram of/C composite nano materials;
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.
Detailed description of the invention
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 any restriction effect is not play to it.
Embodiment 1:
(1) Fe 3o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.3g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 0.819g FeCl 36H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 200 DEG C of reaction 10h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 Fe prepared by experiment (1) 3o 420mmg, is scattered in 35mL water, ultrasonic disperse 10min, then adds the 5mL catechol aqueous solution, stirred for several minute, is transferred in reactor, 180 DEG C of reaction 16h.Be cooled to room temperature, with water cleaning several, in 60 DEG C of vacuum drying chamber dryings, obtain 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 8mL ethanol, adds the Fe of 10mg 3o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 2h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 180 DEG C of reaction 4h, drop to room temperature, with water cleaning, obtain magnetic Fe 3o 4/ C/TiO 2composite nano materials.
Embodiment 2:
(1) Fe 3o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 1.0g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 0.819g FeCl 36H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 230 DEG C of reaction 12h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 Fe prepared by experiment (1) 3o 48mg, is scattered in 37mL water, ultrasonic disperse 10min, then adds the 3mL catechol aqueous solution, stirred for several minute, is transferred in reactor, 200 DEG C of reaction 16h.Be cooled to room temperature, with water cleaning several, in 60 DEG C of vacuum drying chamber dryings, obtain 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 8mL ethanol, adds the Fe of 10mg 3o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, then at room temperature, dropwise add the mixed solution (ethanol/water volume ratio is 5: 1) of 2mL ethanol/water, stirs 16h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 230 DEG C of reaction 10h, drop to room temperature, with water cleaning, obtain magnetic Fe 3o 4/ C/ZrO 2composite nano materials.
Embodiment 3:
(1) Fe 3o 4the preparation of nano particle
Prepared by employing chemical coprecipitation method, take 1.5mmol FeCl 2with 3mmol FeCl 36H 2o is scattered in the 2M HCl aqueous solution of 25mL, stirs 10min under nitrogen atmosphere, then adds 40mL 28% ammoniacal liquor, stirs 1h, Magnetic Isolation, with water cleaning several, in 50 DEG C 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 Fe prepared by experiment (1) 3o 410mg, is scattered in 36mL water, ultrasonic disperse 10min, then adds the 4mL hydroquinones aqueous solution, stirred for several minute, is transferred in reactor, 200 DEG C of reaction 26h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Fe 3o 4/ C microballoon.
(3) Fe 3o 4/ C/Zr x 'ti y 'o 2the preparation of composite nano materials
The ZrOCl of 0.2 ~ 1.8mmol 28H 2o and 1.8 ~ 0.2mmol butyl titanate are scattered in 8mL ethanol, add the Fe of 10mg 3o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 2h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 220 DEG C of reaction 6h, drop to room temperature, with water cleaning, obtain magnetic Fe 3o 4/ C/Zr x 'ti y 'o 2composite nano materials, x ', y ' are positive mark or natural number, and the proportioning that is put to the test determines.
Embodiment 4:
(1) Fe 3o 4the preparation of nano particle
Prepared by employing oxidation-precipitation method, compound concentration is the FeCl of 1g/L respectively 24H 2the NaOH aqueous solution of O and 2M.By the FeCl of 10mL 24H 2the O aqueous solution joins in 50mL ultra-pure water, adds the NaOH aqueous solution of 2M under stirring, and adjust ph is about 10, and room temperature with constant stirs until solution becomes black.Adopt Magnetic Isolation, and with ultra-pure water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Fe 3o 4nano particle.
(2) Fe 3o 4the preparation of/C composite nano materials
Take the Fe that experiment (1) obtains 3o 420mg, ultrasonic disperse, in the 0.02g/mL resorcinol aqueous solution of 10mL, stirs 1h, filters, and with ethanol purge three times, 50 DEG C of vacuum drying.Then, be transferred to by sample in Muffle furnace, under nitrogen atmosphere, 800 DEG C 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, adds the Fe of 15mg 3o 4/ C nano particle, ultrasonic 10min, is transferred in reactor, and 200 DEG C of reaction 18h, obtain Fe 3o 4/ C/SnO 2composite nano materials.
Embodiment 5:
(1) Fe 3o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 1.0g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 1.5g sodium acetate trihydrate, 0.819g FeCl 36H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 220 DEG C of reaction 12h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Fe 3o 4microballoon.
