CN115321529A - Method for green macro preparation of graphene through biological fermentation - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to the field of graphene materials, and particularly relates to a method for green macro-preparation of graphene through biological fermentation. The method utilizes white rot fungi which can efficiently metabolize organic acid and generate oxidoreductase and peroxidase to carry out synchronous biological oxidation and intercalation treatment on graphite, utilizes the oxidation effect of metabolic active substances such as enzyme generated by the white rot fungi to carry out biological oxidation on the graphite, and then carries out membrane filtration separation to obtain biological graphite oxide; synchronously stripping and removing impurities from the obtained biological graphite oxide by using supercritical carbon dioxide to obtain the biological graphene oxide. According to the method, organic acid and other organic micromolecules are inserted between graphite layers, so that the defect of graphene oxide caused by the use of strong acid in a chemical oxidation method is reduced to a great extent; the graphene generated by the biological oxidation stripping method is low in oxidation degree, the generated graphene sheet is excellent in property, and the preparation process is clean and pollution-free.
Description
Technical Field
The invention belongs to the field of graphene materials, and particularly relates to a method for green macro-preparation of graphene through biological fermentation.
Background
Graphene is a sheet of a hexagonal ring-shaped structure formed by covalently bonding hybridized carbon atoms to each other, and many graphene sheets attract each other by van der waals force and are stacked into graphite. The bonding energy among graphite carbon atoms is 345kJ/mol, the C-C bond length among the graphene atoms is about 0.142nm, the van der Waals force bonding energy among layers is 16.7kJ/mol, and the interlayer spacing is 0.3354nm. Because of the large distance between layers and the small binding force, a plurality of chemical substances can be inserted into the gaps between the graphite layers to form the compound between the graphite layers.
At present, the redox method is the most widely applied method for preparing graphene at present, and the most common method is the Hummers method or an improved method thereof. The principle is that strong protonic acid is used as intercalation material and inserted between graphite layers to form graphite intercalation compound, then under the action of oxidant, the carbon atom of graphite is oxidized and inserted into oxygen-containing functional group of carboxyl group, epoxy group, etc. and then the graphite is stripped. However, in the process of preparing graphene by treating graphite with strong acid, the crystal structure of a carbon atom layer is often damaged, and large defects or etching are generated; in addition, the method needs to consume and discharge a large amount of waste liquid containing corrosive strong acid and strong oxidizing compounds, the production cost is relatively high, and the environmental pollution is serious.
Therefore, the chemical method for preparing graphene oxide has the defect that the chemical method is difficult to overcome, not only can a large amount of waste liquid pollution be generated, but also the preparation cost and the environmental burden can be increased, and the chemical method becomes an insurmountable bottleneck for the industrial application.
At present, few relevant reports of the biological preparation method of graphite oxide exist. Although it has been reported that dispersed graphite is biologically oxidized by Thiobacillus ferrooxidans, the medium required for bacterial growth is complicated and contains many inorganic salts, and the major products of bacterial metabolism are also inorganic salts. According to the method, on one hand, the preparation cost of the biological graphite oxide is increased, on the other hand, the hydrochloric acid is required to repeatedly elute the graphite to remove inorganic salt substances, the workload of graphene oxide preparation is increased, and more sewage is still generated. Moreover, the oxidation effect of the thiobacillus ferrooxidans on graphite is relatively weak, so that the development and industrial application of the method are greatly restricted.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing graphene in a green and large-scale manner by biological fermentation.
A method for preparing graphene in a green and macro manner by biological fermentation comprises the following steps:
s1: dispersing graphite into a fermentation culture medium to obtain a graphite dispersion liquid; adding the fungus immobilized material into a fermentation medium to obtain a fermentation liquid; respectively sterilizing the graphite dispersion liquid and the fermentation liquid;
s2: activating fungi, adding into fermentation medium, and shake culturing at constant temperature of 25-55 deg.C and 150-220r/min for 24-36 hr to obtain spore suspension;
s3: adding the spore suspension into the fermentation broth, and culturing at constant temperature of 25-55 deg.C and 150-220r/min for 4-7 days until the mycelium covers the surface of the immobilized material to obtain immobilized fungus fermentation broth;
s4: adding the graphite dispersion liquid into the fermentation liquor of the immobilized fungi, fermenting and culturing for 5-10 days at a constant temperature of 25-55 ℃ and 150-220r/min, and then performing membrane filtration to obtain biological graphite oxide;
s5: and (3) carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
Preferably, in the graphite dispersion liquid of S1, the mass fraction of graphite is 10% -50%.
Preferably, the sterilization conditions in S1 are: sterilizing at 121 deg.C under 0.1MPa for 20min.
Preferably, the spore suspension in S3 accounts for 5-10% of the total mass of the spore suspension and the fermentation broth.
