CN106829934A - Using the rare earth modified method for preparing polymolecularity Graphene - Google Patents
Using the rare earth modified method for preparing polymolecularity Graphene Download PDFInfo
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- CN106829934A CN106829934A CN201710179878.XA CN201710179878A CN106829934A CN 106829934 A CN106829934 A CN 106829934A CN 201710179878 A CN201710179878 A CN 201710179878A CN 106829934 A CN106829934 A CN 106829934A
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- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
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Abstract
The invention discloses using the rare earth modified method for preparing polymolecularity Graphene, the earth solution with ethanol as solvent is first prepared；Heating, pH is adjusted to 5~6, obtains rare earth modified solution；Graphene oxide is immersed in rare earth modified solution, ultrasonic disperse obtains modified graphene oxide dispersion liquid；The hydrazine hydrate solution of mass concentration 80% is added in modified graphene oxide dispersion liquid, reduction obtains graphene solution；Then absolute ethyl alcohol and deionized water washing are multiple, are placed in being dried in baking oven, obtain the rare earth modified graphene powder of polymolecularity.Solve that existing graphene dispersion is poor, the problem of wettability difference, and preparation process is simple, with low cost, environmental protection.
Description
Technical field
The invention belongs to graphenic surface technical field of modification, it is related to one kind to prepare polymolecularity graphite using rare earth modified
The method of alkene.
Background technology
Graphene is carbon atom with sp2The New Two Dimensional atomic crystal that the monoatomic layer of hydridization connection is constituted, be with one
The abundant and peculiar physical property of row：Specific surface area (the 2630m of super large2/ g), it is to be currently known intensity highest material, reach
130GPa；Its carrier mobility reaches 15000cm2/(V·s)；Thermal conductivity is up to 5150W/ (mK), is that proof gold is firm at room temperature
3 times of stone.The unique physics of Graphene, chemistry and mechanical property have established important foundation for the exploitation of composite, are various
The preferable reinforcement of composite, it is expected to develop with composite woods such as rich and varied, excellent properties polymer matrixes, Metal Substrates
Material.
But because Graphene chemical property is very stable, surface is inert, thus Graphene and other matrixes wettability
Very poor, the interface cohesion of graphene composite material is the physical bond based on mechanical bond, in interface both without chemical reaction,
Also without diffusion, cause this composite material tensile strength not high, its application is extremely restricted.Meanwhile, each lamella of Graphene it
Between Van der Waals force greatly, cause to be easy to stacking between lamella to reunite, dispersiveness is poor.Improve Graphene dispersiveness and its
It is the key for solving Graphene application problem with the compatibility between various materials.
Method main at present is that surface modification treatment is carried out to Graphene, and modified method mainly has three kinds：It is organic
Thing is modified, mineral-modified and element doping is modified.At present, organic functional is carried out to Graphene, and modified to be that Graphene is modified grind
The main focus studied carefully.Graphene oxide is obtained by chemical oxidization method has reactivity higher.Graphene after oxidation
Surface and edge introduce many hydrophilic radicals so that graphite oxide has very strong hydrophily, but its dispersiveness without obvious
Improvement.In order to expand the range of application of Graphene, its dispersiveness in the matrix such as organic solvent and polymer is improved,
Need to carry out appropriate surface organic modification to it.The report on organic functional modified graphene seen at present, mainly
Have carries out functional modification using isocyanates, alkylamine, silane coupler, diazol etc. to it, by being modified, Graphene
Dispersiveness makes moderate progress, but these method complex process are cumbersome, and preparation cost is high, larger to environmental hazard, seriously limits stone
The further application and development of black alkene.
The content of the invention
To achieve the above object, the present invention provides a kind of using the rare earth modified method for preparing polymolecularity Graphene, solution
Graphene dispersion of having determined is poor, the problem of wettability difference, and preparation process is simple, with low cost, environmental protection.
The technical solution adopted in the present invention is, a kind of to utilize the rare earth modified method for preparing polymolecularity Graphene, presses
Implement according to following steps：
Step 1, prepares the earth solution with ethanol as solvent；
Step 2, heating water bath is carried out by earth solution, and the pH of earth solution is adjusted into 5~6, obtains rare earth modified solution；
Step 3, according to the ratio of 200~500mg/mL by graphene oxide in immersing rare earth modified solution at 18-22 DEG C
In, ultrasonic disperse obtains modified graphene oxide dispersion liquid；
Step 4, adds the hydrazine hydrate solution of mass concentration 80% in modified graphene oxide dispersion liquid, and reduction obtains stone
Black alkene solution；
Step 5, is then washed repeatedly with 40~60 DEG C of absolute ethyl alcohol and deionized water, until can't detect rare earth from
Son, is placed in being dried in baking oven, obtains the rare earth modified graphene powder of polymolecularity.
