CN105439125A - A method of producing sulfur-doped graphene - Google Patents
A method of producing sulfur-doped graphene Download PDFInfo
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- CN105439125A CN105439125A CN201410427865.6A CN201410427865A CN105439125A CN 105439125 A CN105439125 A CN 105439125A CN 201410427865 A CN201410427865 A CN 201410427865A CN 105439125 A CN105439125 A CN 105439125A
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Abstract
The invention relates to a method of producing sulfur-doped graphene, and mainly overcomes problems of sulfur-doped graphene preparation in the prior art, namely high reaction temperature, long reaction time, high equipment requirements, extremely toxic raw materials and low yields. According to a technical scheme adopted by the method, the method includes a) subjecting graphite oxide to ultrasonic exfoliation in a solvent to obtain a graphene oxide solution, b) mixing the graphene oxide solution and a sulfur-containing organic compound, performing ultrasonic treatment to uniformly disperse and mix the mixture so as to obtain a liquid mixture, and drying the liquid mixture to obtain a solid mixture, and c) subjecting the solid mixture to microwave radiation treatment under inert gas protection, and cooling to room temperature to obtain the sulfur-doped graphene. The problems are overcome by adoption of the technical scheme. The method can be used for industrial production of the sulfur-doped graphene.
Description
Technical field
The present invention relates to a kind of method of producing sulfur doping Graphene.
Background technology
Graphene is with sp by carbon atom
2the two dimensional crystal material of hybridized orbital composition hexagonal network structure, there is very excellent performance, as high electronic mobility, good thermal conductivity, light transmission and good stability, can be applicable to the fields such as semiconductor material, matrix material, battery electrode material, hydrogen storage material, field emmision material and hypersensor.Doping is the effective way changing Graphene electronic structure and chemical property.The lattice that hetero atom is graphene-doped, not only effectively can introduce band gap, and can increase the defect of Graphene and the reactive behavior of local, thus produces many new functions.Research finds that nitrogen, boron or phosphoric also effectively can change its performance by graphene-doped lattice, and relatively less to the research of other element doping.
Element sulphur is a kind of potential doped element theoretically, but sulphur atom differs more with carbon atom radius, and electronegativity is close with carbon atom, therefore element sulphur be not easy graphene-doped lattice.Patent CN201110095599.8 discloses a kind of preparation method of sulfur-doped graphene films, its respectively with sulphur powder and hexane for sulphur source and carbon source, chemical Vapor deposition process is adopted to grow sulfur-doped graphene films on the metallic substrate, but the method need use high temperature chemical vapor deposition reactor, equipment is complicated, temperature of reaction high (up to 900 ~ 1000 DEG C), long reaction time, yield poorly, cost is high, is difficult to scale operation.M ü llen etc. reports a kind of method (AdvancedFunctionalMaterials preparing sulfur doping Graphene and nitrogen-doped graphene on porous silicon plate, 2012, 22, 3634-3640.), it adopts hydrogen sulfide to do reductive agent and doping sulphur source, the element sulphur doping of Graphene is realized while high temperature reduction graphene oxide, but the method need use severe toxicity and severe corrosive hydrogen sulfide, temperature of reaction high (500 ~ 900 DEG C), long reaction time, equipment requirements is harsh, excess air is still needed increase innocent treatment equipment, and to be supported on porous silicon plate due to graphene oxide therefore to be unfavorable for large-scale production.
Summary of the invention
Technical problem to be solved by this invention is the problem that prior art exists that sulfur doping Graphene preparation feedback temperature is high, long reaction time, equipment requirements are high, raw material is extremely malicious, yield poorly, and provides a kind of method of production sulfur doping Graphene newly.The method can be used for preparation of industrialization sulfur doping Graphene, has the advantage that temperature of reaction is low, the reaction times is short, equipment is simple, advantages of nontoxic raw materials is harmful, be easy to industry amplification.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing sulfur doping Graphene, comprises the following steps:
A) by graphite oxide ultrasonic stripping in a solvent, graphene oxide solution is obtained;
B) by described graphene oxide solution and sulfurous organic compound mixing, supersound process makes its dispersing and mixing even, obtains liquid mixture; Dry described liquid mixture, obtains solid mixture;
C) by the microwave exposure process under protection of inert gas of described solid mixture, be cooled to room temperature, obtain described sulfur doping Graphene.
