CN102862978B - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN102862978B CN102862978B CN201210347310.1A CN201210347310A CN102862978B CN 102862978 B CN102862978 B CN 102862978B CN 201210347310 A CN201210347310 A CN 201210347310A CN 102862978 B CN102862978 B CN 102862978B
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Abstract
The invention belongs to the field of two-dimensional nano materials and preparation thereof, and particularly relates to a preparation method of graphene. The method is characterized by comprising the following steps: adding a reducer into a graphite oxide dispersion liquid, heating to react, and carrying out centrifugal separation to obtain the graphene, wherein the reducer is sodium diphenylamine sulfonate. The method has the advantages of more sufficient reduction of graphite oxide, easy product separation and simple purification process. In the preparation process, no stabilizer or dispersant is added, and the obtained graphene contains fewer impurity elements; and the invention has the characteristics of controllable process, short period, atmospheric conditions, simple equipment and excellent graphene properties, is suitable for industrial production, and has wide application prospects in the technical fields of catalysis, energy transfer and storage, sensors and the like.
Description
Technical field
The invention belongs to two-dimension nano materials and preparation field thereof, particularly a kind of preparation method of Graphene.
Background technology
Graphene (Graphene) is sp
2the monoatomic layer flat crystal that hydbridized carbon atoms arranges according to boxwork at two-dimensional space, it is the elementary cell forming soccerballene, carbon nanotube and graphite, since the A.Geim professor of Univ Manchester UK in 2004 and helpmate thereof are successfully prepared so far first time, the nova that Graphene rises rapidly as Materials science and Condensed Matter Physics field, attract the research of numerous scientist for its all respects, research shows, the theoretical specific surface area of Graphene is up to 2630m
2/ g, Young's modulus is 1100Gpa, and breaking tenacity is 125Gpa, and physical strength is 1060Gpa, and thermal conductivity is 5000W/mk, and under room temperature, electronic mobility is 15000cm
2/ VS, these unique excellent performances, make Graphene be with a wide range of applications in fields such as sensor, stored energy and matrix materials.
The preparation method of current Graphene mainly contains: mechanically peel method (K.S.Novoselov, et al, Science, 2004,306,666-669), chemical Vapor deposition process (A.Reina, et al, Nano Lett., 2009,9,30-35), epitaxial growth method (P.W.Sutter, et al, Nat. Mater., 2008,7,406-411), chemistry redox method (D.Li, et al, Nat. Nanotechnol., 2008,3,101-105); These methods have respective merits and demerits, and the Graphene purity that mechanically peel obtains is high, good conductivity, but productive rate is lower and the mix products of Graphene is difficult to be separated; Chemical Vapor deposition process can prepare high quality, large-area Graphene, and epitaxial growth method can prepare single-layer graphene, but these two kinds of methods need adopt High Temperature High Pressure, and experiment condition is harsh, and operating procedure is complicated, and production cost is high; Compared with first three methods, chemistry redox method has that operating procedure is simple, experiment condition is gentle, production cost is low etc. a little, is relatively applicable to scale operation.
The reductive agent that the chemical reduction graphene oxide of current bibliographical information prepares Graphene mainly contains: hydrazine hydrate (Stankovich S, et al, J Mater Chem, 2006,16,155-158), Resorcinol (G.X.Wang, et al, Carbon, 2009,47,1359-1364) and sodium borohydride (J.F.Shen, et al, Chem.Mater., 2009,21,3514-3520) etc.; The shortcoming of hydrazine hydrate and Resorcinol is that toxicity is large, can not meet the needs of environmental protection; Sodium borohydride, due to its facile hydrolysis, makes its reduction efficiency low.Therefore, the preparation method finding green, efficient, nontoxic new reductive agent and applicable industrial production Graphene thereof is urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Graphene, to meet the market demand growing to Graphene, the advantage of the method is that the reduction of graphite oxide is more abundant, and product is easily separated, and purge process is simple; Do not add any stablizer and dispersion agent in preparation process, the impure element of the Graphene obtained is few; Process control, the cycle is short, condition of normal pressure, and equipment is simple, is suitable for industrial production, shows premium properties, is with a wide range of applications in catalysis, the storage of energy biography, sensor technical field.
