CN101837971B - Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method - Google Patents
Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method Download PDFInfo
- Publication number
- CN101837971B CN101837971B CN2010101749071A CN201010174907A CN101837971B CN 101837971 B CN101837971 B CN 101837971B CN 2010101749071 A CN2010101749071 A CN 2010101749071A CN 201010174907 A CN201010174907 A CN 201010174907A CN 101837971 B CN101837971 B CN 101837971B
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite granule
- composite powder
- legal system
- molysite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing graphene/Fe3O4 composite powder by an alcohol thermal method, which comprises the following steps of: (1) weighing oxidated graphite and ferric salt at room temperature, dispersing into a glycol solution, adding polyethylene glycol after dissolving completely, then adding anhydrous sodium acetate, stirring and forming reaction liquid; (2) putting into a reaction kettle, heating to the temperature of 180 to 220 DEG C and reacting for 8 to 16h; and (3) cooling to the room temperature, collecting a product by using a magnet, washing the product by deionized water and drying so as to obtain the graphene/Fe3O4 composite powder. In the invention, the preparation method is simple and is easy for industrialized production; and Fe3O4 in the prepared graphene/Fe3O4 composite powder has pure crystalline phase, little possibility of agglomeration, favorable compounding with graphene and good dispersibility at the surface of the graphene and in the layer of the graphene, and the composite powder has small resistivity and high magnetization intensity.
Description
Technical field
The invention belongs to Graphene/Fe
3O
4The preparation field of composite granule particularly relates to the hot legal system of a kind of alcohol and is equipped with Graphene/Fe
3O
4The method of composite granule.
Background technology
Graphene is found a kind of novel two dimensional surface carbon nanomaterial in 2004, the monoatomic layer structures shape that it is special it have abundant and novel physicals.In the past few years, Graphene has become the research focus that gets most of the attention.Research shows, characteristics such as Graphene has ultra-thin, ultra firm and superpower conductivity are expected to obtain widespread use in fields such as nano electron device, matrix material, energy storage and biomedicines.
Recent study person finds, graphene-based matrix material can significantly improve performances such as the hardness, specific conductivity of mixture.G.Williams etc. utilize TiO last report of ACS Nano 2 (2008) 1487-1491
2Photocatalysis reduction-oxidation graphite prepare Graphene/TiO
2Mixture, the TiO of 2.6～4nm
2Particle is attached on the graphene film that approximately 2.2nm is thick.Y.J.Kin etc. utilize vapour phase epitaxy method to make ZnO nanometer rod vertical-growth on the Graphene surface last report of Applied Physics Letters 95 (2009) 213101-1-213101-3.Y.Fan etc. prepare Graphene/Al in the last employing mechanical ball milling method of having reported of Carbon 48 (2010) 1743-1749
2O
3Composite powder is with Al
2O
3Specific conductivity improved 13～16 one magnitude.
In addition and since the ferrite excellent magnetism can with and at application potential biological, medicine and other fields, Graphene and ferritic mixture also receive much attention gradually.H.P.Cong etc. Small 6 (2) (2010) 169-173 last reported the graphite oxide thermal reduction prepared Graphene after again with Fe
3O
4Carry out compound preparation Graphene/Fe
3O
4The method of mixture.
Yet prepare Graphene/Fe at present
3O
4Mainly there is following defective in the method for mixture: process step is more, cost is higher, and prepared Fe
3O
4Crystallization is incomplete.Therefore seeking single stage method prepares advantages of good crystallization, is difficult for reunion, the higher Graphene/Fe of the specific magnetising moment
3O
4Mixture becomes the focus of research.Do not see at present and adopt pure hot legal system to be equipped with Graphene/Fe
3O
4The report of composite granule.
Summary of the invention
Technical problem to be solved by this invention provides the hot legal system of a kind of alcohol and is equipped with Graphene/Fe
3O
4The method of composite granule, this preparation method is simple, is easy to suitability for industrialized production; Prepared graphene/Fe
3O
4Fe in the composite granule
3O
4Crystalline phase is pure, be difficult for reuniting, with Graphene compound good, in Graphene surface and layer good dispersivity, composite granule resistivity is little, the specific magnetising moment is high.
