CN102602920B - Preparation method of iron-coated graphene nanocomposite material - Google Patents
Preparation method of iron-coated graphene nanocomposite material Download PDFInfo
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- CN102602920B CN102602920B CN2012100879537A CN201210087953A CN102602920B CN 102602920 B CN102602920 B CN 102602920B CN 2012100879537 A CN2012100879537 A CN 2012100879537A CN 201210087953 A CN201210087953 A CN 201210087953A CN 102602920 B CN102602920 B CN 102602920B
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Abstract
A preparation method of an iron-coated graphene nanocomposite material comprises the following steps: (1) conducting thermal-expansion stripping on graphite oxide under a high temperature to obtain multi-layer graphene; (2) putting the multi-layer graphene and an organic solvent into a four-mouth flask, and mechanically stirring and mixing uniformly; (3) introducing pentacarbonyl iron steam into the mixed solution for thermal decomposition under a continuously stirring protection atmosphere; (4) conducting the thermal decomposition in a reflux condensation process; and (5) after the reaction, cooling to room temperature under the nitrogen protection, separating a product by a magnet, then cleaning the product by adopting an organic solvent, and drying the product under the nitrogen protection to obtain the iron-coated graphene nanocomposite material. According to the preparation method, Fe nanoparticles with a size of 20-50nm can be coated on the graphene sheet layers uniformly, the process is simple and controllable, the cost is low, and the industrial production is facilitated.
Description
Technical field
The invention belongs to field of nanocomposite materials, be specifically related to a kind of preparation method of iron coating graphite alkene nano composite material.
Background technology
The research of functional iron-based/carbon nanomaterial mixture mainly concentrates on magnetic fluid, biological medicine and katalysis, and composite form is that nanometer ferromagnetic metal outside coats or carbon nanomaterial in load.People such as A.A.EI-Gendy (Crabon 2009 the 47th phase the 2821st page) adopt chemical Vapor deposition process that metal (iron-cobalt-nickel) cyclopentadienyl compounds is decomposed the nano composite material that has obtained nucleocapsid structure, and its magnetic property is studied.Morjan etc. (Advanced Powder Technology the 2012nd the 23rd phase the 88th page) adopt laser synthesis method, with pentacarbonyl iron and acetylene gas respectively as the chemical feedstocks of iron and carbon, obtained α-iron nano-particle of being covered by graphite linings, this matrix material can effectively prevent the oxidation of nanometer metallic iron.Graphene also is widely used as the wild phase in the matrix material as a kind of novel carbon nanomaterial, and Cong etc. (Small 2010 the 6th phase the 169th page) adopt the synthetic method of original position to prepare Fe
3O
4/ Graphene magnetic composite can be regulated the magnetic property of matrix material by the concentration that changes source of iron, and this material has broad application prospects in fields such as electromagnetic shielding, magnetic recording and biological medicines.
We learn by Theoretical Calculation (International Journal of Plasticity 2011 the 27th phase the 539th page), carbon nanomaterial can improve the elastic stiffness of material and yield strength etc. as the metallic matrix composite wild phase, but because the agglomeration that nano material is prone to causes the theoretical performance of estimating to strengthen and is difficult to realize.In order to improve performance, the mixture of carbon nanomaterial and metallic copper nano-powder is carried out high-energy ball milling to people such as Kim (Compos.Sci.Eng 2006 the 430th phase the 27th page) and sintering process is handled, the sample that obtains has been realized the enhancing of hardness to a certain extent, but still there is more serious reunion, and additional process is introduced impurity easily or is caused the oxidation of matrix, and can't realize transfer good on carbon nanomaterial/metal interface, therefore in metal matrix/carbon nano-composite material development, even dispersion and the surface coating rate of carbon nanomaterial in metallic matrix is to need the major issue that solves in future studies.
Summary of the invention
The technical problem that solves: the invention provides a kind of iron coating graphite alkene nano composite material and preparation method thereof, this method technology is simple, can realize scale operation; In the iron coating graphite alkene nano composite material that obtains, iron granular size homogeneous, and can be coated on effectively and uniformly and form one deck iron film on the Graphene lamella, this method can be adjusted the processing parameter of coating, thereby characteristics such as the clad ratio of control matrix material and pattern.
