CN107128903A - To crimp the method that the halloysite nanotubes of layer structure prepare graphene - Google Patents
To crimp the method that the halloysite nanotubes of layer structure prepare graphene Download PDFInfo
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- CN107128903A CN107128903A CN201710407002.6A CN201710407002A CN107128903A CN 107128903 A CN107128903 A CN 107128903A CN 201710407002 A CN201710407002 A CN 201710407002A CN 107128903 A CN107128903 A CN 107128903A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
To crimp the method that the halloysite nanotubes of layer structure prepare graphene, belong to the preparing technical field of chemical materials, first using water as solvent, small organic molecule is mixed with crimping the powdery halloysite nanotubes of layer structure, the halloysite nanotubes that interlayer is inserted with small organic molecule are obtained；Small organic molecule is replaced with polymer monomer again, it is aggregated, the compound of polymer and halloysite nanotubes is obtained, is washed after calcining using the mixed solution of hydrofluoric acid and hydrochloric acid, obtains graphene powder.The present invention can prepare the graphene with 2~4 Rotating fields, and preparation method is simple, easy to operate, it is low to prepare cost and will not produce pollution to environment.
Description
Technical field
The invention belongs to the preparing technical field of chemical materials, and in particular to the technology of preparing of graphene nano material.
Background technology
2004, Univ Manchester UK physicist Geim and Novoselov succeed first to be isolated from graphite
Single-layer graphene, is used as the most thin, maximum intensity, electrical and thermal conductivity performance having now been found that a kind of most strong novel nano-material, stone
Black alkene is referred to as " dark fund ", is " king of new material ", and scientist even foretells that graphene " will thoroughly change 21 century ".Pole has can
The subversiveness have swept the globe a new technology new industrial revolution can be started.
The preparation method of graphene, mainly have at present mechanical stripping method, crystal epitaxy method, chemistry redox method,
Chemical vapour deposition technique etc..Mechanical stripping method efficiency is low, and cost is high, is not suitable for large-scale production；Epitaxial growth method energy consumption is larger；
Chemical vapour deposition technique complex process, prepares cost higher；Graphene defect prepared by oxidation-reduction method is more, and can be in system
A large amount of waste liquids are produced during standby, are unfavorable for environment.
In recent years, the research for preparing carbon material with organic and inorganic template receives much concern.Generally using larger molecular organicses as
Carbon source, mineral are template, are carbonized under inert gas shielding, then remove the carbon material in template, released mineral template.Sun
Deng [Chemical Communications, 2012,65 (65):8126-8128.] with stratified material hydrotalcite（LDH）As
Template, interlayer is strutted with dodecyl sodium sulfate, and MMA makees to lead to Ar, H at carbon source, 900 DEG C2Calcining carbonization, is finally used under ultrasound
Salt acid attack removes the metal ions such as Mg, Al and has obtained graphene.[the Rsc Advances, 2014,5 (10) such as Zhu:7522-
7528] using the discarded montmorillonite after Liquidity limit dyestuff methylene blue as presoma, preparation N, S are co-doped with miscellany graphene carbon and received
Rice material.[the Angewandte Chemie International Edition, 2012,51 (38) such as Li:9689-92] use
Dicyandiamide and glucose are in N2Then lower 600 DEG C of calcinings, the g-C3N4 structures of in-situ preparation stratiform generate graphite in its interlayer
Alkene.
But the above method is plane using stratiform mould material, and belong to sandwich construction, the graphite of preparation
Alkene or class grapheme material are limited by particle size effect, cause the homogeneity of material poor, and preparation cost is high, complex operation,
More difficult control, it is difficult to prepare high-quality graphene or class grapheme material.
The content of the invention
The purpose of the present invention aims to provide that a kind of method is simple, the graphene preparation method of environmental protection.
The present invention comprises the following steps：
1) under normal temperature condition, using water as solvent, by small organic molecule and the powdery halloysite nanotubes of curling layer structure
Mixing, obtains the halloysite nanotubes that interlayer is inserted with small organic molecule；
2）The small organic molecule is replaced with polymer monomer：Under 60~100 DEG C of temperature environment, by polymer monomer with
Above-mentioned organic molecule intercalation halloysite nanotubes are uniformly mixed into line replacement reaction, obtain polymer monomer intercalation galapectite nanometer
Pipe；Home position polymerization reaction is carried out under the conditions of polymer monomer intercalation halloysite nanotubes are placed in into 200~350 DEG C again, must be polymerize
The compound of thing and halloysite nanotubes；
3) compound of polymer and halloysite nanotubes is placed in after being calcined under 650~1000 DEG C of temperature conditionss, then using hydrogen
The mixed solution of fluoric acid and hydrochloric acid is washed, then through washing, drying, obtains graphene powder.