(2) Fe 3o 4the preparation of/C composite nano materials
Take the Fe that experiment (1) obtains 3o 420mg, is scattered in 30mL water, ultrasonic 15min, adds the 0.02g/mL '-biphenyl diphenol aqueous solution of 10mL, stirs 1h, Magnetic Isolation, and cleans three times with ultra-pure water, 50 DEG C of vacuum drying.Then, be transferred to by sample in Muffle furnace, under nitrogen atmosphere, 500 DEG C of heat treatment 5h, obtain Fe 3o 4/ C microballoon.
(3) Fe 3o 4/ C/CeO 2the preparation of composite nano materials
By 1mmol Ce (NO 3) 46H 2o is dissolved in 30mL ultra-pure water, adds the sample of preparation in 10mg experiment (2), ultrasonic 10min, stirs 1h.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature Keep agitation 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains Fe 3o 4/ C/Ce (OH) 4composite nano materials, finally, sample is dry in 100 DEG C of baking ovens, obtain Fe 3o 4/ C/CeO 2composite nano materials.
Embodiment 6:
(1) CoFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.6g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmol CoCl 2, be stirred to dissolving, then mixed liquor transferred in reactor, 220 DEG C of reaction 15h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL '-biphenyl diphenol aqueous solution, stirred for several minute, be transferred in reactor, 160 DEG C of reaction 36h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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 8mL ethanol, adds the CoFe of 10mg 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, then at room temperature, dropwise add the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, stirs 20h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice, 50 DEG C of vacuum drying chamber dryings, obtain magnetic CoFe 2o 4/ C/TiO 2composite nano materials.
Embodiment 7:
(1) NiFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmolNiCl 26H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 230 DEG C of reaction 16h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL hydroquinones aqueous solution, stir 3h, Magnetic Isolation, and with ultra-pure water cleaning, dry in 50 DEG C of vacuum drying chambers, be transferred in Muffle furnace, under nitrogen atmosphere, 1000 DEG C 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 8mL water, adds the NiFe of 10mg 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, dropwise add the 0.2mL 2M NaOH aqueous solution, stirs 20h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 200 DEG C of reaction 10h, drop to room temperature, with water cleaning, obtain magnetic NiFe 2o 4/ C/ZrO 2composite nano materials.
Embodiment 8:
(1) CuFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mmL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, lmmol CuCl 2, be stirred to dissolving, then mixed liquor transferred in reactor, 210 DEG C of reaction 16h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL resorcinol aqueous solution, stirred for several minute, be transferred in reactor, 160 DEG C of reaction 36h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain CuFe 2o 4/ C microballoon.
3) CuFe 2o 4/ C/Zr x 'ti y 'o 2the preparation of composite nano materials
The ZrOCl of 0.1 ~ 2.9mmol 28H 2o and 2.9 ~ 0.1mmol butyl titanate are scattered in 8mL ethanol, add the CuFe of 10mg 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.2mM nitric acid, and ice-water bath stirs 2h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 220 DEG C of reaction 7h, drop to room temperature, with water cleaning, obtain magnetic CuFe 2o 4/ C/Zr x 'ti y 'o 2composite nano materials, x ', y ' are positive mark or natural number, and the proportioning that is put to the test determines.
Embodiment 9:
(1) CoFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmol CoCl 2, be stirred to dissolving, then mixed liquor transferred in reactor, 230 DEG C of reaction 13h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL '-biphenyl diphenol aqueous solution, stirred for several minute, be transferred in reactor, 180 DEG C of reaction 24h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain CoFe 2o 4/ C microballoon.
(3) CoFe 2o 4/ C/SnO 2the preparation of composite nano materials
Preparation 2.5mmol SnCl 4ethanolic solution 40mL, adds the CoFe of 12mg 2o 4/ C nano particle, ultrasonic 10min, is transferred in reactor, and 180 DEG C of reaction 16h, obtain CoFe 2o 4/ C/SnO 2composite nano materials.
Embodiment 10:
(1) CuFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmol CuCl 2, be stirred to dissolving, then mixed liquor transferred in reactor, 200 DEG C of reaction 10h.Be cooled to room temperature, with ethanol, water cleaning several, dry in 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL catechol aqueous solution, stirred for several minute, be transferred in reactor, 180 DEG C of reaction 36h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain CuFe 2o 4/ C microballoon.