Technical scheme of the present invention is: a kind of preparation method of iron coating graphite alkene nano composite material may further comprise the steps:
(1) graphite oxide is at high temperature carried out the thermal expansion lift-off processing, obtain multi-layer graphene;
(2) multi-layer graphene and organic solvent are put into four-hole boiling flask, mechanical stirring mixes;
(3) constantly stirring under the protective atmosphere, the pentacarbonyl iron steam is being imported in the mixing solutions carry out thermolysis;
(4) thermal decomposition process carries out in the reflux condensation mode process;
(5) after reaction finished, nitrogen protection was cooled to room temperature, with magnet product is separated, and adopted organic solvent to clean then, obtained iron coating graphite alkene nano composite material under the nitrogen protection after the drying.
Typically the isolated sample of magnet is adopted successively octane, dehydrated alcohol and acetone to clean up (1 to 4 time), dry under 50～80 ℃ under nitrogen protection.
Described graphite oxide elevated temperature heat expand rise peel off obtain multi-layer graphene temperature at 300-800 ℃, expand time of peeling off of rising of elevated temperature heat is 3～10min.Be typically and in tube furnace, carry out the thermal expansion processing.
The organic solvent of step (2) uses the liquid hydrocarbon that comprises that C5 is above, alcohols all can, as kerosene, volume is more than 30 times of graphite oxide volume, between 100～800ml, mechanical stirring speed is between 100-300r/min.
Protective atmosphere and guiding gas are N
2, rare gas element such as Ar, airshed imports the iron carbonyl steam of flow between 20-150ml/min in the mixing solutions between 20-150ml/min, heat decomposition temperature is between 180～250 ℃.
Constantly stirring under the protective atmosphere, the pentacarbonyl iron steam is being imported reflux when carrying out thermolysis in the mixing solutions, the thermolysis return time is between 60～1200min.
In the described iron coating graphite alkene nano composite material, the iron particle is 20～50nm.Material is black powder.
The invention has the beneficial effects as follows, in organic solvent, adopt one step of thermolysis process to make iron coating graphite alkene nano composite material.Its advantage is:
(1) can regulate the clad ratio of matrix material and size, the pattern of iron particle by regulating return time, heat decomposition temperature etc.
(2) iron coating graphite alkene nano composite material preparation method of the present invention and materials are simple, and preparation technology is easy and simple to handle, need not complicated synthesis device, and preparation cost is lower;
(3) invention obtains the surface and has Graphene than polyfunctional group, can improve the wettability of carbon nanomaterial and metallic iron, make that carbon nanomaterial is easier to be dispersed in the iron-based, recycling iron carbonyl decomposition technique coats it, obtain iron coating graphite alkene nano composite material, the shortcoming of easily reuniting when in the past directly using carbon nanomaterial as toughener be can overcome, the refinement of product merit and the technology upgrading of carbonyl iron dust realized.
Description of drawings
Fig. 1-2 is SEM Electronic Speculum figure of the present invention, and wherein Fig. 1 is side elevational view, and Fig. 2 is front elevation;
Fig. 3-4 is TEM Electronic Speculum figure of the present invention, and wherein Fig. 3 is 180min for the resolving time, and Fig. 4 is 360min for the resolving time;
Fig. 5 is VSM figure of the present invention;
Fig. 6 is XRD figure of the present invention;
Fig. 7 is reflectivity loss scaling system of the present invention.
Embodiment:
It below is specific embodiment of the present invention.