The hot legal system of a kind of alcohol of the present invention is equipped with Graphene/Fe
3O
4The method of composite granule comprises:
(1) configuration of reaction solution
At room temperature, take by weighing mass ratio and be 1: 1～1: 100 graphite oxide, molysite, be distributed in the ethylene glycol solution that concentration is 98wt%～99.5wt%, be incorporated as the polyoxyethylene glycol of terepthaloyl moietie volume 1/50～1/25 after treating to dissolve fully, add again with molysite in Fe
3+The ratio of mole number be 8: 1～12: 1 anhydrous sodium acetate, stir, make the above-mentioned substance dissolving, form reaction solution;
(2) solvent thermal reaction
Above-mentioned reaction solution is put into reaction kettle, be warming up to 180～220 ℃, reaction 8～16h;
(3) Graphene/Fe
3O
4The collection of composite granule and washing
Be cooled to room temperature, collect product with magnet, the deionized water wash product, oven dry promptly gets.
Molysite in the said step (1) is Iron(III) chloride hexahydrate FeCl
36H
2O.
The molysite in the said step (1) and the mass volume ratio of terepthaloyl moietie are 1g: 20～1000ml.
The molecular weight of the polyoxyethylene glycol in the said step (1) is 200～1000.
Stirring velocity in the said step (1) is 300～600 commentaries on classics/min, and the time is 20～40min.
Bake out temperature in the said step (3) is 40～80 ℃, and the time is 12～24h.
Through regulating the ratio of graphite oxide, molysite, obtain the different Graphene/Fe that form
3O
4Composite granule.
This preparation method is with respect to common liquid phase method, and magnetic nanoparticle is more stable in organic phase, is difficult for generating the impurity phase.Because in liquid phase, magnetic nano-particle is very easily reunited because of the effect that receives solion intensive electrostatic attraction, so present method selects electrostatic stabilization property for use good anhydrous sodium acetate adds as alkaline reagents, to prevent Fe
3O
4Extensive reunion.
Beneficial effect
(1) preparation method of the present invention is simple, and is low to the production unit requirement, is easy to suitability for industrialized production;
(2) prepared graphene/Fe
3O
4Fe in the composite granule
3O
4Crystalline phase is pure, be difficult for reuniting, with Graphene compound good, in Graphene surface and layer good dispersivity, composite granule resistivity is little, the specific magnetising moment is high.
Description of drawings
Fig. 1 is the transmission electron microscope photo of synthetic powder;
Fig. 2 is the high-resolution-ration transmission electric-lens photo of synthetic powder;
Fig. 3 is the X-ray diffractogram of synthetic powder;
Fig. 4 is the magnetic hysteresis loop figure of synthetic powder.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing the high iron(ic)chloride of 500mg, 50mg graphite oxide, add three-necked flask, add 50ml terepthaloyl moietie again, fully stir.Add 0.92g anhydrous sodium acetate, 1.5ml Macrogol 200 again, be 500 rev/mins of following mechanical stirring 30min, after treating to dissolve fully, more above-mentioned solution is poured in the reaction kettle, be warming up to 200 ℃, reaction 12h at revolution.Reaction finishes, and collects product with magnet, and uses the deionized water wash product, with product dry 16h under 60 ℃, obtains Graphene/Fe then
3O
4Composite granule.Fig. 1 is the transmission electron microscope photo of present embodiment synthetic powder, can find out: Fe
3O
4The Nano microsphere particle diameter is at 100～200nm, Fe
3O
4Nano microsphere is not observed the Fe that is free on outside the Graphene equably attached to Graphene surface and interlayer
3O
4Particle.Fig. 2 is the high-resolution-ration transmission electric-lens photo of present embodiment synthetic powder, can find out: the Fe in this composite granule
3O
4Nano microsphere is by a plurality of Fe
3O
4The directed gathering of nanocrystal forms, and its grain size is about 5nm, and spacing is about 0.25nm; Graphene film in this composite granule is made up of 5～20 layer graphenes, and the interlamellar spacing of Graphene is about 0.34nm.Fig. 3 is the X-ray diffractogram of present embodiment synthetic powder, and the diffraction peak among the figure shows: the nano particle in this composite granule is Fe
3O
4Fig. 4 is the magnetic hysteresis loop figure of present embodiment synthetic powder, can find out: the specific magnetising moment of this composite granule is higher, reaches 63.3emu/g.Resistivity measurement is the result show: the resistivity of this composite granule is 0.989 Ω/cm, and it has excellent conducting performance.
