CN106809831A - A kind of method that utilization swelling agent expanded graphite prepares graphene oxide - Google Patents
A kind of method that utilization swelling agent expanded graphite prepares graphene oxide Download PDFInfo
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- CN106809831A CN106809831A CN201611267991.5A CN201611267991A CN106809831A CN 106809831 A CN106809831 A CN 106809831A CN 201611267991 A CN201611267991 A CN 201611267991A CN 106809831 A CN106809831 A CN 106809831A
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- graphite
- swelling agent
- graphene oxide
- expanded graphite
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Abstract
The present invention discloses a kind of method that utilization swelling agent expanded graphite prepares graphene oxide, in the concentrated sulfuric acid that inflatable crystalline flake graphite is added to (98%) solution, is slowly added to fuming nitric aicd, then dries.Microwave expansion, obtains expanded graphite afterwards；Above-mentioned expanded graphite is taken, is added in the concentrated sulfuric acid, K2S2O8 and P2O5 is slowly added to after dispersed with stirring is uniform, obtain pre-oxidizing graphite；Take pre-oxidation graphite to be added in swelling agent, supernatant liquor is outwelled, be centrifuged, washed, 1mHCl is washed 3 times by the suitable reaction temperature of the different choice according to the swelling agent coefficient of expansion, untill ph is 6 or so, obtains graphene oxide dispersion.The method that the expanded graphite prepares graphene oxide can effectively reduce strong acid waste liquid, reduce pollution, and environmental protection is adapted to large-scale production, is applied to industrial every field.
Description
Technical field
The invention belongs to the preparation field of nano material, and in particular to one kind prepares oxidation stone using swelling agent expanded graphite
The method of black alkene.
Background technology
Graphene is a kind of quasi- two-dimensional material of only one of which atomic layer level thickness, be have now been found that most thin, maximum intensity,
A kind of most strong novel nano-material of electrical and thermal conductivity performance, has non-in fields such as mobile device, Aero-Space, new energy batteries
The application prospect of Chang Ju great.The exploitation and popularization of grapheme material very likely start a subversiveness new technology for have swepting the globe
New industrial revolution.
Graphene oxide is a kind of new carbon of excellent performance, abundant with specific surface area higher and surface
Functional group.Graphene oxide is the product after Graphene oxidation, and graphene oxide still keeps the layer structure of Graphene, but every
Many epoxide functional groups are introduced on one layer of Graphene monolithic, these functional groups bring more to the application of grapheme material
Possibility, with application value higher.
But, this method is only applicable to laboratory and prepares for studying on a small quantity, and it is a large amount of prepare easily produce it is substantial amounts of
Spent acid, waste water etc., will cause the pollution of environment.Therefore, it is badly in need of development a kind of simple, the small Graphene preparation side of environmental pollution
Method.The method of expanded graphite of the present invention is it is possible to prevente effectively from using concentrated acid, greatly reduce concentrated acid waste liquid
Discharge, process is simple, energy-conserving and environment-protective.
The content of the invention
Based on the deficiencies in the prior art, oxygen is prepared it is an object of the invention to provide described utilization swelling agent expanded graphite
The method of graphite alkene, its technical scheme is comprised the following steps：
Include successively the concentrated sulfuric acid and concentrated nitric acid and graphite generation compound between graphite layers, microwave obtain expanded graphite, again with
Strong acid reacts must be pre-oxidized graphite, add swelling agent to obtain graphene oxide dispersion.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, the concentrated sulfuric acid and dense nitre
Acid with graphite generation compound between graphite layers in graphite for 300 μm of 3-5g inflatable crystalline flake graphite, the concentrated sulfuric acid be 150-
The concentrated sulfuric acid (98%) of 250ml, concentrated nitric acid is 30-50ml fuming nitric aicds.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, described microwave must expand
Graphite need to use 1000W microwave expansions one minute.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, described pre-oxidation graphite
Need to be added to expanded graphite in the 200-300ml concentrated sulfuric acids by process, be slow added into 3.6-4.2g K2S2O8And 5.4-6.2g
P2O5, whipping temp is 60-80 degrees Celsius, and the time is 4 hours, and the water of dilution is deionized water.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, the big lamella oxygen described in it
Graphite alkene refers to obtained graphene oxide layer number between 10 to 50.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, obtained graphite layers
Compound needs to dry more than 24h at 60 degrees Celsius, makes moisture content below 0.5%.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, deionization is used described in it
Filtering, the purpose of washing are, the graphite removal for expansion, to need carry out several times more after water dilution.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, swelling agent used is tool
There is the salt of the larger coefficient of expansion, volume can expand rapidly at low or elevated temperatures.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, expansible graphite and expansion
Agent is according to 1:1~1:100 ratio mixing, different mixings time are set according to different swelling agents.