Embodiment 1:
Getting graphite oxide 20mg is put in the crucible, wrap with masking foil, pushing 300 ℃ (all can for 500 ℃ or 600 ℃, time, corresponding weak point was a little) tube furnace in carry out 3min thermal expansion handle, the multi-layer graphene 100mg and the 500ml kerosene that obtain are added in the four-hole boiling flask, and four-hole boiling flask connects prolong, temperature controller, mechanical stirrer, inlet pipe respectively.Feed 10 minutes emptying air of nitrogen, low whipping speed is under the condition of 180r/min, adopts electric mantle slowly to heat kerosin to 220 and ℃ carries out condensing reflux.Adopt N
2As guiding gas, the guiding carbonyl iron steam enters kerosene (gasoline or Virahol all can) solution and decomposes N
2Flow velocity is 120ml/min, and reaction continues 180min.At N
2Protection is cooling cooling gradually down, sample is carried out magnetic separate, and use octane, acetone, dehydrated alcohol respectively to wash successively 3 times, and after the following 60 ℃ of dryings of nitrogen protection, the black powder shape sample that obtains is iron coating graphite alkene nano composite material.
Fig. 1 and 2 is the scanning electron microscope diagram of iron coating graphite alkene nano composite material (embodiment 1).Iron particle is evenly distributed on the Graphene surface as can be seen from Figure, and forms one deck iron membrana granulosa gradually; Along with the carrying out of reaction, the new particle that forms is deposited in surface and the edge of iron membrana granulosa gradually, and the size of Fe particle there is no obvious reunion between 20-50nm.
Fig. 3 is the transmission electron microscope figure of iron coating graphite alkene nano composite material (embodiment 1).As can be seen from the figure iron particle is evenly distributed on the Graphene lamella, favorable dispersity, and particle size shows consistent with scanning electron microscope between 20-50nm.
Fig. 5 is the VSM figure of iron coating graphite alkene nano composite material (embodiment 1).From figure we as can be seen, the saturation magnetization of sample is 115emu/g, coercive force is 170Oe, remanent magnetism (Mr) is 14.2emu/g.
Fig. 6 is the X-ray diffractogram of iron coating graphite alkene nano composite material (embodiment 1).We can find out that the strong diffraction peak of isometric system α-Fe appears in material from the XRD figure of matrix material, also have the peak of a little oxide compound, mainly are that iron coating graphite alkene matrix material is exposed in the air due to the partial oxidation.
Fig. 7 is the reflection loss calculation formula figure of iron coating graphite alkene nano composite material (embodiment 1).As can be seen from Figure, when material and paraffin mass ratio are 83: 17, when material thickness is 1.5mm, 10-16GHz range of frequency internal reflection loss all-below the 10dB; When thickness of composite material is 3mm, near 4.3GHz, maximum loss can arrive-25dB about.
Embodiment 2:
Getting graphite oxide 20mg is put in the crucible, wrap with masking foil, pushing the thermal expansion of carrying out 5min in 500 ℃ the tube furnace handles, obtain multi-layer graphene 100mg multi-layer graphene and 500ml kerosene are added in the four-hole boiling flask, four-hole boiling flask connects prolong, temperature controller, mechanical stirrer, inlet pipe respectively.Feed nitrogen (N
2) emptyings in 10 minutes, low whipping speed is under the condition of 180r/min, adopts electric mantle slowly to heat kerosin to 240 and ℃ carries out condensing reflux.Adopt N
2As guiding gas, guiding pentacarbonyl iron steam enters kerosin and decomposes N
2Flow velocity is 120ml/min, and reaction continues 360min.At N
2Protection is cooling cooling gradually down.Sample is carried out magnetic separate, and use octane, acetone, dehydrated alcohol respectively to wash successively 3 times, after the following 60 ℃ of dryings of nitrogen protection, the black powder shape sample that obtains is iron coating graphite alkene nano composite material.
Fig. 4 is the transmission electron microscope figure of iron coating graphite alkene nano composite material (embodiment 2), as can be seen from Figure, prolongs the reaction times, and iron particle clad ratio obviously improves, and particle size is increased to about 50nm, and whole matrix material is sheet structure.
Fig. 5 is the VSM figure of iron coating graphite alkene nano composite material (embodiment 2), and the saturation magnetization of sample is 140emu/g as we know from the figure, and coercive force (Hc) is 193Oe, and remanent magnetism is 29emu/g.Along with the prolongation of return time, the Fe particle is progressively grown up and is increased, and the saturation magnetization of sample, coercive force and remanent magnetism etc. all increase.