(3) CuFe 2o 4/ C/CeO 2the preparation of composite nano materials
By 1mmol Ce (NO 3) 46H 2o is dissolved in 30mL ultra-pure water, adds the sample of preparation in 10mg experiment (2), ultrasonic 10min, stirs 1h.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature Keep agitation 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains CuFe 2o 4/ C/Ce (OH) 4composite nano materials, finally, sample is dry in 100 DEG C of baking ovens, obtain CuFe 2o 4/ C/CeO 2composite nano materials.
Embodiment 11:
(1) NiFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmol NiCl 26H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 200 DEG C of reaction 15h.Be cooled to room temperature, with ethanol, water cleaning several, in 70 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL catechol aqueous solution, stirred for several minute, be transferred in reactor, 160 DEG C of reaction 36h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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 7.9mL ethanol, adds the NiFe of 10mg 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 10h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 230 DEG C of reaction 6h, are down to room temperature, with water cleaning, obtain magnetic NiFe 2o 4/ C/TiO 2composite nano materials.
Embodiment 12:
(1) ZnFe 2o 4the preparation of microballoon
Take 1.5mmol ZnCl 2with 3mmol FeCl 36H 2o is scattered in the 2M HCl aqueous solution of 25mL, stirs 10min under nitrogen atmosphere, then adds 40mL 28% ammoniacal liquor, stirs 1h, Magnetic Isolation, with water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then the 5mL catechol aqueous solution is added, stir 3h, Magnetic Isolation, and clean with ultra-pure water, dry in 50 DEG C of vacuum drying chambers, be transferred in Muffle furnace, under nitrogen atmosphere, 600 DEG C of heat treatment 5h, in 50 DEG C 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 8mL water, adds the ZnFe of 10mg 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the 0.2mL 2M NaOH aqueous solution, and ice-water bath stirs 4h.Finally, gained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 230 DEG C of reaction 6h, drop to room temperature, with water cleaning, obtain magnetic ZnFe 2o 4/ C/ZrO 2composite nano materials.
Embodiment 13:
(1) ZnFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmolZn (NO 3) 26H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 220 DEG C of reaction 13h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then adds the 5mL catechol aqueous solution, stirs 3h, Magnetic Isolation, and with ultra-pure water cleaning, dry in 50 DEG C of vacuum drying chambers, be transferred in Muffle furnace, the lower 800 DEG C 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
The ZrOCl of 0.2 ~ 1.8mmol 28H 2o and 1.8 ~ 0.2mmol butyl titanate are scattered in 8mL ethanol, add the ZnFe of 10mg 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.1mM nitric acid, and ice-water bath stirs 2h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 200 DEG C of reaction 6h, are down to room temperature, with water cleaning, obtain magnetic ZnFe 2o 4/ C/Zr x 'ti y 'o 2composite nano materials, x ', y ' are positive mark or natural number, and the proportioning that is put to the test determines.
Embodiment 14:
(1) MnFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmol MnCl 24H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 200 DEG C of reaction 12h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL catechol aqueous solution, stirred for several minute, be transferred in reactor, 200 DEG C of reaction 16h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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 compound prepared by 10mg experiment (2), ultrasonic 10min, is transferred in reactor, and 200 DEG C of reaction 20h, are down to room temperature, and with ethanol purge, 50 DEG C of vacuum drying, obtain MnFe 2o 4/ C/SnO 2composite nano materials.