Technical solution of the present invention is as follows:
A preparation method for Graphene, is characterized in that: reductive agent is added heating in graphite oxide dispersion and react, namely centrifugation obtains Graphene, and described reductive agent is sodium diphenylaminesulfonate.
Dispersion agent in described graphite oxide dispersion is deionized water, and graphite oxide dispersion concentration is 0.25-1.5mg/mL.
Described sodium diphenylaminesulfonate and the mass ratio of graphite oxide dispersion are 0.271-0.542:30.
Described graphite oxide adopts Hummers method or Hummers to improve one's methods obtained.
The preparation process of described Graphene is as follows:
Step one: by dense H
2sO
4, K
2s
2o
8and P
2o
5mix and be placed in beaker, be heated to 80 DEG C, in beaker, add Graphite Powder 99, reaction 6h, washing and filtering.
Step 2: the Graphite Powder 99 after step one being processed and SODIUMNITRATE are added to the dense H of ice-water bath
2sO
4in, slowly add potassium permanganate under stirring, oil bath reacts 2-3h after being warming up to 35 DEG C, 98 DEG C are warming up to after adding deionized water again, insulation 0.5h, then drip massfraction be 30% hydrogen peroxide reduction not by the potassium permanganate reacted, wash and obtain graphite oxide after centrifuging treatment.
Step 3: the graphite oxide that step 2 is obtained is added to the water, and after then processing 0.5h under the ultrasonic power of 300W, under the speed of 8000rpm after centrifugal 5min, disgorging, obtains graphite oxide dispersion.
Step 4: the graphite oxide dispersion obtained to step 3 adds sodium diphenylaminesulfonate, 80-100 DEG C of backflow 4-8 hour, is cooled to room temperature, centrifugation, obtains Graphene.
The present invention utilizes chemical process to prepare graphite oxide, and employing sodium diphenylaminesulfonate is reductive agent, does not add any stablizer and dispersion agent, and the impure element of the Graphene obtained is few; Process control, the cycle is short, condition of normal pressure, and equipment is simple, is suitable for industrial production, shows premium properties, is with a wide range of applications in catalysis, the storage of energy biography, sensor technical field.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction spectrogram of the Graphene of embodiment 2 sample;
Fig. 2 is transmission electron microscope (TEM) figure of the Graphene of embodiment 2 sample;
Fig. 3 is scanning electron microscope (SEM) figure of the Graphene of embodiment 2 sample;
Fig. 4 is the Raman spectrogram of the Graphene of embodiment 2 sample;
Fig. 5 is the XRD diffraction spectrogram of the Graphene of embodiment 3 sample;
Fig. 6 is the XRD diffraction spectrogram of the Graphene of embodiment 7 sample;
Fig. 7 is the XRD diffraction spectrogram of the Graphene of embodiment 8 sample.
Embodiment
Below in conjunction with embodiment, the present invention will be further elaborated.
embodiment 1:
Step one: by dense for 15mL H
2sO
4, 2.5g K
2s
2o
8with 2.5g P
2o
5mix and be placed in beaker, be heated to 80 DEG C, in beaker, add 5g Graphite Powder 99, reaction 6h, dry after washing and filtering.
Step 2: the Graphite Powder 99 after step one being processed and SODIUMNITRATE are added to the dense 115mL H of ice-water bath
2sO
4in, slowly add potassium permanganate under stirring, oil bath reacts 3h after being warming up to 35 DEG C, 98 DEG C are warming up to after adding deionized water again, insulation 0.5h, then drip massfraction be 30% hydrogen peroxide reduction not by the potassium permanganate reacted, wash and obtain graphite oxide after centrifuging treatment.
Step 3: the graphite oxide that step 2 is obtained is added to the water, and after then processing 0.5h under the ultrasonic power of 300W, under the speed of 8000rpm after centrifugal 5min, disgorging, obtains the graphite oxide dispersion of 1mg/L.
