CN106829927A - A kind of metal oxide graphene composite material and preparation method thereof - Google Patents
A kind of metal oxide graphene composite material and preparation method thereof Download PDFInfo
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- CN106829927A CN106829927A CN201710027467.9A CN201710027467A CN106829927A CN 106829927 A CN106829927 A CN 106829927A CN 201710027467 A CN201710027467 A CN 201710027467A CN 106829927 A CN106829927 A CN 106829927A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
The invention discloses a kind of preparation method of metal oxide graphene composite material, during graphene oxide, phenyl amines organic monomer and inorganic acid evenly spread into the aqueous solution containing ethanol first, then organic monomer polymerization is triggered, then the dedoping in ammoniacal liquor, adulterated with binary or ternary organic carboxyl acid again, soluble metallic salt is subsequently adding, promotes precipitation by metallic ion to generate metal oxide under conditions of alkaline concentrated ammonia liquor and heating, finally obtain metal oxide graphene composite material.The method is that conducting polymer is introduced on graphene sheet layer, then there is the organic acid of chelated metal ions performance in doping, metal ion is promoted to be enriched in graphenic surface, then metal oxide is generated under the alkaline environment of concentrated ammonia liquor to be compounded on Graphene, obtain the metal oxide graphene composite material of heavy load amount.
Description
Technical field
The present invention relates to graphene composite material technical field, a kind of metal oxide Graphene composite wood is specifically related to
Material and preparation method thereof.
Background technology
Graphene is a kind of new two dimension arranged according to hexagon by carbon atom（2D）Carbon material.It is current
A kind of known most thin material, the thickness of single-layer graphene only has 0.34 nm, and it has extremely strong electric conductivity（Charge migration
Rate is up to 200000 cm2V-1s-1）；The intensity of superelevation（Young's modulus is up to 1100 GPa）；Good thermal conductivity（Thermal conductivity 5300
WmK-1）And the specific surface area of super large（The m of theoretical specific surface area 26302g-1）So that grapheme material synthesizes in composite to be led
Domain has very extensive purposes.Metal oxide has many unique performances, such as magnetic, chemical property, catalytic performance,
It has been at present grinding for materials synthesis field by metal oxide with the compound composite that can obtain excellent performance of Graphene
Study carefully focus.But due to the inertia on grapheme material surface, when graphene-based metal oxide composite is prepared, metal oxygen
Compound is typically all to be dispersed in graphenic surface with granule-morphology, therefore metal oxide is compounded in graphite with being difficult to heavy load amount
Alkene surface, causes in graphene composite material that the content of metal oxide is relatively low, is unfavorable for playing the performance of metal oxide,
Also it is unfavorable for making full use of the effective ratio area of Graphene.
The content of the invention
The present invention in view of the shortcomings of the prior art, the invention provides a kind of system of metal oxide graphene composite material
Preparation Method, after the inventive method first introduces conducting polymer on graphene sheet layer, then has chelated metal ions in doping
The organic acid of performance, promotes metal ion to be enriched in graphenic surface, then can the uniform life in heavy load amount ground on Graphene
Metal oxide long, so as to obtain metal oxide graphene composite material, the present invention is answered to prepare metal oxide Graphene
Condensation material provides a kind of novel method.
The technical solution adopted by the present invention is as follows：A kind of preparation method of metal oxide graphene composite material, it is special
Levy and be, comprise the following steps：（1）By the graphene oxide of 0.1 ~ 1.0 weight portion, the organic monomer of 0.1 ~ 1.0 weight portion,
The inorganic acid of 0.1 ~ 1.0 weight portion is evenly spread in the solvent of 50 ~ 100 weight portions；（2）By the initiation of 0.1 ~ 1.0 weight portion
Agent is added in above-mentioned solution, after quickly stirring 1 ~ 10 minute, is reacted 5 ~ 20 hours at -5 ~ 25 DEG C；（3）Product is taken out
Filter, is then distributed to dedoping in ammonia spirit, then again with the organic acid of 1M with after distilled water, absolute ethanol washing successively
Solution is adulterated again, and end product is dried 3 ~ 5 hours at 60 ~ 100 DEG C；（4）The step of taking 0.1 ~ 1.0 weight portion（3）Product,
0.1 ~ 1.0 weight portion soluble metallic salt is evenly spread in 100 parts of aqueous solution, and 60 ~ 95 are then warmed up under nitrogen protection
DEG C, the concentrated ammonia solution of 5 ~ 20 weight portions is disposably added, continue heating stirring and react 1 ~ 5 hour；（5）Stop reaction, will most
End-product filtering and washing, dries 3 ~ 5 hours at 60 ~ 100 DEG C, you can.