The present invention uses the natural halloysite nanotubes with curling layer structure for template, passes through intercalation modifying method system
It is standby go out the graphene with 2~4 Rotating fields.
The advantage of the invention is that：
（1）The template that the present invention is used is galapectite nano-silicon aluminum pipe, as natural clay, not only stores abundant, with low cost,
, can be with large-scale production and stability is good.
（2）The present invention uses intercalation modifying halloysite nanotubes, its preparation method is simple, easy to operate, it is low to prepare cost and
Pollution will not be produced to environment.
（3）The present invention can control the number of plies of graphene, and the defect phase of product by changing the amount of intercalation carbon source
To less.
（4）Galapectite has the mould material of individual layer interlayer structure, and is coiled structure interlayer structure, with using in the past
Plane layer structure is completely inconsistent, therefore, and the number of plies and size of graphene are easier control, can obtain high-quality, layer
Homogeneous, the large-sized grapheme material of number.
In a word, the inventive method lower cost for material, preparation process is simple, and the obtained graphene powder number of plies is single, face
Product is controllable, it is to avoid Second Aggregation, it is easy to scale.
Further, the interlamellar spacing of the powdery halloysite nanotubes of curling layer structure of the present invention is 7~10.Change
Nano lamellar space provides templatespace to prepare number of plies controllable grapheme, can prepare 2~4 layer graphenes, simultaneously because
It is coiled structure, the graphene of formation deploys after template agent removing is removed by the tension force of itself, efficiently solves graphene nano
Between piece the problem of secondary combination.
The small organic molecule is dimethyl sulfoxide (DMSO) or N-methyl formamide or potassium acetate, these three small organic molecules
With linear structure, possess active group, Hydrogenbond can be formed with crimping the surface hydroxyl of layer structure galapectite, held very much
Easily realize intercalation.
In addition, the mass ratio that feeds intake of small organic molecule and the powdery halloysite nanotubes is 10~12: 1.The ratio
Halloysite nanotubes interlayer intercalation rate can be realized up to 100%, it is ensured that graphene has integrality in the layered structure.
The mass ratio that feeds intake for the halloysite nanotubes that the polymer monomer is inserted with small organic molecule with interlayer is 5~8:
1.The ratio can realize that halloysite nanotubes interlayer organic molecule realizes 100% replacement.
The polymer monomer is that acrylamide or propylene are fine.Acrylamide or propylene it is fine can at high temperature itself occur
Can occur thermal polymerization, without introducing other monomers.
The step 2）Middle calcining heat condition is 650~1000 DEG C, and calcination time is 30min~3h.The temperature can
Intercalation polymeric thing is realized carbonization, form graphene.
The step 3）In, the mixed solution of the hydrofluoric acid and hydrochloric acid by volume ratio for 1: 1 hydrofluoric acid aqueous solution and
Combined is constituted, and the mass percent of the hydrofluoric acid aqueous solution is 40%, the quality percentage of the aqueous hydrochloric acid solution
Than for 37%.The mixed acid can realize the complete removal to galapectite template, while not destroying the integrality and matter of graphene
Amount.
Brief description of the drawings
Fig. 1 is preparation process schematic diagram of the invention.
Fig. 2 is the Raman spectrogram of graphene.
Fig. 3 is the scanning electron microscope (SEM) photograph of graphene.
Fig. 4 is the transmission electron microscope picture of graphene.
Embodiment
The internal diameter of the halloysite nanotubes of curling layer structure is 15~20 nm below, and length is 5~10 μm, interlamellar spacing
For 7~10.
The aqueous hydrochloric acid solution that the hydrofluoric acid aqueous solution and mass percent for being 40% by mass percent are 37% is with 1: 1 body
Product forms the mixed solution of hydrofluoric acid and hydrochloric acid than mixing, standby.
With reference to Fig. 1, the preparation technology of the present invention is further described.
