CN101987729B - Method for preparing graphene by reduction of sulfur-contained compound - Google Patents
Method for preparing graphene by reduction of sulfur-contained compound Download PDFInfo
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- CN101987729B CN101987729B CN 201010536982 CN201010536982A CN101987729B CN 101987729 B CN101987729 B CN 101987729B CN 201010536982 CN201010536982 CN 201010536982 CN 201010536982 A CN201010536982 A CN 201010536982A CN 101987729 B CN101987729 B CN 101987729B
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- deionized water
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Abstract
The invention discloses a method for preparing graphene by reduction of a sulfur-contained compound, which concretely comprises the following steps of: dispersing graphene oxide into deionized water or a mixed solution of the deionized water and N,N-dimethylacetylamide to obtain uniform dispersing liquid with the concentration of 1-3mg/ml; then adding 1.35-5mmol of sulfur-contained compound and making the mixture react at 94-96 DEG C for 1-3 hours; and enabling the reaction product to be subjected to the processes of filtration, washing, frozen drying, and the like to obtain high-purity grapheme. The invention has the advantages of simple and safe process and high quality of the grapheme prepared by adopting the method and can be widely used for the preparation of novel grapheme, materials and devices.
Description
Technical field
The invention belongs to chemical preparation Graphene product technical field, be specifically related to a kind of method for preparing Graphene with reduction of sulfur-contained compound.
Background technology
Graphene is a kind of two-dimentional graphite material of monolayer, gets most of the attention because it has potential high conductivity, heat endurance, mechanical strength and special Quantum Properties, is considered to the following comprehensively new material of substituted for silicon.As the basis of using, the technology of preparing of Graphene also has very large developing space at present.Present graphene preparation method mainly comprises mechanical stripping method, chemical vapour deposition technique (CVD method) and chemical reduction method etc.Wherein chemical reduction method is simple because of process, is easy to the characteristics such as in batches preparation and is paid close attention to.Its basic process is first graphite powder to be oxidized to graphene oxide, then reduces, and reducing agent wherein is the emphasis and key of research.
The reducing agent that can be used for the Graphene preparation of having reported at present comprises following system: according to U.S.'s " charcoal " (Carbon, 2007,45,1558-1565) magazine report adopts the hydrazine or derivatives thereof can prepare Graphene as reducing agent; According to the U.S. " physical chemistry magazine C " (J.Phys.Chem.C, 2008,112,8192-8195) report adopts hydrazine hydrate also can reduce the preparation Graphene; According to U.S.'s " chemical material " (Chem.Mater., 2010,22,2213-2218) report adopts amino acid as reducing agent, also can reduce and obtain Graphene; According to U.S.'s " nanometer communication " (Nano lett., 2008,8,1679-1682) magazine report adopts traditional strong reductant such as sodium borohydride, also can reduce the preparation Graphene; According to Britain's " chemical communication " (Chem.Commun., 2010,46,1112-1114) magazine report, vitamin C also can be used as reducing agent and prepares Graphene; The applicant also once find to adopt thermal reduction can prepare Graphene, and Britain's " nanoscale " magazine (Nanoscale, 2010,2, reported this result on 559-563); The applicant has also been developed a kind of method that adopts the microwave fast restore to prepare Graphene in addition, sees U.S.'s " charcoal " (Carbon, 2010,48,1146-1152) magazine report.
The preparation method of the Graphene of above-mentioned these reports has high toxicity and danger, also is easy to make the Graphene of generation to have high nitrogen to mix such as hydrazine, hydrazine hydrate or sodium borohydride at equal defectiveness in varying degrees, affects the purity of Graphene.And adopt amino acid or vitamin as reducing agent, and the electric conductivity of the Graphene that obtains is lower, is difficult to obtain high-quality Graphene, and also there is the not high problem of electric conductivity in the Graphene that heat and microwave reduction prepare.So still need to develop new reduction system, when guaranteeing to prepare Graphene fast, can access high conductivity and low-doped grapheme material.
Summary of the invention
The present invention discloses a kind of employing sulfur-containing compound as reducing agent, prepares the method for high conductivity Graphene.
Technical scheme of the present invention is as follows:
A kind ofly prepare the method for Graphene with reduction of sulfur-contained compound, it is characterized in that: concrete steps are as follows:
(1) graphene oxide is put into the container that fills solvent, and with ultrasonic dissolution assisting 5-8 minute, obtained certain density uniform dispersion, dispersion liquid concentration is 1-3mg/ml, is preferably 1mg/ml;
(2) sulfur-containing compound with 1.35～5mmol joins in the uniform dispersion that contains 50 milligrams of graphene oxides of step (1), constantly stirs, and increases the temperature at 93-96 ℃, and afterreaction finished in 2-4 hour, was down to room temperature;
(3) with the material in the cooled container, filtration, washing, freeze drying obtain highly purified Graphene,
Described solvent is deionized water or deionized water and N, the mixed solution of N-dimethylacetylamide, wherein the ratio of the mixed solution mixed solvent of water and DMA is VH2O: VDMAc=(2-3): 3, and optimal proportion is: VH2O: VDMAc=2: 3
Describedly prepare the method for Graphene with reduction of sulfur-contained compound, it is characterized in that: described sulfur-containing compound is selected from NaHSO
3, Na
2SO
3, Na
2S
2O
3, Na
2S9H
2O, SOCl
2, SO
2In a kind of.