Step 4: the graphite oxide dispersion obtained to step 3 adds sodium diphenylaminesulfonate, mass ratio is 30:0.271,100 DEG C of back flow reaction 8h, and color becomes aterrimus from brown color gradually, is cooled to room temperature, and centrifugation obtains Graphene.
embodiment 2:
By the preparation method of embodiment 1, just change the reaction mass of step 4 ratio into 30:0.407.
Fig. 1 to Fig. 4 sets forth the powder X-ray RD diffraction spectrogram of the Graphene that the present embodiment obtains, transmission electron microscope picture, scanning electron microscope and Raman spectrogram, find out from powder X-ray RD diffraction spectrogram, (001) diffraction peak 11.28 ° of graphite oxide, through too sodium diphenylaminesulfonate reduction reaction, 23.14 ° of appearance (002) diffraction peaks; As can be seen from transmission electron microscope picture and scanning electron microscope (SEM) photograph, graphene film has the mutual packing phenomenon of fold; Find out from Raman spectrogram, the D peak of graphene oxide appears at 1350 cm
-1with G peak at 1602 cm
-1, the D peak of Graphene is at 1347cm
-1and G peak is at 1598cm
-1, similar with relevant report, result shows, prepares Graphene by method graphite oxide of the present invention.
embodiment 3:
By the preparation method of embodiment 1, just change the reaction mass of step 4 ratio into 30:0.542, Fig. 5 is the powder X-ray RD diffraction spectrogram of the Graphene of the present embodiment, result shows, prepare Graphene by method of the present invention, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
embodiment 4:
By the preparation method of embodiment 1, just change the return time of step 4 into 6h, XRD diffraction spectrogram, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
embodiment 5:
By the preparation method of embodiment 1, just change the return time of step 4 into 4h, XRD diffraction spectrogram, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
embodiment 6:
By the preparation method of embodiment 1, just change the concentration 1mg/L of the graphene oxide of step 3 into 0.5mg/L, XRD diffraction spectrogram, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
embodiment 7:
By the preparation method of embodiment 1, just change 100 of step 4 DEG C of backflow 8h into 95 DEG C of backflow 5h, Fig. 6 is the powder X-ray RD diffraction spectrogram of the Graphene of the present embodiment, result shows, prepare Graphene by method of the present invention, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
embodiment 8:
By the preparation method of embodiment 1, just change 100 of step 4 DEG C of backflow 8h into 80 DEG C of backflow 8h, Fig. 7 is the powder X-ray RD diffraction spectrogram of the Graphene of the present embodiment, result shows, prepare Graphene by method of the present invention, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
embodiment 9:
By the preparation method of embodiment 7, just change the reaction mass of step 4 ratio into 30:0.407, XRD diffraction spectrogram, transmission electron microscope picture, scanning electron microscope and Raman spectrogram are similar to Example 2.
Claims (5)
1. a preparation method for Graphene, is characterized in that: reductive agent is added heating in graphite oxide dispersion and react, be cooled to room temperature after reaction, namely centrifugation obtains Graphene, and described reductive agent is sodium diphenylaminesulfonate.
2. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that: the dispersion agent in described graphite oxide dispersion is deionized water, and graphite oxide dispersion concentration is 0.25-1.5mg/mL.
3. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that: described sodium diphenylaminesulfonate and the mass ratio of graphite oxide dispersion are 0.271-0.542:30.
4. the preparation method of a kind of Graphene as claimed in claim 1, it is characterized in that: the preparation method of described graphite oxide dispersion is as follows: graphite oxide is added to the water, then after processing 0.5h under the ultrasonic power of 300W, under the speed of 8000rpm after centrifugal 5min, disgorging, obtains graphite oxide dispersion.
5. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that: described reaction conditions is 80-100 DEG C of backflow 4-8 hour.
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| CN107445148B (en) * | 2016-05-25 | 2020-01-03 | 中国科学院理化技术研究所 | Method for preparing functionalized graphene through ball milling |
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|---|---|---|---|---|
| CN101844762A (en) * | 2010-05-28 | 2010-09-29 | 江苏大学 | Method for preparing hydrophilic graphene |
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|---|---|---|---|---|
| CN101844762A (en) * | 2010-05-28 | 2010-09-29 | 江苏大学 | Method for preparing hydrophilic graphene |
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