Preferably, the method that above-mentioned utilization swelling agent expanded graphite prepares graphene oxide, selects different swelling agents,
Different whipping temps are set according to its coefficient of expansion, during low temperature, the mode of ice bath or liquid nitrogen can be used to expansible graphite
Mixed liquor with swelling agent is lowered the temperature.
(1) in the concentrated sulfuric acid (98%) solution being added to inflatable crystalline flake graphite, after dispersed with stirring is uniform, it is slowly added to
Fuming nitric aicd, then ice bath stirring.Dilution in water is subsequently poured into, washing is filtered after being cooled to normal temperature, dry 24h.Microwave is swollen afterwards
It is swollen, obtain expanded graphite.
(2) above-mentioned expanded graphite is taken, is added in the concentrated sulfuric acid, K is slowly added to after dispersed with stirring is uniform2S2O8And P2O5, stir
Mix, be subsequently poured into dilution, cooling, washing, drying at room temperature 48h in water, obtain pre-oxidizing graphite.
(3) take above-mentioned pre-oxidation graphite to be added in swelling agent, the different choice according to the swelling agent coefficient of expansion is suitable
Reaction temperature, then stirs, after pour into the dilution of 2L water, stand, supernatant liquor outwelled, be centrifuged, washed, 1mHCl washes 3 times, directly
Being 6 or so to ph, that is, obtain graphene oxide dispersion.
2nd, conventional oxidation Graphene is prepared using Hummers methods, with K2MnO4As oxidant, it is demonstrated experimentally that the method is produced
Rate is relatively low.The breakthrough method expanded to graphite interbed using swelling agent of the present invention, which not only simplifies preparation
Step, also reduces waste liquor contamination.
3rd, the wherein described concentrated sulfuric acid and concentrated nitric acid and graphite generate compound between graphite layers and refer to, in strong oxidizer effect
Under, the original plane reticular macromolecular being combined into sp hydridization is transformed into the plane macromolecular with positive charge in graphite crystal,
Sulfuric acid molecule and bisulfate ion anion the insertion graphite linings with polarity are made to form compound between graphite layers.
4th, wherein described microwave obtains expanded graphite and refers to, compound between graphite layers under microwave condition, between plane macromolecular
Polarity sulfuric acid molecule and bisulfate ion anion energy absorption generation SO2Gas is escaped, so that distance between graphite linings
Increase forms expanded graphite.
5th, wherein described reaction with strong acid again must pre-oxidize graphite and refer to, the graphite after microwave expansion expansion, piece
Distance increase, can fully react with strong acid between layer, make more sulfuric acid molecule and bisulfate ion anion with polarity
Insertion graphite linings, are easy to next step swelling agent to insert graphite interbed.
6th, after swelling agent is added to graphite interbed, low temperature or high-temperature process are carried out to it so that swelling agent volumetric expansion, is obtained
To the graphene oxide that performance is more excellent.
Specific embodiment
Embodiment 1
(1) raw material used in this technique is 300 microns of natural flake graphites of 3g, and graphite first is added into the 150ml concentrated sulfuric acids
In, 30ml nitric acid is being slowly added to after dispersed with stirring is uniform, then ice bath is stirred 24 hours.
(2) mixture that will be obtained is poured into the deionized water of 1000ml and diluted, and washing, 60 degree are filtered after being cooled to normal temperature
Dry 24 hours.1000W microwave expansions afterwards, until all graphite are all changed into cotton-shaped.
(3) 3.6g K are being added2SO8With 5.4g P2O5When need to slowly carry out, afterwards 60 degree stirring 5h.Pour into dilute in 2L water
Release, be cooled to suction filtration washing after normal temperature.Drying at room temperature 48h.
(4) the pre-oxidation graphite that will be obtained is added to 300ml Sc2In W solution, 24h is sufficiently stirred at room temperature, then will
Stirring sufficiently pre-oxidizes graphite and Sc2W mixtures refer to rapid cooling in being put into frozen water, obtain pre-oxidizing graphene dispersion
Liquid.
Embodiment 2
First three step is consistent with example 1, will finally pre-oxidize in graphite addition ammonium bicarbonate soln, fully stirs at room temperature
24h is mixed, then sufficiently pre-oxidation graphite is heated with the mixture of ammonium hydrogen carbonate by stirring, obtains pre-oxidation Graphene point
Dispersion liquid.
Above-mentioned specific embodiment, simply to the description of preferential implementation of the invention, can not constitute protection of the present invention
The limitation of scope.The various modification and variation that those skilled in the art make to technical scheme, all should fall into invention
Claims determine protection domain in.