Compare with the preparation method of existing Graphene, because the inventive method takes sulfur-containing compound to replace the contour poison of hydrazine, high risk reagent, the preparation method is safer and green.Particularly adopt the electric conductivity of the Graphene that the reducing agent of the inventive method prepares high, reach 6500Sm
-1, and the electric conductivity of the Graphene that heat and microwave reduction etc. obtain is at 2000Sm
-1Below, even the electric conductivity of the Graphene that the reduction of employing hydrazine obtains under the same reaction condition also only has 5100Sm
-1Simultaneously, the content of nitrogen also obtains the low of Graphene than the hydrazine reduction in the Graphene product that employing the inventive method makes, nitrogen content can be down to 0.18t%, and the hydrazine reduction obtains the nitrogen content of product between 3-5wt%, the existence meeting that nitrogen mixes produces larger impact to the performance of Graphene, still method helpful to preparing high-quality Graphene.
Compare with existing technology, main innovation part of the present invention is:
The inventive method with the little compound of the side effects such as sodium hydrogensulfite, vulcanized sodium as reducing agent, efficient reduction preparation Graphene in aqueous medium.The inventive method has been expanded the reducing agent scope of preparation Graphene, finds that numerous sulfur-containing compounds possesses the ability of redox graphene, so that the preparation of Graphene is safer and simple.The C/O ratio of the Graphene for preparing is high, can reach 7.89; Simultaneously, the ratio of C/ (N+O) can reach 7.66, and the ratio of C/N can reach 224.4 especially, and the C/N that reduces with hydrazine is 22.6.The Graphene quality of taking this method to prepare is high, can be widely used in the preparation of novel graphite alkene and material and device.
Description of drawings
Fig. 1 be graphene oxide (a) with through NaHSO
3The photo of the Graphene (b) of reduction preparation.
Fig. 2 be graphene oxide (a) with through NaHSO
3X-ray photoelectron spectroscopy (XPS) figure of the Graphene (b) of reduction preparation.
Fig. 3 is graphene oxide (GO), through NaHSO
3Fourier transform infrared (FT-IR) collection of illustrative plates of the Graphene (S-CRG) of reduction preparation and the Graphene (N-CRG) for preparing through the hydrazine reduction.
Fig. 4 be graphene oxide with through NaHSO
3LR laser raman (Raman) collection of illustrative plates of the Graphene of reduction preparation.
Fig. 5 is graphene oxide (1), through NaHSO
3The thermogravimetric curve of the Graphene (3) of reduction preparation and the Graphene (2) for preparing through the hydrazine reduction.
Fig. 6 be graphene oxide (a, c) with through NaHSO
3AFM (AFM) figure of the Graphene (b, d) of reduction preparation and corresponding height analysis chart.
Fig. 7 is through NaHSO
3Transmission electron microscope (TEM) photo of the Graphene of reduction preparation, upper right corner illustration is diffraction pattern.
The specific embodiment.
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Feed oxygen functionalized graphene employing U.S.'s " charcoal " (Carbon, 2010,48,1146-1152) method of magazine report is that raw material carries out the oxidation preparation by graphite powder.Detailed process is to add 2g natural graphite powder and 1g sodium nitrate in the beaker of a 250ml, then drips the 46ml concentrated sulfuric acid under ice bath, adds afterwards 6g potassium permanganate, after 5 minutes, removes ice bath, and heating reaction system to 35 ℃ was kept 30 minutes.Slowly add subsequently 92ml water.Remaining potassium permanganate 80ml60 ℃ water and the aqueous hydrogen peroxide solution flush away of 20ml3%, product carries out enrichment through centrifugation.Be washed with water to again neutrality, through freeze drying, obtain graphene oxide.
In the 50ml deionized water, add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its Uniform Dispersion yellowly liquid, add afterwards 1.35 or the reducing agent NaHSO of 2.7mmol
3, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, be down to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, then freeze drying obtains graphene powder.
Fig. 1 has provided the photo of the Graphene (b) that graphene oxide (a) and reduction obtain, and can find out that the Graphene that obtains is black powder, and elementary analysis shows that the C/O ratio that obtains Graphene is 7.89, and reducing degree is high.It can also be seen that this method can realize the batch preparation of Graphene.