Embodiment 1：
Powdery halloysite nanotubes with curling layer structure are put into 100 DEG C of insulating box and dry 24 h.Take 5g angstroms of Lip river
After stone nanotube, 60g dimethyl sulfoxide (DMSO)s and the mixing of 6mL deionized waters, 72h is stirred at room temperature, and ethanol is washed 2-3 times, and 60 DEG C are done
Dry 48h, obtains dimethyl sulfoxide (DMSO)/halloysite nanotubes intercalated compound.
5g dimethyl sulfoxide (DMSO)s/halloysite nanotubes intercalated compound is taken, 33g acrylonitrile is in round-bottomed flask, magnetic at 80 DEG C
After power stirring reaction 6h, product is washed 2-3 times with absolute ethyl alcohol, 60 DEG C of dry 24h, is obtained acrylonitrile/halloysite nanotubes and is inserted
Layer compound.
Acrylonitrile/halloysite nanotubes intercalated compound is heat-treated 5h at 200 DEG C, makes acrylonitrile in-situ polymerization, obtains
To galapectite/polyacrylonitrile compound.
Galapectite-polyacrylonitrile compound is put into tube furnace, under the conditions of 800 DEG C after calcining 2h, with hydrofluoric acid and
The mixed solution of hydrochloric acid is washed, and removes galapectite template, solution then is washed till into neutrality with deionized water, is dried in vacuo
Afterwards, black graphene powder is obtained.
Fig. 2 is the Raman spectrogram of graphene, as seen from Figure 2：The material has the characteristic peak of typical graphene, and
The number of plies is 2~3 layers.
Fig. 3 and Fig. 4 is graphene ESEM and projection electron microscope, can be proved by Fig. 3,4：The layer of the graphene of acquirement
Number is 4 layers.
Embodiment 2：
Powdery halloysite nanotubes with curling layer structure are put into 100 DEG C of insulating box and dry 24 h.Take 5g angstroms of Lip river
Stone nanotube, 60g potassium acetates and 4mL the deionized waters ground and mixed in mortar are uniform, and room temperature is placed after 24h, and absolute ethyl alcohol is washed
Wash 2-3 times, 60 DEG C of dry 24h obtain galapectite/potassium acetate intercalated compound.
40g acrylamides are taken, are added in 50mL ethanol solutions, after stirring is completely dissolved, round-bottomed flask are poured into, and add 5g
Galapectite/potassium acetate intercalated compound, at 100 DEG C after magnetic agitation reaction 10h, product wash 2-3 times with ethanol, dry at 80 DEG C
Dry 24h, obtains galapectite-acrylamide intercalated compound.By galapectite-acrylamide intercalated compound at 350 DEG C at heat
10h is managed, that is, obtains galapectite/polyacrylamide amine compound.
Galapectite-polyacrylamide amine compound is put into tube furnace, in after calcining 2h under the conditions of 700 DEG C, with hydrofluoric acid
Washed with the mixed solution of hydrochloric acid, remove galapectite template, solution is then washed till neutrality with deionized water, be dried in vacuo
Afterwards, black graphene powder is obtained.
Pass through ESEM and projection electron microscope, it was demonstrated that the number of plies of the graphene of acquirement is 2 layers.
Embodiment 3：
Powdery halloysite nanotubes with curling layer structure are put into 100 DEG C of insulating box and dry 24 h.Take 5g angstroms of Lip river
After stone nanotube, 55g N-methyls formamide and the mixing of 7mL deionized waters, stirring reaction 72h at room temperature, then with absolute ethyl alcohol
Ethanol is washed 2-3 times, and 60 DEG C of dry 48h obtain N-methyl formamide/halloysite nanotubes intercalated compound.
5g N-methyls formamide/halloysite nanotubes intercalated compound is taken, 40g acrylonitrile is added in round-bottomed flask, 90 DEG C
After lower magnetic agitation reaction 5h, washed 2-3 times with absolute ethyl alcohol, 60 DEG C of dry 24h, obtain acrylonitrile/halloysite nanotubes and insert
Layer compound.Acrylonitrile/halloysite nanotubes intercalated compound is heat-treated 5h at 350 DEG C, galapectite/polyacrylonitrile is obtained
Compound.
Galapectite-polyacrylonitrile compound is put into tube furnace, in after calcining 1.5h under the conditions of 950 DEG C, with hydrofluoric acid
Washed with the mixed solution of hydrochloric acid, remove galapectite template, solution is then washed till neutrality with deionized water, be dried in vacuo
Afterwards, black graphene powder is obtained.
Pass through ESEM and projection electron microscope, it was demonstrated that the number of plies of graphene is 3 layers.
