CN101987729A - 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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- CN101987729A CN101987729A CN 201010536982 CN201010536982A CN101987729A CN 101987729 A CN101987729 A CN 101987729A CN 201010536982 CN201010536982 CN 201010536982 CN 201010536982 A CN201010536982 A CN 201010536982A CN 101987729 A CN101987729 A CN 101987729A
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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 reduction method and prepare the Graphene product technical field, be specifically related to a kind of method for preparing Graphene with the sulfocompound reduction.
Background technology
Graphene is a kind of two-dimentional graphite material of unimolecular layer, gets most of the attention because of it has potential high conductivity, thermostability, physical strength and special Quantum Properties, is considered to the following novel material of substituted for silicon comprehensively.As the basis of using, the technology of preparing of Graphene also has very big developing space at present.Present graphene preparation method mainly comprises mechanically peel method, chemical Vapor deposition process (CVD method) and chemical reduction method etc.Wherein chemical reduction method is simple because of process, is easy to characteristics such as batch preparations and is paid close attention to.Its primary process is earlier Graphite Powder 99 to be oxidized to graphene oxide, then reduces, and reductive agent wherein is the emphasis and key of research.
The reductive agent of having reported at present that can be used for the Graphene preparation 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 reductive 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 reductive 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, vitamins C also can be used as reductive agent and prepares Graphene; The applicant also once find to adopt hot reducing method 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 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 as hydrazine, hydrazine hydrate or sodium borohydride at equal defectiveness in varying degrees, influences the purity of Graphene.And adopt amino acid or VITAMIN as reductive agent, and the electroconductibility of the Graphene that obtains is lower, is difficult to obtain high-quality Graphene, and also there is the not high problem of electroconductibility 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 sulfocompound as reductive 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 sulfocompound reduction, it is characterized in that: concrete steps are as follows:
(1) graphene oxide is put into the container that fills solvent, and with ultrasonic hydrotropy 5-8 minute, obtained certain density homodisperse liquid, dispersion liquid concentration is 1-3mg/ml, is preferably 1mg/ml;
(2) sulfocompound with 1.35～5mmol joins in the homodisperse liquid that contains 50 milligrams of graphene oxides of step (1), and constantly stirring, and elevated temperature is arrived at 93-96 ℃, and afterreaction finished in 2-4 hour, reduced to room temperature;
(3) with the material in the cooled container, filtration, washing, lyophilize obtain highly purified Graphene,
Described solvent is deionized water or deionized water and N, the mixing solutions of N-N,N-DIMETHYLACETAMIDE, wherein the ratio of the mixing solutions mixed solvent of water and N,N-dimethylacetamide is VH2O: VDMAc=(2-3): 3, and optimum proportion is: VH2O: VDMAc=2: 3
Describedly prepare the method for Graphene with sulfocompound reduction, it is characterized in that: described sulfocompound is selected from NaHSO
3, Na
2SO
3, Na
2S
2O
3, Na
2S9H
2O, SOCl
2, SO
2In a kind of.
Compare with existing preparation method of graphene, because the inventive method takes sulfocompound to replace the contour poison of hydrazine, high risk reagent, the preparation method is safer and green.Particularly adopt the electroconductibility height of the Graphene that the reductive agent of the inventive method prepares, reach 6500Sm
-1, and the electroconductibility of the Graphene that heat and microwave reduction etc. obtain is at 2000Sm
-1Below, even the electroconductibility of the Graphene that same reaction conditions adopts hydrazine to reduce down to be obtained also has only 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 reduced to 0.18t%, and the hydrazine reduction obtains the nitrogen content of product between 3-5wt%, the adulterated existence of nitrogen meeting produces bigger influence to the performance of Graphene, and method is helpful to preparing high-quality Graphene still.
Compare with existing technology, main innovation part of the present invention is:
The inventive method with the little compound of side effects such as sodium bisulfite, sodium sulphite as reductive agent, efficient reduction preparation Graphene in water medium.The inventive method has been expanded the reductive agent scope of preparation Graphene, finds that numerous sulfocompounds possesses the ability of redox graphene, makes that the preparation of Graphene is safer and simple.The C/O ratio height of the Graphene for preparing 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 is 22.6 with hydrazine reductive C/N.The Graphene quality height of taking present method to prepare can be widely used in novel graphite alkene and material and preparation of devices.
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
3Laser 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
3The Graphene of reduction preparation (b, atomic force microscope d) (AFM) figure and corresponding height analysis chart.
Fig. 7 is through NaHSO
3Transmission electron microscope (TFM) photo of the Graphene of reduction preparation, upper right corner illustration is a diffraction pattern.
Embodiment.
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Raw material graphene oxide employing U.S.'s " charcoal " (Carbon, 2010,48,1146-1152) the magazine reported method is that raw material carries out the oxidation preparation by Graphite Powder 99.Detailed process is to add 2g natural graphite powder and 1g SODIUMNITRATE in the beaker of a 250ml, then drips the 46ml vitriol oil under ice bath, adds 6g potassium permanganate afterwards, after 5 minutes, removes ice bath, and reacting by heating system to 35 ℃ was kept 30 minutes.Slowly add 92ml water subsequently.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 neutrality again,, obtain graphene oxide through lyophilize.