Fig. 2 is the Graphene (CRG) that obtains in the present embodiment and the C1s collection of illustrative plates of the x-ray photoelectron spectroscopy (XPS) of its feed oxygen functionalized graphene (GO), wherein at peak, 286.7ev place corresponding be C-O key, peak, 287.4ev place corresponding be C=O key, peak, 284.7ev place corresponding be C=C or C-C key, peak, 288.8ev place corresponding be the O=C-O key.After reduction, the peak intensity of C-O, C=O, C-O and O=C-O key obviously reduces, and shows that graphene oxide is effectively reduced.Remaining peak is mainly corresponding to C=C and the C-C key of Graphene.
Fig. 3 is the Graphene (curve 2) that obtains in the present embodiment and the Fourier transform infrared spectroscopy figure (FT-IR) of its feed oxygen functionalized graphene (curve 1), be contrast, the infrared figure of the Graphene that obtains with the hydrazine reduction under same reaction conditions has been also placed in together (curve 3).Corresponding graphene oxide, peak position corresponding to its characteristic group is respectively: C=O (1734cm
-1), C=C (1624cm
-1), carbonyl C-O (1415cm
-1), epoxy C-O (1228cm
-1) and C-O (1076cm
-1).Through NaHSO
3After the reduction, the peak intensity of oxygen-containing functional group greatly descends or disappears, remaining 1577cm
-1The peak at place is corresponding to the C=C group of Graphene.Can find out and adopt NaHSO
3Reduction and employing hydrazine be original similar effect also.
Fig. 4 is the Graphene (CRG) that obtains in the present embodiment and the laser Raman spectroscopy (Raman) of its feed oxygen functionalized graphene (GO).For graphene oxide, the G band is positioned at 1602cm
-1Through G band after the reduction displacement having occured, has appeared at 1588cm
-1The place closer to the value of graphite, illustrates that graphene oxide has been reduced effectively.
Fig. 5 is the Graphene (curve 3) that obtains in the present embodiment and thermal weight loss (TG) collection of illustrative plates of its feed oxygen functionalized graphene (curve 1), be contrast, the TG figure of the Graphene (curve 2) that obtains with the hydrazine reduction under same reaction conditions has been also placed in together.Corresponding graphene oxide has two main weightless intervals when being heated, be the peak of adsorbed water near 100 ℃, and be the peak that unstable oxygen-containing functional group decomposes near 200 ℃.Through NaHSO
3After the reduction, near the thermal weight loss peak 200 ℃ obviously weakens, and illustrates that oxy radical is effectively removed in reduction process.Contrast by the TG with the hydrazine reduzate, find to adopt NaHSO
3The Graphene that reduction obtains is more stable.
Fig. 6 is the Graphene (b that obtains in the present embodiment, d) with AFM (AFM) picture of its feed oxygen functionalized graphene (a, c), can find out that the size of graphene oxide before the reduction is at micro-meter scale, highly be 0.79nm, be single layer structure.Through NaHSO
3After the reduction, the size of the product that obtains for the micron size, highly is 0.87 nanometer still, still is single layer structure, illustrates that the Graphene that obtains is single layer structure.
Fig. 7 is transmission electron microscope (TEM) picture of the Graphene that obtains in the present embodiment, can see the typical pleated structure of Graphene, and its electron diffraction pattern has also shown the typical diffraction pattern of Graphene simultaneously, and what further proof obtained is single-layer graphene.
In the present embodiment, in the 50ml deionized water, add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its Uniform Dispersion yellowly liquid, add afterwards the reducing agent Na of 5.0mmol
2S9H
2O is warmed up to 95 ℃ after being uniformly dispersed, and under agitation keeps reaction 3 hours.After reaction finishes, be down to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, then freeze drying obtains graphene powder.
In the present embodiment, in the 50ml deionized water, add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its Uniform Dispersion yellowly liquid, add afterwards the reducing agent Na of 5.0mmol
2S
2O
3, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, be down to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, then freeze drying obtains graphene powder.
In the present embodiment, in the 50ml deionized water, add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its Uniform Dispersion yellowly liquid, add afterwards 2.7 or the reducing agent SOCl of 5.0mmol
2, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, be down to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, then freeze drying obtains graphene powder.
In the present embodiment, in the 50ml deionized water, add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its Uniform Dispersion yellowly liquid, be warmed up to 95 ℃, pass into afterwards the reducing agent SO of 2.7mmol
2, and under agitation keep reaction 3 hours.After reaction finishes, be down to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, then freeze drying obtains graphene powder.
Embodiment 6
(V in the mixed solution of 50ml deionized water and DMA (DMAc)
H2O: V
DMAc=2: 3) add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its Uniform Dispersion yellowly liquid, add afterwards the reducing agent NaHSO of 2.7mmol
3, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, be down to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, then freeze drying obtains graphene powder.