Embodiment 2
Take by weighing the high iron(ic)chloride of 50mg, 50mg graphite oxide, add three-necked flask, add 50ml terepthaloyl moietie again, fully stir.Add 80mg anhydrous sodium acetate, 1.0ml PEG 400 again, be 300 rev/mins of following mechanical stirring 40min, after treating to dissolve fully, more above-mentioned solution is poured in the reaction kettle, be warming up to 220 ℃, reaction 8h at revolution.Reaction finishes, and collects product with magnet, and uses the deionized water wash product, with product dry 24h under 40 ℃, obtains Graphene/Fe then
3O
4Composite granule.Transmission electron microscope observing shows: Fe
3O
4The Nano microsphere particle diameter is at 100～200nm, and is compound good with Graphene.High-resolution-ration transmission electric-lens is observed and is shown: the Fe in this composite granule
3O
4Nano microsphere is by a plurality of Fe
3O
4The directed gathering of nanocrystal forms, and graphene film is made up of 5～20 layer graphenes.The XRD test result shows: the nano particle in this composite granule is Fe
3O
4Magnetic hysteresis loop figure test shows: this composite granule has good magnetic performance.Resistivity measurement is the result show: this composite granule has excellent conducting performance.
Embodiment 3
Take by weighing the high iron(ic)chloride of 2.5g, 25mg graphite oxide, add three-necked flask, add 50ml terepthaloyl moietie again, fully stir.Add 9.0g anhydrous sodium acetate, 2.0ml cetomacrogol 1000 again, be 600 rev/mins of following mechanical stirring 20min, after treating to dissolve fully, more above-mentioned solution is poured in the reaction kettle, be warming up to 180 ℃, reaction 16h at revolution.Reaction finishes, and collects product with magnet, and uses the deionized water wash product, with product dry 12h under 80 ℃, obtains Graphene/Fe then
3O
4Composite granule.Transmission electron microscope observing shows: Fe
3O
4The Nano microsphere particle diameter is at 100～200nm, and is compound good with Graphene.High-resolution-ration transmission electric-lens is observed and is shown: the Fe in this composite granule
3O
4Nano microsphere is by a plurality of Fe
3O
4The directed gathering of nanocrystal forms, and graphene film is made up of 5～20 layer graphenes.The XRD test result shows: the nano particle in this composite granule is Fe
3O
4Magnetic hysteresis loop figure test shows: this composite granule has good magnetic performance.Resistivity measurement is the result show: this composite granule has excellent conducting performance.
Claims (5)
1. the hot legal system of alcohol is equipped with Graphene/Fe
3O
4The method of composite granule comprises:
(1) configuration of reaction solution
At room temperature, take by weighing mass ratio and be 1: 1～1: 100 graphite oxide, molysite, be distributed in the ethylene glycol solution that concentration is 98wt%～99.5wt%, be incorporated as the polyoxyethylene glycol of terepthaloyl moietie volume 1/50～1/25 after treating to dissolve fully, add again with molysite in Fe
3+The ratio of mole number be 8: 1～12: 1 anhydrous sodium acetate, stir, make the above-mentioned substance dissolving, form reaction solution; Wherein the molecular weight of polyoxyethylene glycol is 200～1000;
(2) solvent thermal reaction
Above-mentioned reaction solution is put into reaction kettle, be warming up to 180～220 ℃, reaction 8～16h;
(3) Graphene/Fe
3O
4The collection of composite granule and washing
Be cooled to room temperature, collect product with magnet, the deionized water wash product, oven dry promptly gets.
2. the hot legal system of a kind of alcohol according to claim 1 is equipped with Graphene/Fe
3O
4The method of composite granule is characterized in that: the molysite in the said step (1) is Iron(III) chloride hexahydrate FeCl
36H
2O.
3. the hot legal system of a kind of alcohol according to claim 1 is equipped with Graphene/Fe
3O
4The method of composite granule is characterized in that: the molysite in the said step (1) and the mass volume ratio of terepthaloyl moietie are 1g: 20～1000ml.
4. the hot legal system of a kind of alcohol according to claim 1 is equipped with Graphene/Fe
3O
4The method of composite granule is characterized in that: the stirring velocity in the said step (1) is 300～600 commentaries on classics/min, and the time is 20～40min.