Embodiment 15:
(1) MnFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmolMnCl 24H 2o, is stirred to dissolving, then transfers in reactor by mixed liquor, 200 DEG C of reaction 17h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL catechol aqueous solution, stir 3h, Magnetic Isolation, and with ultra-pure water cleaning, dry in 50 DEG C of vacuum drying chambers, be transferred in Muffle furnace, the lower 700 DEG C 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
By 1mmol Ce (NO 3) 46H 2o is dissolved in 30mL ultra-pure water, adds the sample of preparation in 10mg experiment (2), ultrasonic 10min, stirs 30min.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature Keep agitation 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains MnFe 2o 4/ C/Ce (OH) 4composite nano materials, finally, sample is dry in 100 DEG C 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
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 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 transfers in reactor by mixed liquor, 230 DEG C of reaction 18h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Zn x 'co 1-x 'fe 2o 4microballoon.The positive number of x ' for being less than 1, 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL '-biphenyl diphenol aqueous solution, stirred for several minute, be transferred in reactor, 160 DEG C of reaction 30h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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
The butyl titanate of 1.5mmol is scattered in 8mL ethanol, adds the Zn of 10mg xco 1-xfe 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.5mM nitric acid, and ice-water bath stirs 5h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 220 DEG C of reaction 6h, are down to room temperature, with water cleaning, obtain 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
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 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 transfers in reactor by mixed liquor, 180 DEG C of reaction 16h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Zn x 'co 1-x 'fe 2o 4microballoon.The positive number of x ' for being less than 1, 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL hydroquinones aqueous solution, stirred for several minute, be transferred in reactor, 160 DEG C of reaction 20h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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 8mL water, adds the Zn of 10mg xco 1-xfe 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds 0.2mL 2M NaOH solution, and ice-water bath stirs 4h.Finally, gained compound is utilized Magnetic Isolation, ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 180 DEG C of reaction 4h, drop to room temperature, with water cleaning, obtain 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
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 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 transfers in reactor by mixed liquor, 220 DEG C of reaction 12h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Zn x 'co 1-x 'fe 2o 4microballoon.The positive number of x ' for being less than 1, 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 1mL catechol aqueous solution, stirred for several minute, be transferred in reactor, 180 DEG C of reaction 20h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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
The ZrOCl of 0.2 ~ 1.8mmol 28H 2o and 1.8 ~ 0.2mmol butyl titanate are scattered in 8mL ethanol, add the Zn of 10mg x 'co 1-x 'fe 2o 4/ C nano particle, ultrasonic disperse 10min, stirring at room temperature 1h, be then placed in ice-water bath, dropwise adds the mixed solution (ethanol/water volume ratio is 5: 1) of the ethanol/water of 2mL 0.1mM nitric acid, and ice-water bath stirs 6h.Finally, obtained compound is utilized Magnetic Isolation, ethanol purge twice.Ethanol/water mixed solution cleans, and being scattered in 30mL volume ratio is in the ethanol/water solution of 1: 1, is transferred to reactor, and 200 DEG C of reaction 5h, drop to room temperature, with water cleaning, obtain 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
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 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 transfers in reactor by mixed liquor, 200 DEG C of reaction 10h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Zn x 'co 1-x 'fe 2o 4microballoon.The positive number of x ' for being less than 1, 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 10mL catechol aqueous solution, stir 3h, Magnetic Isolation, and with ultra-pure water cleaning, dry in 50 DEG C of vacuum drying chambers, be transferred in Muffle furnace, under nitrogen atmosphere, 1000.DEG C heat treatment 3h, obtains Zn x 'co 1-x 'fe 2o 4/ C microballoon.The positive number of x ' for being less than 1, 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 compound prepared by 10mg experiment (2), ultrasonic 10min, is transferred in reactor, and 200 DEG C of reaction 12h, are down to room temperature, and with ethanol purge, 50 DEG C 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
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 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 transfers in reactor by mixed liquor, 200 DEG C of reaction 10h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Zn x 'co 1-x 'fe 2o 4microballoon.The positive number of x ' for being less than 1, 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL resorcinol aqueous solution, stirred for several minute, be transferred in reactor, 180 DEG C of reaction 36h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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
By 1mmol Ce (NO 3) 46H 2o is dissolved in 30mL ultra-pure water, adds the sample of preparation in 10mg experiment (2), ultrasonic 10min, stirs 1h.Then, dropwise add the NaOH aqueous solution of 10mL 0.3M, room temperature Keep agitation 4h.Adopt Magnetic Isolation, ultra-pure water cleans, and obtains Zn xco 1-xfe 2o 4/ C/Ce (OH) 4composite nano materials, finally, sample is dry in 100 DEG C 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
Prepared by employing oxidation-precipitation method, compound concentration is the FeCl of 1g/L respectively 24H 2the NaOH aqueous solution of O and 2M.By the FeCl of 10mL 24H 2the O aqueous solution joins in 50mL ultra-pure water, adds the NaOH aqueous solution of 2M under stirring, and adjust ph is about 10, and room temperature with constant stirs until solution becomes black.Adopt Magnetic Isolation, and with ultra-pure water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain Fe 3o 4nano particle.