Further, in the step 1, the mass fraction of earth solution various composition is：Rare earth compound 0.05~
5.0%, ammonium chloride 0.1~2.0%, urea 0.01~2.0%, ethylenediamine tetra-acetic acid 0.05%~0.5%.
Further, the rare earth compound is the chloride of lanthanum, cerium, praseodymium or neodymium.
Further, in the step 2, earth solution is carried out into heating water bath to 75~85 DEG C, is incubated 5~10 minutes.
Further, in the step 2, the pH of earth solution is adjusted to 5~6 with nitric acid.
Further, in the step 3, ultrasonic disperse 3~6 hours, ultrasonic power is 900~2000W, and frequency is 20
~75KHz.
Further, in the step 4, modified graphene oxide dispersion liquid is with hydrazine hydrate according to volume ratio 10:7~10:
10 proportionings.
Further, in the step 5,100 DEG C of oven temperature dries 12~15h.
Beneficial effects of the present invention：
(1) Graphene prepared using the method has dispersiveness well, and its surface moist also than having bright before modified
Aobvious improvement.
(2) Graphene prepared using the method, overcomes the problem of Graphene and the wetability difference of metallic matrix, can be real
Existing application of the Graphene in metal-base composites.
(3) preparation method is simple for process, low production cost, environmental protection.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the XRD of modified graphene obtained in the embodiment of the present invention (M-GN) and Graphene (GN).
Fig. 2 is modified graphene SEM figures obtained in the embodiment of the present invention.
Fig. 3 is the principle schematic of rare earth modified graphene oxide.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
A kind of to utilize the rare earth modified method for preparing polymolecularity Graphene, principle is as shown in figure 1, according to following steps reality
Apply：
Step 1, prepares the earth solution with ethanol as solvent, wherein, the mass fraction of earth solution various composition is：It is dilute
Earth compounds 0.05~5.0%, ammonium chloride 0.1~2.0%, urea 0.01~2.0%, ethylenediamine tetra-acetic acid 0.05%~
0.5%.
Step 2, heating water bath to 75~85 DEG C is carried out by earth solution, is incubated 5~10 minutes, then with nitric acid by rare earth
The pH of solution is adjusted to 5~6, obtains rare earth modified solution.
Step 3, immerses rare earth modified by graphene oxide according to the ratio of 200~500mg/mL under the conditions of 18-22 DEG C
In solution, ultrasonic wave disperses 3~6 hours, and ultrasonic power is 900~2000W, and frequency is 20~75KHz, obtains modified oxidized
Graphene dispersing solution.
Step 4, then adds the hydrazine hydrate solution of mass concentration 80% in modified graphene oxide dispersion liquid, and be modified oxygen
Graphite alkene dispersion liquid is with hydrazine hydrate according to volume ratio 10:7~10:10 proportionings, reduction obtains graphene solution.
Step 5, is then washed repeatedly with 40~60 DEG C of absolute ethyl alcohol and deionized water, until can't detect rare earth from
Son, is placed in 100 DEG C of 12~15h of drying in baking oven, obtains the rare earth modified graphene powder of polymolecularity.
Wherein, rare earth compound is the chloride of lanthanum, cerium, praseodymium or neodymium.
Rare earth element has special electronic structure (- 4f0-14) chemical property that is determined, exist hydrogen, oxygen, nitrogen,
In the complex system that typical case's nonmetalloid such as carbon is constituted, because the exchange of electronics and interatomic polarization, atom
Size certainly will change a lot, and rare earth will be polarized, and as active element, can penetrate into unit as surfactant and shallow-layer
Element.Rare earth electronegativity is low, active big, not only can be with the surface of clean Graphene, and can also form Re-C keys or mixed hybridization makes
Its state is more stable.As the rare earth element of Active sites, because its ligancy is very high, can with rare-earth modifier in
Organic active group continues coordination chemistry, and some organic active groups are incorporated into surface of graphene oxide.Additionally,
Ionization rare earth can penetrate into the rejected region of Graphene, produce distortion area, and in distortion area absorption C, the above treatment
The dispersiveness of Graphene can be improved, can also promote Graphene to be reacted with active group, improve Graphene and other substrates
Bond strength.