Step（1）Described in organic monomer be at least one in aniline, ortho-aminotoluene, meta-aminotoluene.
Step（1）Described inorganic acid is at least one in sulfuric acid, hydrochloric acid, phosphoric acid.
Step（1）Described in solvent be ethanol and water mixed solution, its volume ratio be ethanol：Water=（0~4）：1.
Step（2）Described in initiator be the one kind in ammonium persulfate, potassium peroxydisulfate.
Step（3）Described in organic acid be one or more mixing in tartaric acid, malic acid, oxalic acid.
Step（4）Described in soluble metallic salt in soluble ferric iron salt, manganese salt, zinc salt, barium salt, cobalt salt, nickel salt
One or more mixing.Specifically, in the present invention, suitable soluble metallic salt includes iron chloride, frerrous chloride, chlorine
Change zinc, manganese chloride, barium chloride, cobalt chloride, nickel chloride, ferric nitrate, ferrous nitrate, zinc nitrate, manganese nitrate, barium nitrate, cobalt nitrate,
One or more mixing of nickel nitrate, ferric sulfate, ferrous sulfate, zinc sulfate, manganese sulfate, barium sulfate, cobaltous sulfate, nickel sulfate,
Other soluble metal salts can be extended to.
Metal oxide graphene composite material obtained in the inventive method.
Beneficial effect：
After the inventive method first introduces conducting polymer on graphene sheet layer, then there is chelated metal ions performance in doping
Organic acid, promote metal ion to be enriched in graphenic surface, then can on Graphene heavy load amount ground homoepitaxial gold
Category oxide, so as to obtain metal oxide graphene composite material, the present invention is to prepare metal oxide Graphene composite wood
Material is there is provided a kind of novel method.Preparation method of the present invention can be easy to for metal oxide heavy load amount to be compounded in stone
Black alkene surface, improves the content of metal oxide in graphene composite material, can preferably play the performance of metal oxide,
More fully using the effective ratio area of Graphene.
Specific embodiment
Embodiment 1
A kind of preparation method of metal oxide graphene composite material, comprises the following steps：
（1）The citric acid of the graphene oxide of 0.1 weight portion, the aniline monomer of 1.0 weight portions, 1.0 weight portions is dispersed
To in the solvent of 100 weight portions, solvent uses ethanol and water mixed solution, and its volume ratio is ethanol：Water=1；（2）By 1.0 weight
The ammonium persulfate of part is added in above-mentioned solution, after quickly stirring 10 minutes, is reacted 20 hours at -5 DEG C；（3）Reaction is produced
Thing suction filtration, is then distributed to dedoping in ammonia spirit, then again with the lemon of 1M with after distilled water, absolute ethanol washing successively
Lemon acid solution is adulterated again, and end product is dried 3 hours at 100 DEG C；（4）Take above-mentioned product, 1.0 weight portions of 1.0 weight portions
Soluble metal molysite（By ferrous chloride and ferric trichloride, mol ratio is 1：2 uniform mixing）Evenly spread to 100 parts of aqueous solution
In, 95 DEG C are then warmed up under nitrogen protection, the concentrated ammonia solution of 20 weight portions of disposable addition continues heating stirring reaction
5 hours；（5）Stop reaction, final product filtering and washing is dried 5 hours at 100 DEG C.