In the 50ml deionized water, add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its homodisperse yellowly liquid, add 1.35 or the reductive agent NaHSO of 2.7mmol afterwards
3, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, reduce to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, lyophilize then obtains graphene powder.
Fig. 1 has provided the photo of the Graphene (b) that graphene oxide (a) and reduction obtain, and as can be seen, the Graphene that obtains is a black powder, and ultimate analysis shows that the C/O ratio that obtains Graphene is 7.89, the reducing degree height.It can also be seen that present method can realize the batch preparations 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 raw material graphene oxide (GO), wherein 286.7ev place peak correspondence be C-O key, 287.4ev place peak correspondence be C=O key, 284.7ev place peak correspondence be C=C or C-C key, 288.8ev place peak correspondence 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 the 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 raw material graphene oxide (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, the peak position of its characteristic group's correspondence is respectively: C=O (1734c m
-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 descends greatly or disappears, remaining 1577cm
-1The peak at place is corresponding to the C=C group of Graphene.Adopt NaHSO as can be seen
3Reduction and the also original similar effects of employing hydrazine.
Fig. 4 is the Graphene (CRG) that obtains in the present embodiment and the laser Raman spectroscopy (Raman) of its raw material graphene oxide (GO).For graphene oxide, the G band is positioned at 1602cm
-1Through reduction back G band displacement having taken place, has appeared at 1588cm
-1Locate, more approach the value of graphite, illustrate 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 raw material graphene oxide (curve 1), is contrast, and 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 planar 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 TG, find to adopt NaHSO with the hydrazine reduzate
3The Graphene that reduction obtains is more stable.
Fig. 6 is that (b, d) (size of graphene oxide highly is 0.79nm at micro-meter scale to the Graphene that obtains in the present embodiment before the reduction as can be seen, is single layer structure for a, atomic force microscope c) (AFM) picture with its raw material graphene oxide.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 a 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 homodisperse yellowly liquid, add the reductive agent Na of 5.0mmol afterwards
2S9H
2O is warmed up to 95 ℃ after being uniformly dispersed, and under agitation keeps reaction 3 hours.After reaction finishes, reduce to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, lyophilize then 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 homodisperse yellowly liquid, add the reductive agent Na of 5.0mmol afterwards
2S
2O
3, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, reduce to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, lyophilize then 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 homodisperse yellowly liquid, add 2.7 or the reductive agent SOCl of 5.0mmol afterwards
2, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, reduce to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, lyophilize then 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 homodisperse yellowly liquid, be warmed up to 95 ℃, feed the reductive agent SO of 2.7mmol afterwards
2, and under agitation keep reaction 3 hours.After reaction finishes, reduce to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, lyophilize then obtains graphene powder.
Embodiment 6
(V in the mixing solutions of 50ml deionized water and N,N-dimethylacetamide (DMAc)
H20: V
DMAc=2: 3) add the 50mg graphene oxide, and in ultra sonic bath ultrasonic 5 minutes, make its homodisperse yellowly liquid, add the reductive agent NaHSO of 2.7mmol afterwards
3, be warmed up to 95 ℃ after being uniformly dispersed, and under agitation keep reaction 3 hours.After reaction finishes, reduce to room temperature, suction filtration obtains the filter cake of black, and with 50ml water washing 4 times, lyophilize then 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, as can be seen, adopt all reducible graphene oxide of sulfocompound to obtain Graphene.
The results of elemental analyses that the reduction of table 1. sulfocompound 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;
e5mmol, 3h is at H
2Among the O.
Claims (2)
1. one kind prepares the method for Graphene with sulfocompound reduction, 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 hydrotropy 5-8 minute, obtained certain density homodisperse liquid, dispersion liquid concentration is 1-3mg/ml, is preferably 1mg/ml;
(2) sulfocompound with 1.35～5mmol joins in the homodisperse liquid that contains 50 milligrams of graphene oxides of step (1), and constantly stirring, and elevated temperature is arrived at 93-96 ℃, and afterreaction finished in 2-4 hour, reduced to room temperature;
(3) with the material in the cooled container, filtration, washing, lyophilize obtain highly purified Graphene,
Described solvent is the mixing solutions of deionized water or deionized water and N,N-dimethylacetamide, and wherein the ratio of the mixing solutions mixed solvent of deionized water and N,N-dimethylacetamide is VH
2O: VDMAc=(2-3): 3, optimum proportion is: VH
2O: VDMAc=2: 3
2. according to claim 1ly prepare the method for Graphene with sulfocompound reduction, it is characterized in that: described sulfocompound is selected from NaHSO
3, Na
2SO
3, Na
2S
2O
3, Na
2S9H
2O, SOCl
2, SO
2In a kind of.
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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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