CN105129790B - A kind of method that graphene oxide is prepared under condition of supercritical water - Google Patents
A kind of method that graphene oxide is prepared under condition of supercritical water Download PDFInfo
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- CN105129790B CN105129790B CN201510651433.8A CN201510651433A CN105129790B CN 105129790 B CN105129790 B CN 105129790B CN 201510651433 A CN201510651433 A CN 201510651433A CN 105129790 B CN105129790 B CN 105129790B
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Abstract
The invention provides a kind of method that graphene oxide is prepared under condition of supercritical water, the method includes following step：It is 1 in mass ratio graphite and water：After 2～200 ratio mixing, put in supercritical reaction device；To in reactor, first add oxidant, then the closed reactor, graphite with the mass ratio of the addition of oxidant to be：1:0.1～10；Increasing temperature and pressure, makes reaction system reach the supercriticality of water, i.e. 374.3 DEG C of temperature, and critical pressure is more than 22.1MPa, starts reaction；The time of 1min～2h is reacted under the conditions of keeping the supercriticality of water；After reaction terminates, pressure release of lowering the temperature, blowing；Reacted material obtains graphene oxide Jing after ultrasound wave decentralized processing, after filtering, and scrubbed, drying is to butt graphene oxide product.Beneficial effects of the present invention are：Make use of water special characteristics in the supercritical state, by adding the oxidant such as oxygen, can be quickly graphene oxide graphite oxidation, during the not heavy metal such as the substantial amounts of Waste Sulfuric Acid of by-product, manganese, post processing is simple, and product can be easily separated, environmental friendliness.Course of reaction is not related to strong acid, and course of reaction is steady, it is easy to control, and is the new method for meeting green chemical synthesis.
Description
Technical field
The present invention relates to be related to a kind of production method of graphene oxide, and in particular to one kind is made under condition of supercritical water
The method of standby graphene oxide.
Background technology
Graphene has just caused huge sensation, quilt since being found from 2004 first as a kind of novel single-layer material with carbon element
The best material of most hard, electric conductivity in the world is described as, its excellent energy-storage property and big specific surface area, Graphene is added
Range of application is very wide.
Graphene is mainly by mechanically pulling off method and is obtained, additionally, vapour deposition (CVD) method, epitaxial growth method etc. can all be made
The larger graphene film of standby area, but high cost, which has limited its business application.
At present, native graphite oxidation is obtained into graphite oxide, increase graphite layers are away from the later stage is peeled off, and oxidation is obtained
Graphene (graphiteoxide, GO).Graphene is prepared in the way of redox graphene, can be used as a large amount of production graphite
The strategic starting point of alkene.
And graphene oxide is used as the intermedium of Graphene and graphite oxide, which not only inherits graphite to a certain extent
The excellent properties of alkene, and the oxy radical that surface of graphene oxide possesses gives its surface activity, as surface-functionalized place
The active site of reason so as to can preferably merge with organic substrate, prepares the functional material of excellent performance.Therefore, graphite oxide
The type and quantity of alkene Surface oxygen-containing groups determine the quality of the functionalization and performance of composite.
The main method for preparing graphite oxide has Bordie methods, Saudenmaier methods and Hummers methods.This 3 kinds of methods
In, it is the safest and stable with Hummers oxidizing process, therefore graphite oxide is produced using this mode in great majority research.But
It is that Hummers oxidizing process needs to react under strongly acidic conditions, side-product is substantial amounts of acid-bearing wastewater, product separation and waste water
Process it is all extremely difficult, be badly in need of a kind of simple, easy, environmentally friendly, safe production method.
Supercritical water has the property of liquids and gases, the property with vaporous water, and the property with aqueous water.Thus
With special dissolubility, the density of malleable, relatively low viscosity, relatively low surface tension and higher diffusibility, so living
Property it is very good, reactivity it is extremely strong.
When being passed through oxygen in supercritical water, C H keys weaker in active oxygen attack organic molecule produce one very
Important free radical HO2, it generates H2O2 with the H in Organic substance, and H2O2 is further broken into the very strong free radical HO of electrophilicity,
Free radical HO generates free radical R with the effect of Organic substance containing H, and free radical R generates peroxylradicals ROO with oxygen effect.
Formal this characteristic using supercritical water of the invention, carries out oxidation graphite and prepares graphene oxide, reaction tool
Have quick, safe, the advantage such as environmental protection significantly reduces ambient pressure, and subsequent treatment becomes simple so that graphene oxide
Synthesis realize greenization, environmental protection, cost degradation.With especially great meaning.
The content of the invention
The purpose of the present invention is precisely in order to overcome the shortcomings of above-mentioned technology, and provide one kind and prepare under condition of supercritical water
The method of graphene oxide.