Claims (10)
1. a kind of method that utilization swelling agent expanded graphite prepares graphene oxide, it is characterised in that：Successively include the concentrated sulfuric acid and
Concentrated nitric acid and graphite generation compound between graphite layers, microwave obtain expanded graphite, reacted with strong acid again and must pre-oxidize graphite, add
Swelling agent obtains graphene oxide dispersion.
2. the method that utilization swelling agent expanded graphite according to claim 1 prepares graphene oxide, it is characterised in that institute
It is the inflatable crystalline flake graphite of 300 μm of 3-5g that the concentrated sulfuric acid and concentrated nitric acid are stated with graphite in graphite generation compound between graphite layers,
The concentrated sulfuric acid is the concentrated sulfuric acid (98%) of 150-250ml, and concentrated nitric acid is 30-50ml fuming nitric aicds.
3. the method that utilization swelling agent expanded graphite according to claim 1 and 2 prepares graphene oxide, its feature exists
In described microwave obtains expanded graphite and need to use 1000W microwave expansions one minute.
4. the method that the utilization swelling agent expanded graphite according to any one of claim 1-3 prepares graphene oxide, its
It is characterised by, need to be added to expanded graphite in the 200-300ml concentrated sulfuric acids by described pre-oxidation graphite process, be slow added into
3.6-4.2g K2S2O8With 5.4-6.2g P2O5, whipping temp is 60-80 degrees Celsius, and the time is 4 hours, the water of dilution for go from
Sub- water.
5. the method that the utilization swelling agent expanded graphite according to any one of claim 1-4 prepares graphene oxide, its
It is characterised by, the big lamella graphene oxide described in it refers to obtained graphene oxide layer number between 10 to 50.
6. the method that the utilization swelling agent expanded graphite according to any one of claim 1-5 prepares graphene oxide, its
It is characterised by, obtained compound between graphite layers need to dry more than 24h at 60 degrees Celsius, makes moisture content below 0.5%.
7. the method that the utilization swelling agent expanded graphite according to any one of claim 4-6 prepares graphene oxide, its
It is characterised by, described in it is that, the graphite removal for being expansion, need to carry out with filtering, the purpose washed after deionized water dilution more
Several times.
8. the method that the utilization swelling agent expanded graphite according to any one of claim 1-7 prepares graphene oxide, its
It is characterised by, swelling agent used is the salt with the larger coefficient of expansion, volume can expand rapidly at low or elevated temperatures.
9. the method that the utilization swelling agent expanded graphite according to any one of claim 1-8 prepares graphene oxide, its
It is characterised by, expansible graphite is with swelling agent according to 1:1~1:100 ratio mixing, sets different according to different swelling agents
Mixing time.
10. the method that the utilization swelling agent expanded graphite according to any one of claim 1-9 prepares graphene oxide, its
It is characterised by, selects different swelling agents, different whipping temps are set according to its coefficient of expansion, during low temperature, ice can be used
Mixed liquor cooling of the mode of bath or liquid nitrogen to expansible graphite and swelling agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673341A (en) * | 2017-11-02 | 2018-02-09 | 湖南衡义材料科技有限公司 | A kind of method that large-area high-quality graphene is prepared using expansible graphite |
| CN108190876A (en) * | 2018-02-26 | 2018-06-22 | 北京环境特性研究所 | A kind of graphene composite absorber and preparation method thereof |
| CN113511652A (en) * | 2019-08-22 | 2021-10-19 | 常州富烯科技股份有限公司 | Graphene oxide film and preparation method thereof |
| CN114702030A (en) * | 2022-05-18 | 2022-07-05 | 山东大学 | Preparation method of ultrathin flexible graphene film |
-
2016
- 2016-12-31 CN CN201611267991.5A patent/CN106809831A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673341A (en) * | 2017-11-02 | 2018-02-09 | 湖南衡义材料科技有限公司 | A kind of method that large-area high-quality graphene is prepared using expansible graphite |
| CN108190876A (en) * | 2018-02-26 | 2018-06-22 | 北京环境特性研究所 | A kind of graphene composite absorber and preparation method thereof |
| CN113511652A (en) * | 2019-08-22 | 2021-10-19 | 常州富烯科技股份有限公司 | Graphene oxide film and preparation method thereof |
| CN113511652B (en) * | 2019-08-22 | 2022-08-19 | 常州富烯科技股份有限公司 | Graphene oxide film and preparation method thereof |
| CN114702030A (en) * | 2022-05-18 | 2022-07-05 | 山东大学 | Preparation method of ultrathin flexible graphene film |
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Application publication date: 20170609 |