CN111847439A - Preparation method of graphene oxide - Google Patents
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Abstract
The application discloses a preparation method of graphene oxide, which at least comprises the following steps: (a) reacting a mixture I containing a graphite raw material, concentrated sulfuric acid, potassium permanganate and dry ice to obtain a mixed solution I; (b) reacting a mixture II containing the mixed solution I and the intercalation agent to obtain a mixed solution II; (c) and reacting the mixed solution II to obtain the graphene oxide. The method introduces dry ice and ferric trichloride to optimize low-temperature intercalation effect, greatly reduces the use of concentrated sulfuric acid (by 60%), greatly reduces the cost of laboratory and industrial production of graphene oxide, greatly improves the oxygen content of the graphene oxide, reduces the particle size of the graphene oxide, obtains high-quality graphene oxide materials, and has wide application prospect in the fields of electronics, information, energy, materials and the like.
Description
Technical Field
The application relates to graphene oxide, and belongs to the field of graphene materials.
Background
Graphene oxide is used as a precursor of graphene, a large number of active groups such as carboxyl and hydroxyl are arranged on a sheet layer of the graphene oxide, and the oxidized functional groups enrich the performance of the graphene and bring more possibility to the application of the graphene.
At present, the main methods for synthesizing graphene oxide include a Brodie method, a staudenmier method and a Hummers method, wherein the Hummers method has good timeliness in the preparation process, is relatively safe in the preparation process, and is one of the most commonly used methods for laboratory and even industrial synthesis. The Hummer method prepares expanded graphite by intercalation of concentrated sulfuric acid and potassium permanganate on graphite powder in a low-temperature process, and then strips and oxidizes the expanded graphite in a medium-temperature and high-temperature process to obtain graphene oxide with thinner lamella thickness. However, the Hummers method needs to use a large amount of concentrated sulfuric acid for intercalation between graphite layers, the concentrated sulfuric acid has strong acidity, strong dehydration property and strong oxidizing property, and the use amount is huge, so that the concentrated sulfuric acid becomes the most important factor for limiting the cost of industrialized graphene, and a large amount of residual sulfate ions in waste liquid needs to be treated. The use amount of concentrated sulfuric acid is reduced as much as possible, and the bottleneck of large-scale industrialization of graphene oxide is formed.
As the fields of electrons, information, energy and the like which are developed most rapidly at present, the requirements on the quality of graphene oxide, such as particle size, oxidation degree, lamella thickness and the like, are higher and higher, and high oxidation degree means more reaction sites and more loading capacity when the graphene oxide is compounded with other substances in the field of semiconductors; smaller particle size means deeper and deeper degradation in the field of oil exploration, or application to oil fields with lower permeability; the thinner sheet thickness is more indicative of the quality of the graphene oxide. Therefore, a new preparation method for preparing graphene oxide raw materials with higher oxidation degree, smaller particle size and lower cost is more and more urgently needed.
Disclosure of Invention
According to one aspect of the application, a preparation method of graphene oxide is provided, and the method is an improved Hummers method graphene oxide preparation method, and can reduce the particle size of graphene oxide and improve the oxidation degree.
The preparation method of the graphene oxide at least comprises the following steps:
(a) reacting a mixture I containing a graphite raw material, concentrated sulfuric acid, potassium permanganate and dry ice to obtain a mixed solution I;
(b) reacting a mixture II containing the mixed solution I and the intercalation agent to obtain a mixed solution II;
(c) and reacting the mixed solution II to obtain the graphene oxide.
Optionally, in the step (a), the mass ratio of the graphite raw material, concentrated sulfuric acid, potassium permanganate and dry ice is as follows:
1：15～25：4～8：0.6～1.2。
optionally, the mass ratio of the graphite raw material, the concentrated sulfuric acid, the potassium permanganate and the dry ice is as follows:
1：18～22：5～6：0.8～1。
optionally, step (a) comprises at least:
(a1) reacting a mixture containing a graphite raw material and concentrated sulfuric acid for 5-10min to obtain a mixed solution;
(a2) adding dry ice to the mixed solution for the first time, and then adding KMnO4And then supplementing dry ice again, and continuing to react for 0.8-1.2 h to obtain a mixed solution I.