The purpose of the present invention is by following technical solution completing.It is this that oxidation stone is prepared under condition of supercritical water
The method of black alkene, the method include following step：
A. it is 1 in mass ratio graphite and water：After 2～200 ratio mixing, put in supercritical reaction device；
B. in reactor, first add oxidant, then the closed reactor, graphite with the mass ratio of the addition of oxidant to be：
1:0.1～10；
C. increasing temperature and pressure, makes reaction system reach the supercriticality of water, i.e. 374.3 DEG C of temperature, and critical pressure is
More than 22.1MPa, starts reaction；
D. the time of 1min～2h is reacted under the conditions of the supercriticality for keeping water；
E. after reaction terminates, pressure release of lowering the temperature, blowing；
F. reacted material obtains graphene oxide, scrubbed, drying Jing after ultrasound wave decentralized processing, after filtering
Butt graphene oxide product is obtained.
The oxidant of the addition in b step is oxygen, hydrogen peroxide, ozone, SODIUM PERCARBONATE, potassium percarbonate, Na2O2Deng each
Plant the material with oxidisability or other meet the material that water release oxygen, the preferred hydrogen peroxide of the present invention.
It is reaction promoter to add hydrochloric acid, sulphuric acid or acidic materials in b step, and acid adding amount is the H for controlling reactant liquor+Concentration
For 0～30%, the speed of reaction is properly increased, being not added with the reaction can also be carried out.
Beneficial effects of the present invention are：Present invention utilizes water special characteristics in the supercritical state, by adding oxygen
Deng oxidant, can quickly graphite oxidation be graphene oxide, during not the substantial amounts of Waste Sulfuric Acid of by-product, manganese etc. a huge sum of money
Category, post processing are simple, and product can be easily separated, environmental friendliness.Course of reaction is not related to strong acid, and course of reaction is steady, it is easy to control,
It is the method for meeting green chemical synthesis.
Description of the drawings
Fig. 1 is the ultraviolet-visible light analysis of spectrum schematic diagram of the present invention.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, and embodiment will facilitate a better understanding of this
It is bright, but the present invention is not limited only to following embodiments.
This method that graphene oxide is prepared under condition of supercritical water, the method include following step：
A. it is 1 in mass ratio graphite and water：After 2～200 ratio mixing, put in supercritical reaction device；
B. in reactor, first add oxidant, then the closed reactor, graphite with the mass ratio of the addition of oxidant to be：
1:0.1～10；
C. increasing temperature and pressure, makes reaction system reach the supercriticality of water, i.e. 374.3 DEG C of temperature, and critical pressure is
More than 22.1MPa, starts reaction；
D. the time of 1min～2h is reacted under the conditions of the supercriticality for keeping water；
E. after reaction terminates, pressure release of lowering the temperature, blowing；
F. reacted material obtains graphene oxide, scrubbed, drying Jing after ultrasound wave decentralized processing, after filtering
Butt graphene oxide product is obtained.
The oxygen for decomposing generation in dispensing is formed active oxygen, in graphite using the high activity of supercritical water by the present invention
Interlayer forms carboxyl, hydroxyl etc., directly prepares graphite oxide, then by ultrasonic separation, obtains graphene oxide product.The party
Method includes following step：The oxidant such as selected graphite and water, hydrogen peroxide is mixed, is put in reactor, it is closed, so
Afterwards more than the supercriticality (374.3 DEG C of temperature, critical pressure is 22.1MPa) of reaction system temperature-pressure to water, carry out
Oxidation reaction, response time 1min～2h, pressure and temperature reducing blowing, blowing mother solution pass through ultrasonic Treatment, then sedimentation filtration
Insoluble matter is removed, pulpous state graphene oxide product is obtained final product, butt graphene oxide product after drying, is obtained.
Embodiment 1,1g native graphites, 20ml water are taken, the hydrogen peroxide of 4ml27.5% pours the supercritical water reaction of 250mL into
In device, sealing, then by beginning to warm to 380 DEG C, is pressurized to 25MPa so that the water in reaction system is in supercritical state
State, keeps response time 20min, pressure release, cools to 50 DEG C or so, blowing, then carry out break process, time with Ultrasound Instrument
20min, filters, and washing obtains sample a after being dried.
Embodiment 2,1g native graphites, 40ml water are taken, the hydrogen peroxide of 8ml27.5% pours the supercritical water reaction of 250mL into
In device, sealing, then by beginning to warm to 400 DEG C, is pressurized to 30MPa so that the water in reaction system is in supercritical state
State, keeps response time 5min, pressure release, cools to 50 DEG C or so, blowing, then carry out break process, time with Ultrasound Instrument
20min, filters, and washing obtains sample b after being dried.
Embodiment 3,1g native graphites, 40ml water are taken, poured in the supercritical water reaction device of 250mL, being passed through 2g oxygen,
Sealing, then by beginning to warm to 400 DEG C, is pressurized to 35MPa so that the water in reaction system is in a supercritical state, protects
Hold response time 40min, pressure release, cool to 50 DEG C or so, blowing, then carry out break process with Ultrasound Instrument, time 20min,
Filter, washing obtains sample c after being dried.