Embodiment 4：
Powdery halloysite nanotubes with curling layer structure are put into 100 DEG C of insulating box and dry 24 h.Take 10g angstroms of Lip river
Stone nanotube, 80g potassium acetates and 5.0mL deionized waters are uniformly mixed, and are placed at room temperature after 48h, absolute ethyl alcohol washing 2-3
Secondary, 60 DEG C of dry 48h obtain potassium acetate/halloysite nanotubes intercalated compound.
10g potassium acetates/halloysite nanotubes intercalated compound and 65g acrylonitrile is taken to be put into round-bottomed flask, at 90 DEG C
After magnetic agitation reaction 10h, after being washed 2-3 times with absolute ethyl alcohol, 24h is dried at 80 DEG C, acrylonitrile/halloysite nanotubes are obtained
Intercalated compound.Acrylonitrile/halloysite nanotubes intercalated compound is heat-treated 5h at 300 DEG C, galapectite/polypropylene is obtained
Nitrile compound.
Galapectite-polyacrylonitrile compound is put into tube furnace, under the conditions of 650 DEG C after calcining 3h, with hydrofluoric acid and
The mixed solution of hydrochloric acid is washed, and removes galapectite template, solution then is washed till into neutrality with deionized water, is dried in vacuo
Afterwards, black graphene powder is obtained.
Pass through ESEM and projection electron microscope, it was demonstrated that the number of plies of graphene is 3 layers.
Embodiment 5：
Powdery halloysite nanotubes with curling layer structure are put into 100 DEG C of insulating box and dry 24 h.Take 10g angstroms of Lip river
After stone nanotube, 120g dimethyl sulfoxide (DMSO)s and the mixing of 8mL deionized waters, magnetic agitation 72h at 60 DEG C, absolute ethyl alcohol washing 2-3
It is secondary, 48h is dried at 60 DEG C, dimethyl sulfoxide (DMSO)/halloysite nanotubes intercalated compound is obtained.
50g acrylamides are taken, are added in 100mL ethanol solutions, after stirring is completely dissolved, are poured into round-bottomed flask, and are added
Enter magnetic agitation at 10g dimethyl sulfoxide (DMSO)s/halloysite nanotubes intercalated compound, 90 DEG C and react 10h, washed with absolute ethyl alcohol
2-3 times, 80 DEG C of dry 24h obtain acrylamide/halloysite nanotubes intercalated compound.By acrylamide/halloysite nanotubes
Intercalated compound is heat-treated 10h at 250 DEG C, obtains galapectite/polyacrylamide amine compound.
Galapectite-polyacrylamide amine compound is put into tube furnace, in after calcining 2h under the conditions of 750 DEG C, with hydrofluoric acid
Washed with the mixed solution of hydrochloric acid, remove galapectite template, solution is then washed till neutrality with deionized water, be dried in vacuo
Afterwards, black graphene powder is obtained.
Pass through ESEM and projection electron microscope, it was demonstrated that the number of plies of graphene is 2 layers.
Embodiment 6：
Powdery halloysite nanotubes with curling layer structure are put into 100 DEG C of insulating box and dry 24 h.Take 6g angstroms of Lip river
After stone nanotube, 60g N-methyls formamide and the mixing of 6.6mL deionized waters, 72h, absolute ethyl alcohol washing 2-3 are stirred at room temperature
Secondary, 60 DEG C of dry 48h obtain N-methyl formamide/halloysite nanotubes intercalated compound.
30g acrylamides are taken, are added in 30mL ethanol solutions, after stirring is completely dissolved, are poured into round-bottomed flask, and add
After 5g N-methyls formamide/halloysite nanotubes intercalated compound, 60 DEG C of magnetic agitation reaction 8h, absolute ethyl alcohol washing 2-3
It is secondary, 24h is dried at 80 DEG C, acrylamide/halloysite nanotubes intercalated compound is obtained.By acrylamide/halloysite nanotubes
Intercalated compound is placed in crucible, is put into Muffle furnace, and 10h is calcined at 250 DEG C, that is, is obtained galapectite/polyacrylamide and be combined
Thing.
Galapectite-polyacrylamide amine compound is put into tube furnace, in after calcining 0.5h under the conditions of 1000 DEG C, with hydrogen fluorine
The mixed solution of acid and hydrochloric acid is washed, and removes galapectite template, solution then is washed till into neutrality with deionized water, vacuum is done
After dry, black graphene powder is obtained.