Optionally, in the step (a2), the mass ratio of the first dry ice addition to the graphite raw material is: 0.2-0.4: 1;
the mass ratio of the replenished dry ice to the graphite raw material is as follows: 0.4-0.8: 1;
adding KMnO4The duration of the time is 8-15 min.
Optionally, in step (b), the intercalant is selected from at least one of ferric chloride and zinc chloride.
Optionally, the intercalant is ferric chloride.
Optionally, in the step (b), the mass ratio of the graphite raw material to the intercalation agent is 3-8: 1.
optionally, the mass ratio of the graphite raw material to the intercalation agent is 4-6: 1.
in this application, the concentrated sulfuric acid radiating effect has greatly been promoted to the dry ice (compare in ice bath formula heat dissipation, directly add the dry ice in solution, the condition of local overheat has been avoided, the radiating rate has been improved greatly), and the low temperature intercalation effect of concentrated sulfuric acid and potassium permanganate has been promoted, the technical problem of the intercalation efficiency of concentrated sulfuric acid and potassium permanganate has been solved, and impurity can not be introduced, and this kind of low temperature intercalation, the space of ferric trichloride further intercalation has been given, the graphene oxide lamella thickness that peels off during this kind of secondary intercalation method makes the medium and high temperature reaction time is thinner, specific surface is bigger, the oxidation degree that is favorable to graphene oxide improves, thinner lamella thickness also more is favorable to the supersound to be cuted, make graphene oxide's particle diameter littleer.
Alternatively, in step (a), the conditions of reaction I are: the reaction temperature is 0-5 ℃, the reaction time is 1-2 h, and the stirring speed is 100-200 rpm.
Alternatively, in step (b), the conditions of reaction II are: the reaction temperature is 0-5 ℃, the reaction time is 1-2 h, and the stirring speed is 100-200 rpm.
Optionally, in step (c), the reaction is a high-temperature reaction after a medium-temperature reaction, and the medium-temperature reaction conditions are as follows: the reaction temperature is 40-50 ℃, the reaction time is 1.5-2.5 h, and the stirring speed is 100-200 rpm; the high-temperature reaction conditions are as follows: the reaction temperature is 80-90 ℃, the reaction time is 4-6 h, and the stirring speed is 100-200 rpm.
Optionally, the method further comprises the following steps:
(d) adding H to the product obtained in step (c)2O2And alkali liquor, adjusting the pH value to 11-13, centrifuging at a low speed, and then washing with acid and water;
(e) and (d) ultrasonically dispersing the solution centrifuged in the step (d) and ultrasonically shearing to obtain the graphene oxide.
In step (d), iron ion impurities are removed by centrifugation.
By adding small amounts of H2O2To further complete the reaction, the acid used for washing may be 5% by volume HCl, the pH may be adjusted by sodium hydroxide, and the precipitated impurities may be removed by centrifugation.
Optionally, the specific steps are as follows:
carrying out ball milling pretreatment on microcrystalline graphite powder;
step (2), taking the mass ratio of the graphite powder to the concentrated sulfuric acid in the step (1) as 1: 15-1: 25 percent (namely 5g of graphite powder corresponding to 40 to 70ml of concentrated sulfuric acid, 95 percent) is put into an ice water bath and stirred and mixed for 5 to 10 minutes;
and (3) adding the graphite powder into the mixed solution obtained in the step (2) in a mass ratio of 1: 5-2: 5 dry ice, and slowly adding KMnO into the mixed solution4Adding powder (the mass ratio of the powder to the graphite powder is 4: 1-8: 1, and the adding process is carried outLasting for about 10 minutes), observing the temperature of the mixed solution in the adding process, and supplementing dry ice to keep the temperature above or below 5 ℃ when the temperature of the mixed solution is higher than 5 ℃ (the mass ratio of the supplemented dry ice to the graphite powder is 2: 5-4: 5). Keeping the ice water bath at low temperature and stirring for 1 h;
and (4) taking the graphite powder according to the mass ratio of 1: 8-1: adding the ferric trichloride powder of 3 into the solution of the step (3), and continuing stirring in an ice-water bath for 1 h;
step (5), transferring the solution in the step (4) to a 45 ℃ medium temperature water bath kettle, and stirring for reaction for 2 hours;
and (6) continuously and slowly adding 100ml of ice water into the solution in the step (5) along the wall of the cup (the whole process is about 30min), controlling the reaction temperature not to exceed 90 ℃, naturally stirring and cooling (about 5h) to room temperature after the addition is finished, and then pouring 200ml of deionized water. And a small amount of H is added2O2Finishing the reaction;
and (7) adjusting the pH value to 12 by using sodium hydroxide, and centrifuging at low speed at 500 revolutions to remove precipitated impurities. The mixture was centrifuged several times at 5000 rpm using 5% by volume HCl and deionized water.