Embodiment 4,1g native graphites, 40ml water are taken, the hydrogen peroxide of 8ml27.5% pours the supercritical water reaction of 250mL into
The concentrated sulphuric acid of 10ml 98% in device, is added, is sealed, is then begun to warm to 400 DEG C, be pressurized to 30MPa so that reactant
Water in system is in a supercritical state, keeps response time 2min, pressure release, cools to 50 DEG C or so, blowing, then uses Ultrasound Instrument
Break process is carried out, time 20min is filtered, and washing obtains sample d after being dried.
4 samples of above-mentioned a, b, c, d are used into ultraviolet-visible light analysis of spectrum respectively, at ultraviolet-visible spectrum area 230nm
There is absworption peak (such as Fig. 1),
According to related data, the absworption peak may be considered be graphene oxide characteristic peak.
Finally it is pointed out that above example is only the more representational example of the present invention.Obviously, technical side of the invention
Case is not limited to examples detailed above, can also have many deformations, and one of ordinary skill in the art can be from present disclosure
The all deformations directly derived or associate, are considered as protection scope of the present invention.
Claims (3)
1. a kind of method that graphene oxide is prepared under condition of supercritical water, it is characterised in that：The method includes following
Step：
A. it is 1 in mass ratio graphite and water：After 2～200 ratio mixing, put in supercritical reaction device；
B. in reactor, first add oxidant, then the closed reactor, graphite with the mass ratio of the addition of oxidant to be：1:
0.1～10；
C. increasing temperature and pressure, makes reaction system reach the supercriticality of water, i.e. 374.3 DEG C of temperature, critical pressure be 22.1MPa with
On, start reaction；
D. the time of 1min～2h is reacted under the conditions of the supercriticality for keeping water；
E. after reaction terminates, pressure release of lowering the temperature, blowing；
F. reacted material obtains graphene oxide, scrubbed, drying Jing after ultrasound wave decentralized processing, after filtering
To butt graphene oxide product.
2. the method that graphene oxide is prepared under condition of supercritical water according to claim 1, it is characterised in that：In b
The oxidant of the addition in step is oxygen, hydrogen peroxide, ozone, SODIUM PERCARBONATE, potassium percarbonate, Na2O2Or other are met water and release oxygen
Material.
3. the method that graphene oxide is prepared under condition of supercritical water according to claim 1, it is characterised in that：In b
It is reaction promoter to add hydrochloric acid or sulphuric acid in step.
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| CN106044764B (en) * | 2016-08-17 | 2019-02-12 | 新奥科技发展有限公司 | The overcritical device and method for preparing graphene |
| CN106044765A (en) * | 2016-08-17 | 2016-10-26 | 新奥科技发展有限公司 | Apparatus and method of supercritically preparing graphene |
| CN106395808B (en) * | 2016-10-31 | 2019-01-15 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of graphene oxide |
| CN106744910A (en) * | 2017-01-16 | 2017-05-31 | 王奉瑾 | A kind of preparation method of graphene oxide |
| CN106829938B (en) * | 2017-03-09 | 2018-10-23 | 辽宁兰晶科技有限公司 | The method that overcritical sulfur hexafluoride stripping prepares graphene or graphene nanometer sheet |
| CN106966382A (en) * | 2017-04-11 | 2017-07-21 | 齐鲁工业大学 | A kind of method of overcritical continuous hydrothermal synthesizing graphite alkene quantum dot |
| CN108609613B (en) * | 2018-07-27 | 2021-09-17 | 郑州大学 | Preparation method of defect-free graphene |
| CN108706581A (en) * | 2018-08-08 | 2018-10-26 | 多凌新材料科技股份有限公司 | The method that supercritical fluid auxiliary prepares graphene oxide |
| CN108689403A (en) * | 2018-08-30 | 2018-10-23 | 多凌新材料科技股份有限公司 | The method that supercritical fluid auxiliary prepares expansible graphite |
| CN112209371A (en) * | 2020-10-15 | 2021-01-12 | 北京石墨烯研究院有限公司 | Supercritical preparation method of graphene oxide |
| CN112300456B (en) * | 2020-11-09 | 2021-09-24 | 江苏加富新材料科技有限公司 | Composition for anti-static rubber floor, anti-static rubber floor and preparation method thereof |
| CN112320771B (en) * | 2020-11-11 | 2021-10-12 | 深圳大学 | Thin-layer porous g-C prepared by supercritical water3N4Method (2) |
| CN114639889B (en) * | 2022-03-29 | 2023-07-14 | 西安交通大学 | Method for in-situ restoration of waste lithium battery anode material by supercritical water |
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| CN102115078B (en) * | 2011-01-19 | 2012-12-26 | 上海交通大学 | Method for preparing graphene by using supercritical fluid |
| CN104229787B (en) * | 2014-09-18 | 2016-08-24 | 上海交通大学 | The method that native graphite pretreatment is improved preparing graphene by using supercritical fluid productivity |
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