Claims (5)
1. the preparation method of an iron coating graphite alkene nano composite material is characterized in that may further comprise the steps:
(1) graphite oxide is at high temperature carried out the thermal expansion lift-off processing, obtain multi-layer graphene; Graphite oxide elevated temperature heat expand peel off obtain multi-layer graphene temperature at 300-800 ℃, elevated temperature heat time of peeling off of expanding is 3～10min;
(2) multi-layer graphene and organic solvent are put into four-hole boiling flask, mechanical stirring mixes; Organic solvent is kerosene, and volume is more than 30 times of graphite oxide volume, and between 100～800mL, mechanical stirring speed is between 100-300r/min;
(3) constantly stirring under the protective atmosphere, the pentacarbonyl iron steam is being imported in the mixing solutions carry out thermolysis; Protective atmosphere is N
2Or the Ar rare gas element, airshed imports the iron carbonyl steam of flow between 20-150mL/min in the mixing solutions between 20-150mL/min, and heat decomposition temperature is between 180～250 ℃;
(4) thermal decomposition process carries out in the reflux condensation mode process;
(5) after reaction finished, nitrogen protection was cooled to room temperature, with magnet reaction product is separated, and adopted organic solvent to clean then, obtained iron coating graphite alkene nano composite material under the nitrogen protection after the drying.
2. the preparation method of iron coating graphite alkene nano composite material according to claim 1; it is characterized in that: constantly stirring under the protective atmosphere; the pentacarbonyl iron steam imported reflux when carrying out thermolysis in the mixing solutions, the thermolysis return time is between 60～1200min.
3. the preparation method of iron coating graphite alkene nano composite material according to claim 1 is characterized in that: described reaction product is separated and is adopted magnet, and the reaction product washing is used octane, dehydrated alcohol, these three kinds of solvent repetitive scrubbings of acetone 1-4 time successively.
4. the preparation method of iron coating graphite alkene nano composite material according to claim 1 is characterized in that: when reaction product is dry at N
2Protection is following, temperature is between 50～80 ℃.
5. the preparation method of iron coating graphite alkene nano composite material according to claim 1, it is characterized in that: in the described iron coating graphite alkene nano composite material, the iron particle is 20～50nm; Iron coating graphite alkene nano composite material is black powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102887506A (en) * | 2012-09-28 | 2013-01-23 | 南京大学 | Method for preparing iron coated multi-layer graphene nano composite material by performing gaseous decomposition on pentacarbonyl iron |
| CN103011328A (en) * | 2012-12-21 | 2013-04-03 | 清华大学 | Novel efficient grapheme loaded nano-iron material for adsorbing phosphorus in water |
| CN103212714B (en) * | 2013-04-27 | 2015-04-22 | 安徽大地熊新材料股份有限公司 | Method for preparing neodymium iron boron material |
| CN105329851B (en) * | 2015-11-02 | 2017-02-01 | 杭州电子科技大学 | Preparation method of nano iron oxide-multilayered graphene composite material |
| CN106270553B (en) * | 2016-08-30 | 2018-10-26 | 铱格斯曼航空科技集团有限公司 | A kind of preparation method of Ni-Co alloy particles cladding graphene oxide composite material |
| CN109368620A (en) * | 2018-12-11 | 2019-02-22 | 中国科学院兰州化学物理研究所 | A kind of preparation method of extra small sub-nanometer hole porous graphene |
| CN111320165B (en) * | 2018-12-13 | 2023-07-18 | 山东欧铂新材料有限公司 | Graphene oxide/carbonyl iron composite material, preparation method thereof and graphene-based wave-absorbing material |
| CN111625149B (en) * | 2020-06-03 | 2024-04-16 | 上海天马微电子有限公司 | Conductive shielding module, manufacturing method thereof and display device |
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| CN1676244A (en) * | 2005-01-17 | 2005-10-05 | 武汉科技大学 | Carbon-clad metal nano particle and its preparing method |
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| CN1676244A (en) * | 2005-01-17 | 2005-10-05 | 武汉科技大学 | Carbon-clad metal nano particle and its preparing method |
| CN101983101A (en) * | 2008-02-27 | 2011-03-02 | 巴斯夫欧洲公司 | Method for the production of iron-doped carbons |
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