Step (8) ultrasonically dispersing the solution centrifuged in the step (7) for 1h, then diluting the solution to 2000ppm by using deionized water, and ultrasonically shearing the solution for 1h by using a cell disruptor to obtain a target product;
step (9) diluting the graphene oxide prepared in the step (8) to 50ppm by using deionized water (the concentration of a stock solution is calibrated by using an ultraviolet method in advance), transferring the graphene oxide to a cuvette, and placing the cuvette into a Malvern laser particle sizer to test the particle size;
and (10) drying the graphene oxide prepared in the step (8), scraping a sample, carrying out organic element analysis by using a combustion method, and measuring the oxygen content.
Optionally, the particle size of the graphene oxide is 170-200 nm.
Optionally, the oxygen content of the graphene oxide is 40-43%.
According to another aspect of the present application, there is provided an application of the graphene oxide prepared by the above graphene oxide preparation method in the fields of electronics, information, energy, semiconductors, materials, and oil field hypotonic.
In the present application, "concentrated sulfuric acid" refers to concentrated sulfuric acid having a mass fraction of 95%.
The beneficial effects that this application can produce include:
compared with the traditional Hummers method for preparing graphene oxide, the method for preparing graphene oxide introduces dry ice and ferric trichloride to optimize low-temperature intercalation effect, greatly reduces the use of concentrated sulfuric acid (by 60%), greatly reduces the cost of laboratory and industrial production of graphene oxide, greatly improves the oxygen content of graphene oxide, reduces the particle size of graphene oxide, obtains high-quality graphene oxide materials, and has wide application prospect in the fields of electronics, information, energy, materials and the like.
Drawings
FIG. 1 is a graph showing the particle size distribution of sample No. 1.
Fig. 2 is a particle size distribution diagram of sample 2 #.
FIG. 3 is a graph showing the particle size distribution of sample D1 #.
FIG. 4 is a graph showing the particle size distribution of sample D2 #.
FIG. 5 is a graph showing the particle size distribution of sample D3 #.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified. Unless otherwise specified, the analytical methods in this application are generally performed using conventional analytical methods and conventional instrumentation.
The analysis method in the examples of the present application is as follows:
particle size test analysis was performed using a malvern laser particle sizer, instrument model Zetasizer Nano ZSE.
And (3) performing organic element analysis by using a CHNS/O organic element analyzer to determine the oxygen content of the organic element, wherein the model of the CHNS/O organic element analyzer is PE2400 II. The oxygen content refers to the mass fraction of oxygen element contained.
Example 1
Carrying out ball milling pretreatment on 5g of microcrystalline graphite powder; after treatment, 60ml of concentrated sulfuric acid is added, the mixture is placed in an ice-water bath and mixed and stirred for 10min, 2g of dry ice is added, 30g of potassium permanganate is slowly added in batches (about 10min in total), the temperature of the mixed solution is observed in the adding process, when the temperature is higher than 5 ℃, the dry ice is supplemented (about 3g of dry ice is supplemented in total), the solution is kept at 5 ℃ or above, and the mixture is stirred for 1h at low temperature and the rotating speed is 150rpm under the ice-water bath condition. Adding 1g of ferric trichloride into the solution, continuing stirring in an ice water bath for 1h, transferring the solution to a 45 ℃ medium temperature water bath kettle, and stirring for reaction for 2h at the rotating speed of 150 rpm. And (3) slowly adding 100ml of ice water into the solution along the wall of the cup, testing the temperature of the solution to ensure that the temperature is not higher than 90 ℃, reacting for 5 hours at the rotating speed of 150rpm, naturally cooling to room temperature, then pouring 200ml of deionized water, and adding 2ml of hydrogen peroxide to finish the reaction. Then adjusting the pH value to 12 by using sodium hydroxide, centrifuging at a low speed at 500 revolutions for removing precipitated impurities, centrifuging for several times by using HCl with a volume fraction of 5% and deionized water at a rotating speed of 5000 revolutions, ultrasonically dispersing the centrifuged solution for 1 hour, then diluting the solution to 2000ppm by using the deionized water, and ultrasonically shearing the solution for 1 hour by using a cell disruptor to obtain a target product; the obtained graphene oxide is marked as sample # 1.