(2) Fe 3o 4the preparation of/C composite nano materials
Take the Fe that experiment (1) obtains 3o 420mg, ultrasonic disperse, in the 0.02g/mL resorcinol aqueous solution of 10mL, stirs 1h, filters, and with ethanol purge three times, 50 DEG C of vacuum drying.Then, be transferred to by sample in Muffle furnace, under nitrogen atmosphere, 800 DEG C 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, adds the Fe of 15mg 3o 4/ C nano particle, ultrasonic 10min, is transferred in reactor, and 200 DEG C of reaction 12h, obtain Fe 3o 4/ C/ZnO composite nano materials.
Embodiment 22:
(1) CoFe 2o 4the preparation of microballoon
Prepared by employing solvent thermal process, take 0.318g bis-citric acid monohydrate trisodium and be scattered in 30mL ethylene glycol, stir 9 hours until dissolve, then add 3.0g sodium acetate trihydrate, 2mmol FeCl 36H 2o, 1mmol CoCl 2, be stirred to dissolving, then mixed liquor transferred in reactor, 230 DEG C of reaction 13h.Be cooled to room temperature, with ethanol, water cleaning several, in 50 DEG C 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 sample 20mg prepared by experiment (1), be scattered in 35mL water, ultrasonic disperse 10min, then add the 5mL '-biphenyl diphenol aqueous solution, stirred for several minute, be transferred in reactor, 180 DEG C of reaction 30h.Be cooled to room temperature, with water cleaning several, in 50 DEG C of vacuum drying chamber dryings, obtain 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, adds the CoFe of 12mg 2o 4/ C nano particle, ultrasonic 10min, is transferred in reactor, and 180 DEG C of reaction 16h, obtain CoFe 2o 4/ C/ZnO composite nano materials.
All examples of implementation show through test above, are the magnetic MFe of carbon source based on phenol organic molecule 2o 4/ C/AO xcomposite, core is MFe 2o 4magnetic nano-particle, intermediate layer be based on the carbonization of phenol organic molecule produce carbon-coating, thickness is 1 ~ 30nm, and 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 and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any amendments and improvement etc. made in spirit of the present invention, all should be included within protection scope of the present invention.

Claims (3)

1. one kind is the magnetic MFe of carbon source based on phenol organic molecule 2o 4/ C/AO xthe preparation method of compound, the core of this compound is MFe 2o 4magnetic nano-particle, intermediate layer be based on the carbonization of phenol organic molecule produce carbon-coating, thickness is 1 ~ 30nm, and 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, Cu element; Metal oxide AO xtiO 2, SnO 2, ZrO 2, ZnO or CeO 2in one or more combination, X is positive integer, it is characterized in that step is followed successively by:
The first step, takes 0.3 ~ 1.0g bis-citric acid monohydrate trisodium and is scattered in 25 ~ 35mL ethylene glycol, stirs 8 ~ 10 hours until dissolve, then adds 1.5-3.0g sodium acetate trihydrate, 2.5 ~ 3.5mmol MCl y, wherein, M is one or more in Fe, Co, Mn, Ni, Zn, Cu, and Y is positive integer, is stirred to dissolving, then transfers in reactor by mixed liquor, and 200 ~ 230 DEG C of reaction 10 ~ 20h, prepare magnetic nano-particle;
Second step, by the ultrasonic 10 ~ 30min of magnetic nano-particle obtained, be dispersed in water, add a certain amount of phenol organic molecule aqueous solution, now, 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, transfer mixed solution is in reactor, and 160 ~ 200 DEG C, reaction 10 ~ 36h, naturally cools to room temperature, prepare magnetic MFe 2o 4/ C compound;
Or by the ultrasonic 10 ~ 30min of magnetic nano-particle obtained, be dispersed in water, add a certain amount of phenol organic molecule aqueous solution, now, the mass concentration of magnetic nano-particle is 0.1 ~ 5mg/mL, the mass ratio of magnetic nano-particle and phenol organic molecule is 1: 1 ~ 1: 20, stir 1 hour or 3 hours, by mixed solution Magnetic Isolation, ultra-pure water cleans, vacuum drying, then sample is transferred in Muffle furnace, calcine under inert gas, inert gas is nitrogen, argon gas, one or both mists in helium, calcination temperature range is at 500 ~ 1000 DEG C, and maintain 3-5h at such a temperature, prepare magnetic MFe 2o 4/ C nano particle,