In technique scheme, preferably, step a) ultrasonic splitting time be 0.5 ~ 2 hour.
In technique scheme, preferably, step b) sonication treatment time is 5 ~ 30 minutes.
In technique scheme, preferably, the concentration of described graphene oxide solution is 0.1 ~ 7 mg/ml.More preferably, the concentration of described graphene oxide solution is 0.5 ~ 5 mg/ml.
In technique scheme, preferably, described solvent is water, ethanol, Virahol, hexanaphthene, benzene, acetone, tetrahydrofuran (THF), methyl-2-pyrrolidone, ethyl pyrrolidone, dimethyl formamide or N,N-DIMETHYLACETAMIDE.
In technique scheme, preferably, described sulfocompound is Diphenyl disulfide ether, two (octadecyl) disulfide, xylyl disulfide, 3, at least one in 3-dihydroxyl diphenyl disulfide, 4,4-dimercapto diphenyl sulfides, dibenzyl sulfide, three beneze methane thiols, 2-thionaphthol or dibenzothiophene.
In technique scheme, preferably, microwave exposure process is carried out in microwave reactor.
In technique scheme, preferably, the power of described microwave reactor is 350 ~ 1200 watts, and irradiation time is 30 seconds ~ 10 minutes.
In technique scheme, preferably, in described sulfocompound and graphene oxide solution, the weight ratio of graphene oxide is 1 ~ 50.
In technique scheme, preferably, described rare gas element is at least one in nitrogen, argon gas or helium.
In the present invention, take graphite oxide as presoma, obtain homodisperse graphene oxide solution by ultrasonic stripping; Under microwave exposure effect, the hydroxyl, carboxyl, carbonyl etc. of surface of graphene oxide decompose rapidly containing oxygen luminous energy group, release amount of heat, system temperature is made to be elevated to 500 ~ 1000 DEG C fast, sulfurous organic compound decomposes becomes hydrogen sulfide etc. to contain the gas of element sulphur, itself and graphene oxide react, while redox graphene, generate sulfur doping Graphene.
Compared with prior art, strong from exothermic effect when the present invention utilizes the strong sorption of the selectivity of polarity oxygen-containing functional group to microwave of surface of graphene oxide and oxygen-containing functional group to decompose, avoid the shortcoming that convective heating mode heat transfer rate is in the past slow, warm up time is long, shorten the reaction times, decrease energy consumption of reaction; In the present invention, sulfocompound decomposes, the reduction of graphene oxide and doping carry out at the same temperature fast, avoids the oxygen-containing functional group of surface of graphene oxide before doping reaction, namely decomposes in warm, improve element sulphur doping; The present invention replaces the malicious high risk reagent of this height of hydrogen sulfide to do sulphur source with sulfurous organic compound, and preparation method is safer; The microwave exposure technique that the present invention adopts is without the need to using metal or silicon chip substrate; therefore treatment capacity is large; be easy to mass-producing amplify; can be applicable in the suitability for industrialized production of sulfur doping Graphene; meet the fields such as absorption, catalysis and energy storage material to the throughput requirements of sulfur doping Graphene, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction spectrum (XRD) figure of natural graphite, graphite oxide and sulfur doping Graphene in the present invention's [embodiment 1].Wherein, A is natural graphite, and B is graphite oxide, and C is sulfur doping Graphene.
Fig. 2 is scanning electronic microscope (SEM) figure of sulfur doping Graphene prepared by the present invention's [embodiment 1].
Fig. 3 is transmission electron microscope (TEM) figure of sulfur doping Graphene prepared by the present invention's [embodiment 1].
Fig. 4 is x-ray photoelectron power spectrum (XPS) figure of S2p in the sulfur doping Graphene prepared of the present invention's [embodiment 1].