Example 2
The procedure is as in example 1, except that the subsequent addition of dry ice is reduced to 2g and the KMnO addition is slowed down continuously in order to maintain the temperature below 5 ℃4The temperature rise is slowed down by the speed of (about 15min), and the obtained graphene oxide is recorded as sample # 2.
Comparative example 1
Preparing graphene oxide by adopting a traditional Hummers method, wherein the preparation method is referred to Hummers WS, Offemann RE. (80) 1339. for transverse comparison, the same method as in example 1 was used after completion of synthesis, and the graphene oxide obtained was treated with ultrasonic shearing for 1h using a cell disruptor, and was recorded as sample D1 #.
Comparative example 2
The procedure of example 1 was repeated, except that the step of adding dry ice was omitted, and the obtained graphene oxide was designated as sample D2 #.
Comparative example 3
The operation is the same as that in example 1, except that the step of adding the intercalation agent of ferric trichloride is omitted, and the obtained graphene oxide is marked as sample D3 #.
Example 3
The particle size test was performed on the samples prepared in the above examples and comparative examples. Figures 1-5 are particle size distribution diagrams from a malvern laser granulometer test, respectively. Table 1 shows the specific test results. The Z-average particle diameter means the average particle diameter, and PDI means the polydispersity. It can be seen that the Z average particle diameters of samples 1# and 2# are about 180nm, which is much smaller than the Z average particle diameters of samples D1#, D2# and D3#, which indicates that the particle diameters of graphene oxide can be greatly reduced by adding dry ice and ferric trichloride, and the PDI of samples 1# and 2# is about 0.27, which is also smaller than the PDI of samples D1#, D2# and D3 #.
TABLE 1 Table of particle size data for samples prepared in examples and comparative examples
| 1# | 2# | D1# | D2# | D3# | |
| Z average particle diameter | 174.2nm | 183.3nm | 541.1nm | 346nm | 379nm |
| PDI | 0.286 | 0.257 | 0.406 | 0.305 | 0.347 |
Oxygen content analysis tests were performed on the samples prepared in the above examples and comparative examples. Table 2 shows the results of the specific oxygen content tests, and it can be seen that the addition of dry ice and ferric chloride increased the elemental oxygen content. Table 3 shows the results of the element content tests.
TABLE 2 oxygen content data of samples prepared in examples and comparative examples
| 1# | 2# | D1# | D2# | D3# | |
| Oxygen content | 42.3％ | 41.6％ | 30.1％ | 37.5％ | 38.2％ |
Table 3 data table of element contents (mass fractions) of samples prepared in examples and comparative examples
| C | O | H | N | |
| Example 1 | 49.6％ | 42.3％ | 3.12％ | 0.09％ |
| Example 2 | 49.9％ | 41.6％ | 3.31％ | 0.07％ |
| Comparative example 1 | 57.7％ | 30.1％ | 4.58％ | 0.04％ |
| Comparative example 2 | 56.1％ | 37.5％ | 4.71％ | 0.08％ |
| Comparative example 3 | 54.8％ | 38.2％ | 4.18％ | 0.12％ |
In conclusion, the particle size of the graphene oxide can be greatly reduced and the oxygen content of the graphene oxide can be increased due to the addition of the dry ice and the ferric trichloride. Compared with the traditional ice bath, the direct contact of the dry ice and the solution greatly accelerates the heat dissipation efficiency, thereby reducing the use amount of concentrated sulfuric acid, improving the intercalation degree of potassium permanganate to graphite powder and improving the oxidation degree. And because the intercalation degree of the step is improved, a foundation is laid for the further intercalation of ferric trichloride of the intercalating agent in the next step. The secondary intercalation method ensures that the thickness of the exfoliated graphene oxide lamella is thinner and the specific surface area is larger during medium-high temperature reaction, is beneficial to improving the oxidation degree of the graphene oxide, and is also more beneficial to ultrasonic shearing due to the thinner lamella thickness, so that the particle size of the graphene oxide is smaller.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of graphene oxide is characterized by at least comprising the following steps:
(a) reacting a mixture I containing a graphite raw material, concentrated sulfuric acid, potassium permanganate and dry ice to obtain a mixed solution I;
(b) reacting a mixture II containing the mixed solution I and the intercalation agent to obtain a mixed solution II;
(c) and reacting the mixed solution II to obtain the graphene oxide.