5. the hot legal system of a kind of alcohol according to claim 1 is equipped with Graphene/Fe
3O
4The method of composite granule is characterized in that: the bake out temperature in the said step (3) is 40～80 ℃, and the time is 12～24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101749071A CN101837971B (en) | 2010-05-14 | 2010-05-14 | Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101749071A CN101837971B (en) | 2010-05-14 | 2010-05-14 | Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101837971A CN101837971A (en) | 2010-09-22 |
| CN101837971B true CN101837971B (en) | 2012-01-11 |
Family
ID=42741684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101749071A Expired - Fee Related CN101837971B (en) | 2010-05-14 | 2010-05-14 | Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101837971B (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
| CN102173411B (en) * | 2011-01-13 | 2012-07-11 | 东华大学 | Preparation method of water-dispersible graphene/ferroferric oxide (Fe3O4) composite powder |
| CN102229425B (en) * | 2011-03-29 | 2013-01-02 | 东华大学 | Method for preparing cobalt/graphene composite material by alcohol thermal method |
| CN102276244A (en) * | 2011-05-19 | 2011-12-14 | 东华大学 | Alcohol-heating method for preparing cobalt nickel ferrite / graphene magnetic nano composite powder |
| CN102295913A (en) * | 2011-06-14 | 2011-12-28 | 哈尔滨工程大学 | Graphite alkene and ferriferrous oxide nano-material capable of absorbing high frequency electromagnetic wave and preparation method thereof |
| CN102344775A (en) * | 2011-07-24 | 2012-02-08 | 哈尔滨工程大学 | Grapheme-ferroferric oxide composite material for absorbing high-frequency electromagnetic waves and preparation method thereof |
| CN102515284B (en) * | 2011-12-23 | 2014-04-02 | 东华大学 | Preparation method for Fe3O4/graphene composite powder |
| CN102533216B (en) * | 2011-12-27 | 2014-01-01 | 合肥希创电子科技有限公司 | Ferroferric oxide/reduced graphene oxide composite wave-absorbing material with hollow hemisphere structure and preparation method |
| CN102522565B (en) * | 2012-01-10 | 2015-09-09 | 吉林大学 | The method of tri-iron tetroxide charge and discharge cycles ability is improved by doped with oxygen graphite |
| CN102544457B (en) * | 2012-02-17 | 2014-12-03 | 合肥工业大学 | Method for preparing graphene oxide-iron sesquioxide nanotube composite material by using in-situ method |
| CN103373725B (en) * | 2012-04-28 | 2015-07-15 | 夏华松 | Preparation method of crystalloid graphite micropowder with unidirectional electromagnetic property |
| CN103007944A (en) * | 2012-12-13 | 2013-04-03 | 同济大学 | Preparation method of graphene-based magnetic composite visible light catalysis material Fe3O4-G-TiO2 |
| CN103007886B (en) * | 2012-12-25 | 2014-12-03 | 复旦大学 | Synthetic method of magnetic graphene mesoporous material used for separation and enrichment in peptideomics |
| CN103191698B (en) * | 2013-03-22 | 2015-01-07 | 聊城大学 | Method for preparing graphene/ferroferric oxide composite microspheres |
| CN103274396A (en) * | 2013-06-20 | 2013-09-04 | 电子科技大学 | Preparation method of grapheme and ferriferrous oxide composite nanometer material |
| CN103496693B (en) * | 2013-09-23 | 2015-04-29 | 郑州大学 | Method for preparing Fe3O4 nanoparticle/graphene composite material by sol electrostatic self-assembly process and application thereof |
| CN103693639A (en) * | 2013-12-13 | 2014-04-02 | 天津工业大学 | Preparation method of iron/manganese oxide doped graphene composite material |
| CN104261487A (en) * | 2014-09-23 | 2015-01-07 | 南昌航空大学 | Method for preparing ferroferric oxide/graphene magnetic nano composite material by solvothermal one-step method |
| CN104810509B (en) * | 2015-03-31 | 2017-08-04 | 浙江大学 | Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application |
| CN105271202B (en) * | 2015-11-16 | 2018-01-16 | 江苏城工建设科技有限公司 | A kind of preparation method and applications of graphene |
| CN105428623A (en) * | 2015-12-04 | 2016-03-23 | 天津大学 | Method for synthesizing ferroferric oxide-loaded carbon nanotube-reinforced graphene composite material and application |
| CN106179230A (en) * | 2016-10-08 | 2016-12-07 | 聊城大学 | A kind of magnetic ferroferric oxide nano-particles graphene composite material and preparation method and application |
| CN107230558B (en) * | 2017-06-21 | 2021-03-23 | 太原理工大学 | Fe3O4Preparation method of/graphene composite material |