Embodiment 2
A kind of preparation method of metal oxide graphene composite material, comprises the following steps：
（1）By the graphene oxide of 1.0 weight portions, the aniline of 0.1 weight portion and ortho-aminotoluene mix monomer, 0.1 weight portion
Sulfuric acid is evenly spread in the solvent of 50 weight portions, and solvent uses ethanol and water mixed solution, and its volume ratio is ethanol：Water=4
（2）The potassium peroxydisulfate of 0.1 weight portion is added in above-mentioned solution, after quickly stirring 10 minutes, is reacted 5 hours at 0 DEG C；
（3）By product suction filtration, then dedoping in ammonia spirit is distributed to, then with after distilled water, absolute ethanol washing successively
Adulterated again with the citric acid solution of 1M again, end product is dried 5 hours at 60 DEG C；（4）Take 0.1 weight portion above-mentioned product,
0.1 weight portion soluble metallic salt（It is ferric nitrate and manganese nitrate, mol ratio is 2：1 uniform mixing）Evenly spread to 100 parts of water
In solution, 90 DEG C are then warmed up under nitrogen protection, the concentrated ammonia solution of 5 weight portions of disposable addition continues heating stirring
Reaction 2 hours；（5）Stop reaction, final product filtering and washing is dried 5 hours at 80 DEG C.
Embodiment 3
A kind of preparation method of metal oxide graphene composite material, comprises the following steps：
（1）The inorganic acid of the graphene oxide of 1.0 weight portions, the aniline monomer of 1.0 weight portions, 1.0 weight portions is dispersed
To in the solvent of 100 weight portions, solvent uses ethanol and water mixed solution, and its volume ratio is ethanol：Water=2；（2）By 1.0 weight
The ammonium persulfate of part is added in above-mentioned solution, after quickly stirring 5 minutes, is reacted 20 hours at ~ 5 DEG C；（3）By product
Suction filtration, is then distributed to dedoping in ammonia spirit, then again with the winestone of 1M with after distilled water, absolute ethanol washing successively
Acid solution is adulterated again, and end product is dried 3 hours at 80 DEG C；（4）Above-mentioned product, 0.5 weight portion for taking 0.5 weight portion are solvable
Property slaine（By ferric nitrate and nickel nitrate, mol ratio is 2：1 uniform mixing）In evenly spreading to 100 parts of aqueous solution, Ran Hou
95 DEG C are warmed up under nitrogen protection, the concentrated ammonia solution of 10 weight portions of disposable addition continues heating stirring and reacts 3 hours；（5）
Stop reaction, final product filtering and washing is dried 3 hours at 90 DEG C.
Embodiment 4
A kind of preparation method of metal oxide graphene composite material, comprises the following steps：
（1）By the graphene oxide of 1.0 weight portions, the aniline of 0.2 weight portion and meta-aminotoluene mix monomer, 0.2 weight portion
Inorganic acid is evenly spread in the water of 80 weight portions；（2）The ammonium persulfate of 0.2 weight portion is added in above-mentioned solution, quickly
After stirring 5 minutes, reacted 20 hours at 0 DEG C；（3）By product suction filtration, distilled water, absolute ethanol washing are then used successively
Afterwards, dedoping in ammonia spirit is distributed to, is then adulterated again with the oxalic acid solution of 1M again, it is small that end product dries 3 at 80 DEG C
When；（4）Take above-mentioned product, the 0.1 weight portion soluble metallic salt of 0.1 weight portion（It is ferric nitrate, manganese nitrate and nickel nitrate, rubs
You are than being 4：1：1 uniform mixing）Evenly spread in 100 parts of aqueous solution, 90 DEG C are then warmed up under nitrogen protection, disposably
The concentrated ammonia solution of 5 weight portions is added, is continued heating stirring and is reacted 3 hours；（5）Stop reaction, by final product filtering and washing,
Dried 3 hours at 90 DEG C.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of metal oxide graphene composite material, it is characterised in that comprise the following steps：（1）Will
The graphene oxide of 0.1 ~ 1.0 weight portion, the organic monomer of 0.1 ~ 1.0 weight portion, the inorganic acid of 0.1 ~ 1.0 weight portion uniformly divide
It is scattered in the solvent of 50 ~ 100 weight portions；（2）The initiator of 0.1 ~ 1.0 weight portion is added in above-mentioned solution, 1 is quickly stirred
After ~ 10 minutes, reacted 5 ~ 20 hours at -5 ~ 25 DEG C；（3）By product suction filtration, distilled water, absolute ethyl alcohol are then used successively
After washing, dedoping in ammonia spirit is distributed to, is then adulterated again with the organic acid soln of 1M again, end product is at 60 ~ 100 DEG C
Lower drying 3 ~ 5 hours；（4）The step of taking 0.1 ~ 1.0 weight portion（3）Product, 0.1 ~ 1.0 weight portion soluble metallic salt uniformly divide
It is scattered in 100 parts of aqueous solution, 60 ~ 95 DEG C is then warmed up under nitrogen protection, disposably adds the concentrated ammonia liquor of 5 ~ 20 weight portions
Solution, continues heating stirring and reacts 1 ~ 5 hour；（5）Stop reaction, by final product filtering and washing, 3 are dried at 60 ~ 100 DEG C
~ 5 hours, you can.