The selection of the various composition in earth solution is analyzed by test of many times, and how composition is not in the scope, is modified
Graphene oxide afterwards goes poor dispersion.Water-bath controls the control of temperature and time in step 2, on the one hand prevents in modifying agent
The decomposition of side organic solvent, on the one hand causes that ethanedioic acid tetraacethyl and rare earth ion form the water soluble complex of stabilization, chelating
It is in hgher efficiency.In step 3, parameter selection dispersion effect in this parameter area is preferably less than this parameter in ultrasonic wave dispersion,
Reaction is not thorough.More than this power bracket and time, the dispersiveness of Graphene is not changed.The power of ultrasonic wave reaches necessarily
When degree, catalysis can be played to some chemical reactions.Selection hydrazine hydrate is strong reductant, its reproducibility phase herein
It is more preferable than in other reagent reduction effects.In step 5 modifying process, urea, ethanedioic acid etc. belongs to organic solvent, and modified oxygen
The water solubility of graphite alkene is not fine, is soluble in ethanol, in order to remove unreacted material, is finally washed with deionized water
Wash, solution is not allowed perishable into neutrality, drying.The temperature finally dried is too high equivalent to heating, can influence material physics and
The stability of chemical property, while the part oxygen functional group on graphene oxide can be removed.
Embodiment 1
The earth solution with ethanol as solvent is prepared, wherein, the mass fraction of earth solution various composition is：Rare earth chemical combination
Thing 0.05%, ammonium chloride 2.0%, urea 0.01%, ethylenediamine tetra-acetic acid 0.5%.Earth solution is carried out into heating water bath to 75
DEG C, 10 minutes are incubated, the pH of earth solution is then adjusted to 5 with nitric acid, obtain rare earth modified solution.According to the ratio of 200mg/mL
Example immerses in rare earth modified solution graphene oxide under the conditions of 18 DEG C, and ultrasonic wave disperses 3 hours, and ultrasonic power is
2000W, frequency is 75KHz, obtains modified graphene oxide dispersion liquid.Matter is then added in modified graphene oxide dispersion liquid
The hydrazine hydrate solution of concentration 80% is measured, modified graphene oxide dispersion liquid is with hydrazine hydrate according to volume ratio 10:7 proportionings, reduce
To graphene solution.Then washed repeatedly with 40 DEG C of absolute ethyl alcohol and deionized water, until can't detect rare earth ion, juxtaposition
12h is dried in 100 DEG C in baking oven, the rare earth modified graphene powder of polymolecularity is obtained.
Embodiment 2
The earth solution with ethanol as solvent is prepared, wherein, the mass fraction of earth solution various composition is：Rare earth chemical combination
Thing 5.0%, ammonium chloride 0.1%, urea 2.0%, ethylenediamine tetra-acetic acid 0.05%%.Earth solution is carried out into heating water bath to 85
DEG C, 5 minutes are incubated, the pH of earth solution is then adjusted to 6 with nitric acid, obtain rare earth modified solution.According to the ratio of 500mg/mL
Example immerses in rare earth modified solution graphene oxide under the conditions of 22 DEG C, and ultrasonic wave disperses 6 hours, and ultrasonic power is
900W, frequency is 20KHz, obtains modified graphene oxide dispersion liquid.Matter is then added in modified graphene oxide dispersion liquid
The hydrazine hydrate solution of concentration 80% is measured, modified graphene oxide dispersion liquid is with hydrazine hydrate according to volume ratio 10:10 proportionings, reduce
To graphene solution.Then washed repeatedly with 60 DEG C of absolute ethyl alcohol and deionized water, until can't detect rare earth ion, juxtaposition
15h is dried in 100 DEG C in baking oven, the rare earth modified graphene powder of polymolecularity is obtained.
Embodiment 3
The earth solution with ethanol as solvent is prepared, wherein, the mass fraction of earth solution various composition is：Rare earth chemical combination
Thing 3%, ammonium chloride 1%, urea 1%, ethylenediamine tetra-acetic acid 0.3%.Earth solution is carried out into heating water bath to 80 DEG C, insulation 7
Minute, the pH of earth solution is then adjusted to 6 with nitric acid, obtain rare earth modified solution.Ratio according to 350mg/mL will be aoxidized
Graphene immerses in rare earth modified solution under the conditions of 20 DEG C, and ultrasonic wave disperses 4 hours, and ultrasonic power is 1200W, and frequency is
50KHz, obtains modified graphene oxide dispersion liquid.Mass concentration 80% is then added in modified graphene oxide dispersion liquid
Hydrazine hydrate solution, modified graphene oxide dispersion liquid is with hydrazine hydrate according to volume ratio 10:8 proportionings, reduction obtains graphene solution.
Then being washed repeatedly with 50 DEG C of absolute ethyl alcohol and deionized water, until can't detect rare earth ion, be placed in 100 DEG C in baking oven
13h is dried, the rare earth modified graphene powder of polymolecularity is obtained.