| CN107398265A (en) * | 2017-08-09 | 2017-11-28 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method based on graphene oxide catalysis material |
| CN108585059A (en) * | 2017-11-16 | 2018-09-28 | 华侨大学 | A kind of graphene/Fe3O4The preparation method of/carbon nano-tube composite powder |
| CN110627108A (en) * | 2019-09-27 | 2019-12-31 | 东华大学 | Zinc oxide/reduced graphene oxide composite material and preparation method and application thereof |
| CN112501161B (en) * | 2020-12-23 | 2023-03-28 | 华南师范大学 | Double-magnetic-particle-intervention DNA extraction and purification method |
| CN117226806A (en) * | 2023-09-26 | 2023-12-15 | 广东工业大学 | Cluster magnetic control micro-nano robot and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486455A (en) * | 2009-02-25 | 2009-07-22 | 厦门大学 | Hydroxy and amino functionalized hollow carbon nanosphere and preparation thereof |
-
2010
- 2010-05-14 CN CN2010101749071A patent/CN101837971B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486455A (en) * | 2009-02-25 | 2009-07-22 | 厦门大学 | Hydroxy and amino functionalized hollow carbon nanosphere and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曹慧群等.新型碳纳米管磁性复合材料的制备及磁性能.《硅酸盐学报》.2008,第36卷(第9期),1247－1250，1276. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101837971A (en) | 2010-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101837971B (en) | Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method | |
| CN102173411B (en) | Preparation method of water-dispersible graphene/ferroferric oxide (Fe3O4) composite powder | |
| Li et al. | Graphene-CoO/PEG composite phase change materials with enhanced solar-to-thermal energy conversion and storage capacity | |
| Wang et al. | Fe 3 O 4-functionalized graphene nanosheet embedded phase change material composites: efficient magnetic-and sunlight-driven energy conversion and storage | |
| CN102515284B (en) | Preparation method for Fe3O4/graphene composite powder | |
| Sahan et al. | Thermal enhancement of paraffin as a phase change material with nanomagnetite | |
| Chao et al. | Carbonized wood flour matrix with functional phase change material composite for magnetocaloric-assisted photothermal conversion and storage | |
| CN104672357B (en) | A kind of composite material and preparation method thereof of graphene/carbon nanotube hybrid thing enhancing polymer | |
| Zhu et al. | Birnessite-type MnO2 nanowalls and their magnetic properties | |
| CN102276244A (en) | Alcohol-heating method for preparing cobalt nickel ferrite / graphene magnetic nano composite powder | |
| CN101800105A (en) | Method for preparing MWCNTs/Co1-xZnxFe2O4 magnetic nanocomposite material | |
| CN113786856B (en) | Preparation method of bamboo-like nitrogen-doped carbon nano tube loaded with metal monoatoms and nano particles | |
| CN101891483B (en) | Method for preparing Co1-xNixFe2O4 magnetic nano-powder by solvothermal method | |
| CN102350282A (en) | Preparation method of magnetic nano compound material of cobalt-nickel ferrite/multi-wall carbon nano pipe | |
| CN108264037B (en) | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene | |
| CN101481107B (en) | Preparation of nickel-zine ferrite (Ni1-xZnxFe2O4) coated carbon nano-tube magnetic nano composite material | |
| Xu et al. | Synthesis and super capacitance of goethite/reduced graphene oxide for supercapacitors | |
| CN102489252A (en) | Ferroferric oxide nano crystal loaded on acid-modified carbon nano tube and preparation method thereof | |
| CN108249482B (en) | Magnetic Fe2O3Preparation method of nano particles and method for compounding nano particles with nano carbon material | |
| CN106876670A (en) | The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application | |
| CN102936050A (en) | Preparation method of ferroferric oxide nano sheet | |
| CN102229425B (en) | Method for preparing cobalt/graphene composite material by alcohol thermal method | |
| Zhang et al. | Construction of chiral-magnetic-dielectric trinity composites for efficient microwave absorption with low filling ratio and thin thickness | |
| Zhao et al. | A general and facile method for improving carbon coat on magnetic nanoparticles with a thickness control | |
| CN103183343A (en) | Preparation method of aminated magnetic graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120111 Termination date: 20140514 |