CN109019585A - Fenton reagent prepares graphene oxide - Google Patents
Fenton reagent prepares graphene oxide Download PDFInfo
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- CN109019585A CN109019585A CN201811138234.7A CN201811138234A CN109019585A CN 109019585 A CN109019585 A CN 109019585A CN 201811138234 A CN201811138234 A CN 201811138234A CN 109019585 A CN109019585 A CN 109019585A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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Abstract
The invention belongs to graphene sciemtifec and technical spheres, and in particular to a kind of preparation method of graphene oxide.A kind of Fenton reagent of the present invention prepares graphene oxide method, the specific steps are as follows: (1) pretreatment of raw material: after mixing by graphite and aqueous solution, regulation system pH value, heating obtains acidic mixed material；(2) aoxidize: after the cooling of acidic mixed material, addition Fenton reagent, aqueous solution are reacted, and obtain graphite oxide solution；(3) it washes: centrifugation, washing graphite oxide solution to neutrality；(4) ultrasonic: step (3) acquired solution to be diluted, ultrasound, freeze-drying obtains graphene oxide product.A kind of preparation method of graphene oxide of the present invention is easy to operate, mild condition and pollution-free, and the graphene oxide single layer rate of preparation is high.
Description
Technical field
The present invention relates to technical field of graphene, and in particular to a kind of Fenton reagent prepares graphene oxide method.
Technical background
Graphene is by carbon atom with sp2The honeycomb flat film that hydridization form is constituted, only one atomic layer level thickness
Quasi- two-dimensional material, also known as monoatomic layer graphite.The design feature of graphene, make it have good intensity, it is flexible, lead
The performances such as electric, thermally conductive, optics, are widely used in every field.Graphene oxide is the oxide of graphene, ratio with higher
Surface area and surface functional group abundant.Currently, it is mainly improved Hummer method that Fenton reagent, which prepares graphene oxide method,
Deng.The strong oxidizers such as the strong acid such as the concentrated sulfuric acid, perchloric acid, concentrated nitric acid and potassium permanganate are all employed in the methods of Hummer preparation,
So that preparation process risk is high, seriously polluted, at high cost, and preparation process is cumbersome, efficiency is lower.Pass through Hummers method
Graphene obtained, conjugated structure seriously affect its performance by very havoc.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of Fenton reagents to prepare graphene oxide method.The present invention
The Fenton reagent prepares graphene oxide method, the specific steps are as follows:
(1) pretreatment of raw material: after mixing by graphite and aqueous solution, regulation system pH value, heating obtains acidic mixture
Material；
(2) aoxidize: after the cooling of acidic mixed material, addition Fenton reagent, aqueous solution are reacted, and it is molten to obtain graphite oxide
Liquid；
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: step (3) acquired solution to be diluted, ultrasound, freeze-drying obtains graphene oxide product.
Wherein:
In step (1), the graphite is crystalline flake graphite or expanded graphite or pre-oxidation graphite.Because expanded graphite and just
Graphite oxide short texture is walked, piece interlamellar spacing is larger, is conducive to the progress of oxidation reaction, and lamella is easily peeled off.
In step (1), the range of the pH value is 2 ~ 5.Preferably, pH value 3.
In step (1), the reaction temperature is 50 ~ 90 DEG C, and the reaction time is 0.5 ~ 8 h.
It is described to be cooled to 30 ~ 70 DEG C in step (2), the reaction time is 2 ~ for 24 hours.Reaction temperature is excessively high, so that Fenton reagent
Bury in oblivion, influences the degree of oxidation of graphite；Reaction temperature is too low, so that Fenton reagent utilization rate is low.
In step (2), the Fenton reagent be hydrogen peroxide (hereinafter referred to as: H2O2)/ferrous sulfate (hereinafter referred to as:
FeSO4) system, H2O2With FeSO4Quality Wei not 7:1 ~ 11:1.Preferably, H2O2With FeSO4Quality Wei not 8:1.
In step (2), the reaction system is under water bath condition or under water-bath and ultraviolet lamp irradiation condition or water-bath and super
Under the conditions of sound or under the conditions of electrochemical redox.Preferably, system reaction is under water-bath and ultraviolet lamp irradiation condition or water-bath
With under ultrasound condition or under the conditions of electrochemical redox.
In step (4), the graphite oxide diluted concentration is 0.5 ~ 2 g/L, and the ultrasonic time is 0.5 ~ 5 h.It is excellent
Choosing, the graphite oxide diluted concentration is 1 g/L.
Compared with the prior art, the present invention has the following beneficial effects:
The green Fenton reagent that the present invention uses is oxidant, and reaction speed is fast, and reaction condition is mild, and equipment is simple, and energy consumption is small,
Other impurities, the complete H of unreacted are not introduced in oxidation process2O2It can voluntarily decompose, secondary pollution will not be caused.Fenton reagent generates
Hydroxyl radical free radical and carbon-carbon double bond addition reaction occurs, the reticular structure of graphene oxide is destroyed smaller, is conducive to prepare
The high graphene of conductivity；Hydroxyl radical free radical small volume, is easily inserted graphite flake layer, increases spacing between layers,
Convenient for preparing the high graphene oxide of single layer rate.