Pass through ESEM and projection electron microscope, it was demonstrated that the number of plies for taking graphene is 2 layers.
Claims (8)
1. to crimp the method that the halloysite nanotubes of layer structure prepare graphene, it is characterised in that comprise the following steps：
1) under normal temperature condition, using water as solvent, by small organic molecule and the powdery halloysite nanotubes of curling layer structure
Mixing, obtains the halloysite nanotubes that interlayer is inserted with small organic molecule；
2）The small organic molecule is replaced with polymer monomer：Under 60~100 DEG C of temperature environment, by polymer monomer with
Above-mentioned organic molecule intercalation halloysite nanotubes are uniformly mixed into line replacement reaction, obtain polymer monomer intercalation galapectite nanometer
Pipe；Home position polymerization reaction is carried out under the conditions of polymer monomer intercalation halloysite nanotubes are placed in into 200~350 DEG C again, must be polymerize
The compound of intercalation halloysite nanotubes；
3) compound of polymer and halloysite nanotubes is placed in after being calcined under 650~1000 DEG C of temperature conditionss, then using hydrogen
The mixed solution of fluoric acid and hydrochloric acid is washed, then through washing, drying, obtains graphene powder.
2. the method according to claim 1 for preparing graphene, it is characterised in that the powdery angstrom of the curling layer structure
The interlamellar spacing of Lip river stone nanotube is 7~10.
3. the method according to claim 1 for preparing graphene, it is characterised in that the small organic molecule and the powder
The mass ratio that feeds intake of shape halloysite nanotubes is 10~12: 1.
4. the method for preparing graphene according to claim 1 or 3, it is characterised in that the small organic molecule is diformazan
Base sulfoxide or N-methyl formamide or potassium acetate.
5. the method according to claim 1 for preparing graphene, it is characterised in that the polymer monomer is inserted with interlayer
The mass ratio that feeds intake of the halloysite nanotubes of small organic molecule is 5~8: 1.
6. the method for graphene is prepared according to claim 1 or 5, it is characterised in that described polymer monomer is propylene
Acid amides or propylene are fine.
7. the method according to claim 1 for preparing graphene, it is characterised in that the step 2）Described in calcination time
For 30min~3h.
8. the method according to claim 1 for preparing graphene, it is characterised in that the step 3）In, the hydrofluoric acid and
The mixed solution of hydrochloric acid is made up of volume ratio for 1: 1 hydrofluoric acid aqueous solution and combined, and the hydrofluoric acid is water-soluble
The mass percent of liquid is 40%, and the mass percent of the aqueous hydrochloric acid solution is 37%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456598A (en) * | 2018-05-29 | 2019-03-12 | 浙江上青元电力科技有限公司 | A kind of selfcurable insulative packaging material |
| CN111501133A (en) * | 2020-05-28 | 2020-08-07 | 中国科学院化学研究所 | Carbon nanofiber based on inorganic structure template and preparation method thereof |
| CN113224275A (en) * | 2021-04-20 | 2021-08-06 | 阳原县仁恒精细粘土有限责任公司 | Graphene/clay nano composite electrode material and preparation method thereof |
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| CN105967167A (en) * | 2016-05-17 | 2016-09-28 | 扬州大学 | Method for preparing one-dimensional carbon nano material |
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| CN105967167A (en) * | 2016-05-17 | 2016-09-28 | 扬州大学 | Method for preparing one-dimensional carbon nano material |
Non-Patent Citations (2)
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| ZHI-LIN CHENG ET AL.: "Templated synthesis of graphene nanosheets within curling layered nanostructure of halloysite nanotubes", 《MATERIALS LETTERS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456598A (en) * | 2018-05-29 | 2019-03-12 | 浙江上青元电力科技有限公司 | A kind of selfcurable insulative packaging material |
| CN111501133A (en) * | 2020-05-28 | 2020-08-07 | 中国科学院化学研究所 | Carbon nanofiber based on inorganic structure template and preparation method thereof |
| CN111501133B (en) * | 2020-05-28 | 2021-05-25 | 中国科学院化学研究所 | Carbon nanofiber based on inorganic structure template and preparation method thereof |
| CN113224275A (en) * | 2021-04-20 | 2021-08-06 | 阳原县仁恒精细粘土有限责任公司 | Graphene/clay nano composite electrode material and preparation method thereof |
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Application publication date: 20170905 |