Adopt determination of elemental analysis above-mentioned all case study on implementation obtain the content of C, H, O, N and the S of product, the results are summarized in the table 1, can find out, adopt sulfur-containing compound all reducible graphene oxide obtain Graphene.
The results of elemental analyses that table 1. reduction of sulfur-contained compound prepares Graphene gathers
a: 1.35mmol, 3h is at H
2Among the O;
b: 2.7mmol, 3h is at H
2Among the O;
c: 2.7mmol, 3h is at DMAc/H
2Among the O;
d: 1.35mmol, 24h is at H
2Among the O;
e: 5mmol, 3h is at H
2Among the O;
Claims (2)
1. one kind prepares the method for Graphene with reduction of sulfur-contained compound, and it is characterized in that: concrete steps are as follows:
(1) graphene oxide is put into the container that fills solvent, and with ultrasonic dissolution assisting 5-8 minute, obtained certain density uniform dispersion, dispersion liquid concentration is 1-3mg/ml;
(2) sulfur-containing compound with 1.35～5mmol joins in the uniform dispersion that contains 50 milligrams of graphene oxides of step (1), constantly stirs, and increases the temperature at 93-96 ℃, and afterreaction finished in 2-4 hour, was down to room temperature;
(3) with the material in the cooled container, filtration, washing, freeze drying obtain highly purified Graphene,
Described solvent is the mixed solution of deionized water or deionized water and DMA, and wherein the ratio of the mixed solution mixed solvent of deionized water and DMA is V
H2O: V
DMAc=(2-3): 3;
Described sulfur-containing compound is selected from NaHSO
3, Na
2SO
3, Na
2S
2O
3, Na
2S9H
2O, SOCl
2, SO
2In a kind of.
2. according to claim 1ly prepare the method for Graphene with reduction of sulfur-contained compound, it is characterized in that: the described dispersion liquid concentration of step (1) is 1mg/ml; The ratio of the mixed solution mixed solvent of described deionized water and DMA is V
H2O: V
DMAc=2: 3.
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| CN103187570B (en) * | 2011-12-28 | 2015-09-30 | 清华大学 | The preparation method of sulphur-graphene composite material |
| CN103187558B (en) * | 2011-12-28 | 2015-07-01 | 清华大学 | Preparation method for sulfur-graphene composite |
| CN103253653B (en) * | 2012-02-15 | 2016-01-27 | 国家纳米科学中心 | Graphene oxide membrane, graphene film and its preparation method and application |
| CN103682358A (en) * | 2012-09-24 | 2014-03-26 | 东丽先端材料研究开发（中国）有限公司 | High-dispersity graphene composition and preparation method thereof as well as electrode applied to lithium ion secondary battery |
| CN103224228A (en) * | 2013-04-07 | 2013-07-31 | 怀化学院 | Selectively reduced graphene oxide and preparation method |
| CN103435034A (en) * | 2013-08-14 | 2013-12-11 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene based non-metallic oxygen reduction catalyst |
| CN105366662B (en) * | 2014-08-27 | 2017-11-21 | 中国石油化工股份有限公司 | The preparation method of sulfur doping graphene |
| CN106145101B (en) * | 2016-07-06 | 2018-08-10 | 北京光科博冶科技有限责任公司 | A kind of bigger serface nitrogen-doped graphene and preparation method thereof |
| CN107579201B (en) * | 2017-09-14 | 2023-07-18 | 珠海格力电器股份有限公司 | Multilayer body and preparation method thereof |
| CN109876845B (en) * | 2019-03-22 | 2021-03-19 | 北京交通大学 | M-g-C3N4Preparation method and application of/rGOA composite adsorption visible light catalytic material |
| CN110048102B (en) * | 2019-04-12 | 2022-02-01 | 欣旺达电动汽车电池有限公司 | TiS2Preparation method of @ graphene composite nano material and application of material in lithium ion battery |
| CN114133735A (en) * | 2021-12-07 | 2022-03-04 | 东莞市鸿亿导热材料有限公司 | graphene-PI film and preparation method thereof |
| CN114410329B (en) * | 2022-02-10 | 2022-10-28 | 山西沁新能源集团股份有限公司 | High carbon coke with hybrid carbon and method for producing same |
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| JP2010108986A (en) * | 2008-10-28 | 2010-05-13 | Hitachi Chem Co Ltd | Material forming gate insulating film layer, field effect transistor and process for fabricating field effect transistor |
| CN101870467A (en) * | 2010-06-02 | 2010-10-27 | 天津大学 | Optical responsive azobenzene graft grapheme material and preparation method thereof |
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| CN101870467A (en) * | 2010-06-02 | 2010-10-27 | 天津大学 | Optical responsive azobenzene graft grapheme material and preparation method thereof |
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