2. the preparation method of a kind of metal oxide graphene composite material according to claim 1, it is characterised in that：Step
Suddenly（1）Described in organic monomer be at least one in aniline, ortho-aminotoluene, meta-aminotoluene.
3. the preparation method of a kind of metal oxide graphene composite material according to claim 1, it is characterised in that：Step
Suddenly（1）Described inorganic acid is at least one in sulfuric acid, hydrochloric acid, phosphoric acid.
4. the preparation method of a kind of metal oxide graphene composite material according to claim 1, it is characterised in that：Step
Suddenly（1）Described in solvent be ethanol and water mixed solution, its volume ratio be ethanol：Water=（0~4）：1.
5. the preparation method of a kind of metal oxide graphene composite material according to claim 1, it is characterised in that：Step
Suddenly（2）Described in initiator be the one kind in ammonium persulfate, potassium peroxydisulfate.
6. the preparation method of a kind of metal oxide graphene composite material according to claim 1, it is characterised in that：Step
Suddenly（3）Described in organic acid be one or more mixing in tartaric acid, malic acid, oxalic acid.
7. the preparation method of a kind of metal oxide graphene composite material according to claim 1, it is characterised in that：Step
Suddenly（4）Described in soluble metallic salt be one or more in soluble ferric iron salt, manganese salt, zinc salt, barium salt, cobalt salt, nickel salt
Mixing.
8. metal oxide Graphene obtained in the preparation method of the metal oxide graphene composite material described in claim 1
Composite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117482A (en) * | 2019-05-28 | 2019-08-13 | 苏州科技大学 | A kind of preparation method of graphene-based electric heating phase-change material |
| CN114316655A (en) * | 2022-01-17 | 2022-04-12 | 山东金利特新材料有限责任公司 | Preparation process and application of graphene oxide/nano barium sulfate composite material |
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| CN103971942A (en) * | 2014-05-23 | 2014-08-06 | 武汉工程大学 | Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof |
| CN105161314A (en) * | 2015-08-26 | 2015-12-16 | 西南石油大学 | Nano nickel oxide/nickel/graphene composite material and preparation method and application thereof |
| CN105845907A (en) * | 2016-04-11 | 2016-08-10 | 河南工程学院 | Preparation method for lithium titanate-graphene composite negative electrode material |
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| CN103971942A (en) * | 2014-05-23 | 2014-08-06 | 武汉工程大学 | Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof |
| CN105161314A (en) * | 2015-08-26 | 2015-12-16 | 西南石油大学 | Nano nickel oxide/nickel/graphene composite material and preparation method and application thereof |
| CN105845907A (en) * | 2016-04-11 | 2016-08-10 | 河南工程学院 | Preparation method for lithium titanate-graphene composite negative electrode material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117482A (en) * | 2019-05-28 | 2019-08-13 | 苏州科技大学 | A kind of preparation method of graphene-based electric heating phase-change material |
| CN114316655A (en) * | 2022-01-17 | 2022-04-12 | 山东金利特新材料有限责任公司 | Preparation process and application of graphene oxide/nano barium sulfate composite material |
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