Fig. 1 is X-ray diffraction spectrum (XRD) figure of natural graphite, graphite oxide and sulfur doping Graphene.Sulfur doping Graphene is in 2 θ=26.6 belonging to graphite
0place, and 2 θ=10.8 of graphite oxide
0place, all without obvious XRD diffraction peak, has Graphene X ray diffracting characteristic.
Fig. 2 is scanning electronic microscope (SEM) figure of sulfur doping Graphene.Transparent spun silk shape graphene sheet layer is mutually stacking, forms the Graphene particle of bulk multi-hole.
Fig. 3 is transmission electron microscope (TEM) figure of sulfur doping Graphene, a few near-transparent of graphene film under electron beam irradiation, the gauffer that surface presentation is intrinsic.
Fig. 4 is x-ray photoelectron power spectrum (XPS) figure of S2p in sulfur doping Graphene, and wherein peak, 163.9eV place corresponds to C-S-C2p
3/2key, peak, 165.1eV place corresponds to C-S-C2p
1/2key, peak, 168.5eV place corresponds to C-SO
x-C key, show part sulphur atom alternate c atoms enter in Graphene lattice.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
The ultrasonic stripping in 100 milliliters of ethanol of 300 milligrams of graphite oxides is prepared 3 mg/ml graphene oxide solution for 1.5 hours, then adds 3 grams of dibenzothiophene wherein, within ultrasonic 15 minutes, dispersing and mixing is even, and drying obtains solid mixture; By solid mixture under protection of inert gas, power is radiation treatment 1 minute in 1200 watts of microwave reactors, is cooled to room temperature, i.e. obtained sulfur doping Graphene, and wherein the atomic percentage conc of sulphur is 1.73%.
Obtained sulfur doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electronic microscope (SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS) figure is shown in accompanying drawing, show sulphur atom alternate c atoms enter in Graphene lattice.
[embodiment 2]
The ultrasonic stripping in 100 milliliters of ethanol of 50 milligrams of graphite oxides is prepared 0.5 mg/ml graphene oxide solution for 1 hour, then adds 2.5 grams of dibenzothiophene wherein, within ultrasonic 10 minutes, dispersing and mixing is even, and drying obtains solid mixture; By solid mixture under protection of inert gas, power is radiation treatment 10 minutes in 350 watts of microwave reactors, is cooled to room temperature, i.e. obtained sulfur doping Graphene, and wherein the atomic percentage conc of sulphur is 2.07%.
Obtained sulfur doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electronic microscope (SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS) figure is similar to [embodiment 1].
[embodiment 3]
The ultrasonic stripping in 100 milliliters of ethanol of 500 milligrams of graphite oxides is prepared 5 mg/ml graphene oxide solution for 2 hours, then adds 0.5 gram of dibenzothiophene wherein, within ultrasonic 10 minutes, dispersing and mixing is even, and drying obtains solid mixture; By solid mixture under protection of inert gas, power is radiation treatment 3 minutes in 1200 watts of microwave reactors, is cooled to room temperature, i.e. obtained sulfur doping Graphene, and wherein the atomic percentage conc of sulphur is 1.31%.
Obtained sulfur doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electronic microscope (SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS) figure is similar to [embodiment 1].
[embodiment 4]
The ultrasonic stripping in 100 milliliters of Virahols of 200 milligrams of graphite oxides is prepared 2 mg/ml graphene oxide solution for 1.5 hours, then 4 gram 3 is added wherein, 3-dihydroxyl diphenyl disulfide, within ultrasonic 25 minutes, dispersing and mixing is even, and drying obtains solid mixture; By solid mixture under protection of inert gas, power is radiation treatment 5 minutes in 1000 watts of microwave reactors, is cooled to room temperature, i.e. obtained sulfur doping Graphene, and wherein the atomic percentage conc of sulphur is 1.39%.
Obtained sulfur doping Graphene X-ray diffraction spectrum (XRD) figure, scanning electronic microscope (SEM) figure, transmission electron microscope (TEM) figure, and x-ray photoelectron power spectrum (XPS) figure is similar to [embodiment 1].