Specific embodiment
Embodiment 1
A kind of Fenton reagent prepares graphene oxide method, and steps are as follows:
(1) pretreatment of raw material: after mixing by 1 g crystalline flake graphite and aqueous solution, the value of regulation system pH=4 is warming up to 85 DEG C instead
1h is answered, acidic mixed material is obtained；
(2) it aoxidizes: acidic mixed material being cooled to 60 DEG C, Fenton reagent, aqueous solution is added, 2 h are reacted under water-bath, are obtained
Graphite oxide solution, the Fenton reagent: H2O2With FeSO4Quality Wei not 8:1；
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: it is 1 g/L, 1.5 h of ultrasound that step (3) acquired solution, which is diluted concentration, and freeze-drying obtains oxidation stone
Black alkene product.
Embodiment 2
A kind of Fenton reagent prepares graphene oxide method, and steps are as follows:
(1) pretreatment of raw material: after mixing by 1 g expanded graphite and aqueous solution, the value of regulation system pH=3 is warming up to 80 DEG C instead
1.5 h are answered, acidic mixed material is obtained；
(2) it aoxidizes: acidic mixed material being cooled to 70 DEG C, Fenton reagent, aqueous solution is added, 8 h are reacted under water-bath, are obtained
Graphite oxide solution, the Fenton reagent: H2O2With FeSO4Quality Wei not 8:1.5；
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: it is 1.5 g/L, 5 h of ultrasound that step (3) acquired solution, which is diluted concentration, and freeze-drying obtains oxidation stone
Black alkene product.
Embodiment 3
A kind of Fenton reagent prepares graphene oxide method, and steps are as follows:
(1) pretreatment of raw material: 1 g is pre-oxidized into graphite and aqueous solution after mixing, the value of regulation system pH=5 is warming up to 90 DEG C
2h is reacted, acidic mixed material is obtained；
(2) it aoxidizes: acidic mixed material being cooled to 50 DEG C, Fenton reagent, aqueous solution is added, reacts for 24 hours, obtains under water-bath
Graphite oxide solution, the Fenton reagent: H2O2With FeSO4Quality Wei not 10:1；
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: it is 0.5 g/L, 2 h of ultrasound that step (3) acquired solution, which is diluted concentration, and freeze-drying obtains oxidation stone
Black alkene product.
Embodiment 4
A kind of Fenton reagent prepares graphene oxide method, and steps are as follows:
(1) pretreatment of raw material: after mixing by 1 g expanded graphite and aqueous solution, the value of regulation system pH=3 is warming up to 90 DEG C instead
2 h are answered, acidic mixed material is obtained；
(2) aoxidize: acidic mixed material being cooled to 50 DEG C, Fenton reagent, aqueous solution is added, water-bath and wavelength be 185 ~
6 h are reacted under the ultraviolet light irradiation of 250nm, obtain graphite oxide solution, the Fenton reagent: H2O2With FeSO4Quality be not
8:1；
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: it is 0.5 g/L, 1.5 h of ultrasound that step (3) acquired solution, which is diluted concentration, and freeze-drying is aoxidized
Graphene product.
Embodiment 5
A kind of Fenton reagent prepares graphene oxide method, and steps are as follows:
(1) pretreatment of raw material: after mixing by 1 g expanded graphite and aqueous solution, the value of regulation system pH=3,
90 DEG C of 2 h of reaction are warming up to, acidic mixed material is obtained；
(2) it aoxidizes: acidic mixed material being cooled to 50 DEG C, Fenton reagent, aqueous solution is added, in water-bath and 40KHz, 500W is super
Ultrasound is lower in sound washer reacts 10 h, the Fenton reagent: H2O2With FeSO4Quality Wei not 8:1；
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: it is 0.5 g/L, 4 h of ultrasound that step (3) acquired solution, which is diluted concentration, and freeze-drying obtains oxidation stone
Black alkene product.
Embodiment 6
A kind of Fenton reagent prepares graphene oxide method, and steps are as follows:
(1) pretreatment of raw material: after mixing by 1 g expanded graphite and aqueous solution, the value of regulation system pH=3 is warming up to 90 DEG C instead
2 h are answered, acidic mixed material is obtained；
(2) it aoxidizes: successively by acidic mixed material, H2O2, be added electrochemical reactor in, in reactor with plate iron be sun
Pole, porous carbon electrodes are cathode, and electrode both end voltage is 30V, and 12 h are reacted under electrochemical redox, obtain graphite oxide
Solution.