3rd step, preparation, containing the ethanolic solution 7 ~ 9mL of 0.5 ~ 3mmol slaine, adds the MFe of 9 ~ 11mg 2o 4/ C nano particle, ultrasonic disperse 8 ~ 12min, stirring at room temperature 0.8 ~ 1.2h, then under being placed in ice-water bath or room temperature, dropwise add the mixed solution of the ethanol/water of 2mL 0 ~ 0.5mM nitric acid, in the mixed solution of the ethanol/water of this nitric acid, ethanol/water volume ratio is 4 ~ 6: 1 or dropwise adds 1.8 ~ 2.2M NaOH aqueous solution, stir 2 ~ 24h, finally, obtained compound is utilized Magnetic Isolation, cleaning, being scattered in 25 ~ 35mL volume ratio is in the ethanol/water solution of 0.8 ~ 1.2: 1, be transferred to reactor, 160 ~ 230 DEG C of reaction 3 ~ 10h, drop to room temperature, clean with water, obtain crystallinity magnetic MFe 2o 4/ C/AO xcomposite nano materials, metal oxide AO xtiO 2, SnO 2, ZrO 2, ZnO or CeO 2in one or more combination, X is positive integer, described metal oxide AO xmetallic element presoma be one or more in its fluoride, chloride, bromide, sulfate, nitrate, acetate, oxide, isopropoxide and ester salt thereof.
2. preparation method according to claim 1, is characterized in that described phenol organic molecule is the one in phenol, catechol, hydroquinones, resorcinol, '-biphenyl diphenol.
3. preparation method according to claim 1, is characterized in that, step second step, and the mass ratio of described magnetic nano-particle and phenol organic molecule is 1: 10, and reaction temperature is 180 DEG C.
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CN107512738B (en) * 2016-06-18 2021-09-03 合肥杰事杰新材料股份有限公司 Porous MnFe2O4Nano material and preparation method thereof
CN105999277B (en) * 2016-08-05 2018-08-10 东北师范大学 A kind of fusiformis Fe3O4@C/Zn3(PO4)2The preparation method of nano-particle
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
CN109569518B (en) * 2018-08-13 2021-08-24 兰州交通大学 Preparation method of cysteine functionalized magnetic hollow manganese ferrite nano composite adsorbent
CN110787795B (en) * 2019-09-11 2022-04-19 浙江工业大学 Multilayer double-hole structure composite photocatalyst and preparation and application thereof
CN111302381A (en) * 2020-03-04 2020-06-19 巢湖学院 Magnetic cerium oxide and preparation method thereof
CN111939923B (en) * 2020-08-07 2022-06-28 浙江工业大学 Magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst and preparation method and application thereof
CN113457741B (en) * 2021-06-03 2023-04-11 四川农业大学 Preparation method and application of multi-enzyme active three-layer FeOx @ ZnMnFeOy @ Fe-Mn bimetal organogel
CN114084910B (en) * 2021-10-15 2023-12-05 闽都创新实验室 Cerium-nickel-cobalt doped ferrite nano material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102125699A (en) * 2010-01-12 2011-07-20 中国科学院宁波材料技术与工程研究所 Fe3O4/TiO2 composite nano-particles as well as preparation method and application thereof in magnetic resonance imaging contrast medium
CN102146288A (en) * 2011-01-05 2011-08-10 中国科学院宁波材料技术与工程研究所 Preparation method of water-soluble material in core-shell or core-corona-shell structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102125699A (en) * 2010-01-12 2011-07-20 中国科学院宁波材料技术与工程研究所 Fe3O4/TiO2 composite nano-particles as well as preparation method and application thereof in magnetic resonance imaging contrast medium
CN102146288A (en) * 2011-01-05 2011-08-10 中国科学院宁波材料技术与工程研究所 Preparation method of water-soluble material in core-shell or core-corona-shell structure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Dawei Qi et al..Magnetically Responsive Fe3O4CSnO2 Core-Shell Microspheres:Synthesis,Characterization and Application in Phosphoproteomics.《J. Phys. Chem. C》.2009,第113卷(第36期), *

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