Claims (10)
1. produce a method for sulfur doping Graphene, comprise the following steps:
A) by graphite oxide ultrasonic stripping in a solvent, graphene oxide solution is obtained;
B) by described graphene oxide solution and sulfurous organic compound mixing, supersound process makes its dispersing and mixing even, obtains liquid mixture; Dry described liquid mixture, obtains solid mixture;
C) by the microwave exposure process under protection of inert gas of described solid mixture, be cooled to room temperature, obtain described sulfur doping Graphene.
2. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that step a) ultrasonic splitting time be 0.5 ~ 2 hour, step b) sonication treatment time is 5 ~ 30 minutes.
3. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that the concentration of described graphene oxide solution is 0.1 ~ 7 mg/ml.
4. produce the method for sulfur doping Graphene according to claim 3, it is characterized in that the concentration of described graphene oxide solution is 0.5 ~ 5 mg/ml.
5. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that described solvent is water, ethanol, Virahol, hexanaphthene, benzene, acetone, tetrahydrofuran (THF), methyl-2-pyrrolidone, ethyl pyrrolidone, dimethyl formamide or N,N-DIMETHYLACETAMIDE.
6. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that described sulfurous organic compound is Diphenyl disulfide ether, two (octadecyl) disulfide, xylyl disulfide, 3, at least one in 3-dihydroxyl diphenyl disulfide, 4,4-dimercapto diphenyl sulfides, dibenzyl sulfide, three beneze methane thiols, 2-thionaphthol or dibenzothiophene.
7. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that microwave exposure process is carried out in microwave reactor.
8. produce the method for sulfur doping Graphene according to claim 7, it is characterized in that the power of described microwave reactor is 350 ~ 1200 watts, irradiation time is 30 seconds ~ 10 minutes.
9. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that the weight ratio of graphene oxide in described sulfurous organic compound and graphene oxide solution is 1 ~ 50.
10. produce the method for sulfur doping Graphene according to claim 1, it is characterized in that described rare gas element is at least one in nitrogen, argon gas or helium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106006625A (en) * | 2016-07-07 | 2016-10-12 | 重庆德领科技有限公司 | Method for removing valence electrons of graphene |
| CN106975446A (en) * | 2017-03-30 | 2017-07-25 | 肖硕 | Synthetic method for the sulfur doping reduced graphene of Adsorption of Organic |
| CN108587565A (en) * | 2018-05-15 | 2018-09-28 | 青岛大学 | A kind of highly conductive graphite ene-type lightweight absorbing material of sulfur doping and its preparation method and application |
| CN113912051A (en) * | 2021-11-22 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
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| CN102191476A (en) * | 2011-04-11 | 2011-09-21 | 兰州大学 | Method for preparing sulfur-doped graphene films |
| CN103840160A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene composite material and preparation method thereof |
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2014
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| CN102191476A (en) * | 2011-04-11 | 2011-09-21 | 兰州大学 | Method for preparing sulfur-doped graphene films |
| CN103840160A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene composite material and preparation method thereof |
Non-Patent Citations (2)
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| ZEGAO WANG ET AL.，: "Pure thiophene–sulfur doped reduced graphene oxide: synthesis, structure, and electrical properties", 《NANOSCALE》 * |
| ZHI YANG，ET AL.，: "Sulfur-Doped Graphene as an Efficient Metal-free Cathode Catalyst for Oxygen Reduction", 《ACS NANO》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006625A (en) * | 2016-07-07 | 2016-10-12 | 重庆德领科技有限公司 | Method for removing valence electrons of graphene |
| CN106975446A (en) * | 2017-03-30 | 2017-07-25 | 肖硕 | Synthetic method for the sulfur doping reduced graphene of Adsorption of Organic |
| CN108587565A (en) * | 2018-05-15 | 2018-09-28 | 青岛大学 | A kind of highly conductive graphite ene-type lightweight absorbing material of sulfur doping and its preparation method and application |
| CN108587565B (en) * | 2018-05-15 | 2021-02-26 | 青岛大学 | Sulfur-doped high-conductivity graphene type light wave-absorbing material and preparation method and application thereof |
| CN113912051A (en) * | 2021-11-22 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
| CN113912051B (en) * | 2021-11-22 | 2022-11-29 | 北京石墨烯技术研究院有限公司 | Preparation method of doped graphene |
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