Fig. 1,2 are product obtained in embodiment 3, from figure 1 it appears that diffraction maximum of the modified Graphene at 23 °
Intensity enhancing, narrowed width.From figure 2 it can be seen that the distribution of polymolecularity Graphene is very uniform obtained in embodiment hereof.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent substitution and improvements made within the spirit and principles in the present invention etc., are all contained in protection scope of the present invention
It is interior.
Claims (8)
1. it is a kind of to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that to implement according to following steps：
Step 1, prepares the earth solution with ethanol as solvent；
Step 2, heating water bath is carried out by earth solution, and the pH of earth solution is adjusted into 5~6, obtains rare earth modified solution；
Step 3, surpasses graphene oxide in being immersed in rare earth modified solution at 18-22 DEG C according to the ratio of 200~500mg/mL
Sound disperses, and obtains modified graphene oxide dispersion liquid；
Step 4, adds the hydrazine hydrate solution of mass concentration 80% in modified graphene oxide dispersion liquid, and reduction obtains Graphene
Solution；
Step 5, is then washed repeatedly with 40~60 DEG C of absolute ethyl alcohol and deionized water, until can't detect rare earth ion, and
It is placed in baking oven and dries, obtains the rare earth modified graphene powder of polymolecularity.
2. it is according to claim 1 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
In step 1, the mass fraction of earth solution various composition is：Rare earth compound 0.05~5.0%, ammonium chloride 0.1~2.0%,
Urea 0.01~2.0%, ethylenediamine tetra-acetic acid 0.05%~0.5%.
3. it is according to claim 2 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
Rare earth compound is the chloride of lanthanum, cerium, praseodymium or neodymium.
4. it is according to claim 1 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
In step 2, earth solution is carried out into heating water bath to 75~85 DEG C, be incubated 5~10 minutes.
5. it is according to claim 1 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
In step 2, the pH of earth solution is adjusted to 5~6 with nitric acid.
6. it is according to claim 1 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
In step 3, ultrasonic disperse 3~6 hours, ultrasonic power is 900~2000W, and frequency is 20~75KHz.
7. it is according to claim 1 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
In step 4, modified graphene oxide dispersion liquid is with hydrazine hydrate according to volume ratio 10:7~10:10 proportionings.
8. it is according to claim 1 to utilize the rare earth modified method for preparing polymolecularity Graphene, it is characterised in that described
In step 5,100 DEG C of oven temperature dries 12~15h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109233109A (en) * | 2018-10-15 | 2019-01-18 | 江西江铃集团奥威汽车零部件有限公司 | A kind of foamed material of automotive seat and its preparation method and application |
| CN114414333A (en) * | 2022-01-10 | 2022-04-29 | 湘潭大学 | Preparation method and application of rare earth modified graphene oxide composite solder |
| CN114774182A (en) * | 2022-05-26 | 2022-07-22 | 中国科学院过程工程研究所 | Lubricating oil additive and preparation method and application thereof |
| CN115926586A (en) * | 2023-02-01 | 2023-04-07 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
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| CN102534586A (en) * | 2012-02-15 | 2012-07-04 | 上海交通大学 | Method for preparing rare earth modified reduction-oxidation graphene film on surface of titanium alloy |
| CN102584334A (en) * | 2012-01-13 | 2012-07-18 | 上海交通大学 | Method for preparing graphene composite thin film on surface of silicon slice |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102584334A (en) * | 2012-01-13 | 2012-07-18 | 上海交通大学 | Method for preparing graphene composite thin film on surface of silicon slice |
| CN102534586A (en) * | 2012-02-15 | 2012-07-04 | 上海交通大学 | Method for preparing rare earth modified reduction-oxidation graphene film on surface of titanium alloy |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233109A (en) * | 2018-10-15 | 2019-01-18 | 江西江铃集团奥威汽车零部件有限公司 | A kind of foamed material of automotive seat and its preparation method and application |
| CN114414333A (en) * | 2022-01-10 | 2022-04-29 | 湘潭大学 | Preparation method and application of rare earth modified graphene oxide composite solder |
| CN114774182A (en) * | 2022-05-26 | 2022-07-22 | 中国科学院过程工程研究所 | Lubricating oil additive and preparation method and application thereof |
| CN114774182B (en) * | 2022-05-26 | 2023-04-18 | 中国科学院过程工程研究所 | Lubricating oil additive and preparation method and application thereof |
| CN115926586A (en) * | 2023-02-01 | 2023-04-07 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN115926586B (en) * | 2023-02-01 | 2023-08-18 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
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