2. The method for preparing graphene oxide according to claim 1, wherein in the step (a), the mass ratio of the graphite raw material, concentrated sulfuric acid, potassium permanganate and dry ice is as follows:
1：15～25：4～8：0.6～1.2；
preferably, the mass ratio of the graphite raw material, concentrated sulfuric acid, potassium permanganate and dry ice is as follows:
1：18～22：5～6：0.8～1。
3. the method for preparing graphene oxide according to claim 1, wherein the step (a) includes at least:
(a1) reacting a mixture containing a graphite raw material and concentrated sulfuric acid for 5-10min to obtain a mixed solution;
(a2) adding dry ice to the mixed solution for the first time, and then adding KMnO4And then supplementing dry ice again, and continuing to react for 0.8-1.2 h to obtain a mixed solution I.
4. The method for preparing graphene oxide according to claim 3, wherein in the step (a2), the mass ratio of the first dry ice added to the graphite raw material is as follows: 0.2-0.4: 1;
the mass ratio of the replenished dry ice to the graphite raw material is as follows: 0.4-0.8: 1;
adding KMnO4The duration of the time is 8-15 min.
5. The method for preparing graphene oxide according to claim 1, wherein in the step (b), the intercalation agent is selected from at least one of ferric trichloride and zinc chloride;
preferably, the intercalating agent is ferric chloride.
6. The preparation method of graphene oxide according to claim 5, wherein the mass ratio of the graphite raw material to the intercalation agent is 3-8: 1;
preferably, the mass ratio of the graphite raw material to the intercalation agent is 4-6: 1.
7. the method for preparing graphene oxide according to claim 1, wherein in step (a), the conditions of reaction I are as follows: the reaction temperature is 0-5 ℃, the reaction time is 1-2 h, and the stirring speed is 100-200 rpm;
in the step (b), the conditions of the reaction II are as follows: the reaction temperature is 0-5 ℃, the reaction time is 1-2 h, and the stirring speed is 100-200 rpm;
in the step (c), the reaction is a high-temperature reaction after a medium-temperature reaction, and the medium-temperature reaction conditions are as follows: the reaction temperature is 40-50 ℃, the reaction time is 1.5-2.5 h, and the stirring speed is 100-200 rpm; the high-temperature reaction conditions are as follows: the reaction temperature is 80-90 ℃, the reaction time is 4-6 h, and the stirring speed is 100-200 rpm.
8. The method for preparing graphene oxide according to claim 1, further comprising the steps of:
(d) adding H to the product obtained in step (c)2O2And alkali liquor, adjusting the pH value to 11-13, centrifuging at a low speed, and then washing with acid and water;
(e) and (d) ultrasonically dispersing the solution centrifuged in the step (d) and ultrasonically shearing to obtain the graphene oxide.
9. The method for preparing graphene oxide according to claim 1, wherein the particle size of the graphene oxide is 170 to 200 nm;
preferably, the oxygen content of the graphene oxide is 40-43%.
10. The graphene oxide prepared by the preparation method of the graphene oxide according to any one of claims 1 to 9 is applied to the fields of electronics, information, energy, semiconductors, materials and oil field hypotonic.
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