(3) it washes: centrifugation, washing graphite oxide solution to neutrality；
(4) ultrasonic: it is 0.5 g/L, 1 h of ultrasound that step (3) acquired solution, which is diluted concentration, and freeze-drying obtains oxidation stone
Black alkene product.
Claims (8)
1. a kind of Fenton reagent prepares graphene oxide method, it is characterised in that: specific step is as follows:
Pretreatment of raw material: after mixing by graphite and aqueous solution, regulation system pH value, heating obtains acidic mixed material；
Oxidation: after the cooling of acidic mixed material, addition Fenton reagent, aqueous solution are reacted, and obtain graphite oxide solution；
Washing: centrifugation, washing graphite oxide solution to neutrality；
Ultrasound: step (3) acquired solution is diluted, and ultrasound, freeze-drying obtains graphene oxide product.
2. a kind of Fenton reagent according to claim 1 prepares graphene oxide method, it is characterised in that: the graphite
For crystalline flake graphite or expanded graphite or pre-oxidation graphite.
3. a kind of Fenton reagent according to claim 1 prepares graphene oxide method, it is characterised in that: the pH value
Range be 2 ~ 5.
4. a kind of preparation method of graphene oxide according to claim 1, it is characterised in that: the reaction temperature is
50 ~ 90 DEG C, the reaction time is 0.5 ~ 8 h.
5. a kind of Fenton reagent according to claim 1 prepares graphene oxide method, it is characterised in that: described to be cooled to
30 ~ 70 DEG C, the reaction time be 2 ~ for 24 hours.
6. a kind of Fenton reagent according to claim 1 prepares graphene oxide method, it is characterised in that: the Fenton
Reagent be hydrogen peroxide (hereinafter referred to as: H2O2)/ferrous sulfate is (hereinafter referred to as: FeSO4) system, H2O2With FeSO4Quality it
It Wei not 7:1 ~ 11:1.
7. a kind of Fenton reagent according to claim 1 prepares graphene oxide method, it is characterised in that: the reactant
Tie up under water bath condition or water-bath and ultraviolet lamp irradiation condition under or water-bath and ultrasound condition under or electrochemical redox condition
Under.
8. a kind of Fenton reagent according to claim 1 prepares graphene oxide method, it is characterised in that: the oxidation
Graphite diluted concentration is 0.5 ~ 2 g/L, and the ultrasonic time is 0.5 ~ 5 h.
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| CN201811138234.7A CN109019585A (en) | 2018-09-28 | 2018-09-28 | Fenton reagent prepares graphene oxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112899805A (en) * | 2020-12-14 | 2021-06-04 | 江苏新泰材料科技有限公司 | Preparation method and application of hydrophobic material |
| EP3983336A4 (en) * | 2019-06-17 | 2024-01-10 | Univ Kansas State | Graphene/graphene oxide core/shell particulates and methods of making and using the same |
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| CN105347430A (en) * | 2015-11-05 | 2016-02-24 | 南京信息工程大学 | Method for effective degradation of graphene oxide in sewage |
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| US20170152141A1 (en) * | 2015-11-27 | 2017-06-01 | Institute Of Process Engineering Chinese Academy Of Sciences | Method for preparing heterogeneous metal-free fenton catalyst and application |
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2018
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| CN105347430A (en) * | 2015-11-05 | 2016-02-24 | 南京信息工程大学 | Method for effective degradation of graphene oxide in sewage |
| US20170152141A1 (en) * | 2015-11-27 | 2017-06-01 | Institute Of Process Engineering Chinese Academy Of Sciences | Method for preparing heterogeneous metal-free fenton catalyst and application |
| CN106672957A (en) * | 2016-07-18 | 2017-05-17 | 中国科学院兰州化学物理研究所 | Method for preparing graphene oxide according to Fenton oxidation method |
| CN106362746A (en) * | 2016-09-22 | 2017-02-01 | 常州大学怀德学院 | Magnetic Fenton-like catalyst, and preparation method and application thereof |
| CN107720742A (en) * | 2017-10-30 | 2018-02-23 | 嘉兴烯成新材料有限公司 | It is a kind of to use the graphene oxide preparation method containing hydrogen peroxide catalyzed system |
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| ABDOLLAH GHOLAMIAKERDI ET AL: ""Comparative study of GO and reduced GO coated graphite electrodes for decolorization of acidic and basic dyes from aqueous solutions through heterogeneous electro-Fenton process"", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3983336A4 (en) * | 2019-06-17 | 2024-01-10 | Univ Kansas State | Graphene/graphene oxide core/shell particulates and methods of making and using the same |
| CN112899805A (en) * | 2020-12-14 | 2021-06-04 | 江苏新泰材料科技有限公司 | Preparation method and application of hydrophobic material |
| CN112899805B (en) * | 2020-12-14 | 2023-10-24 | 江苏新泰材料科技有限公司 | Preparation method and application of hydrophobic material |
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Application publication date: 20181218 |