Preferably, the adding amount of the graphite dispersion liquid in S4 accounts for 10-30% of the total mass of the mixture of the graphite dispersion liquid and the fermentation liquor of the immobilized fungi.
Preferably, S5 specifically includes: and introducing carbon dioxide into the biological graphite oxide, controlling the pressure to reach 7-15MPa, then carrying out ultrasonic stripping on the graphite for 20-30min by using an ultrasonic probe, keeping the pressure and the temperature at 7-15MPa and 40-60 ℃ in the stripping process, and discharging the carbon dioxide to obtain the microbial graphene oxide.
Preferably, the fungus in S2 is a white rot fungus.
Preferably, the white rot fungi is one of penicillium, aspergillus, trichoderma, mucor and rhizopus.
Compared with the prior art, the invention has the beneficial effects that:
(1) The oxidation of metabolic active substances such as enzyme generated by white rot fungi is utilized to carry out biological oxidation on graphite, organic acid and other organic micromolecules are utilized to be inserted between graphite layers, and the defect of graphene oxide caused by the use of strong acid in a chemical oxidation method is reduced to a great extent; (2) Graphene generated by a biological oxidation stripping method is low in oxidation degree, large in specific surface area and excellent in property of generated graphene sheets; (3) The biological graphite oxide and the preparation method thereof provided by the invention are simple to operate and do not need to be repeatedly washed; (4) The biological graphite oxide and the preparation method thereof provided by the invention have the advantages of mild fermentation conditions, clean preparation process, no pollution, no generation of a large amount of waste liquid, low cost and wide industrial application value and significance.
Drawings
FIG. 1 is a transmission electron micrograph of the biological graphene oxide obtained in example 1;
fig. 2 is an AFM test chart of the bio-graphene oxide obtained in example 1.
Detailed Description
The invention is further described with reference to specific examples.
Source of raw materials
Aspergillus was purchased from Ningbo Test Tuo biology under the cat number TS284005;
penicillium is purchased from Ningbo Test Tuo, cat # TS277257;
trichoderma was purchased from Ningbo Test Tuo, cat # TS280512;
mucor is purchased from Ningbo Test Tuo biology under the product number TS283985;
rhizopus is purchased from Ningbo Tesla Tuo, cat # TS285843;
expanded graphite is obtained from Hezhou ink (particle size 2-30 μm);
PDA plate culture medium: from the microorganism of the Kjeldahl, product number CP0010;
fermentation medium: the components of the wheat bran flour comprise 15g/L of sucrose, 2g/L of yeast powder, 15g/L of wheat bran and MgSO 4 ·7H 2 O 0.5g/L、KH 2 PO 4 1.5g/L, vitamin B 1 4mg/L, glucose 20g/L and water;
fungus immobilization material: using poplar, pine or cedar sawdust (the granularity is 0.05-0.3 cm).
Example 1
A microbial graphene oxide is prepared by the following steps:
the first step is as follows: taking 70g of fermentation medium, adding 30g of graphite into the fermentation medium, and carrying out ultrasonic stirring and dispersion on the expanded graphite for 1 hour at the temperature of 4 ℃, the ultrasonic power of 300W and the stirring speed of 150r/min to obtain graphite dispersion liquid; adding 0.19g of fungus immobilized material (poplar sawdust) into a fermentation culture medium to obtain 95g of fermentation liquid; then respectively sterilizing the graphite dispersion liquid and the fermentation liquor at 121 ℃ and 0.1MPa for 20min;
activating aspergillus on a PDA plate culture medium, beating the activated strain into a bacterial disc with the diameter of 6mm under the aseptic condition by using an aseptic puncher (with the inner diameter of 6 mm) after 4 days, inoculating 3 bacterial discs into 100mL of fermentation culture medium which is inactivated for 20min at the temperature of 121 ℃ and the pressure of 0.1MPa, and carrying out constant-temperature shaking culture for 24 hours under the conditions of 25 ℃ and 160r/min to obtain a spore suspension;
thirdly, 5g of spore suspension is sucked and inoculated into 95g of inactivated fermentation liquor, and the mixture is cultured for 7 days at constant temperature under the conditions of 25 ℃ and 160r/min until hypha covers the surface of the immobilized material, so that the fermentation liquor of the immobilized fungi is obtained;
fourthly, weighing 20g of sterilized graphite dispersion liquid, adding the weighed graphite dispersion liquid into the fermentation liquid of the immobilized fungi, continuously fermenting and culturing for 5 days at a constant temperature under the conditions of 25 ℃ and 160r/min, and then performing membrane filtration (0.22 micron) to obtain biological graphite oxide;
and fifthly, carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide. The method comprises the following specific steps: putting biological graphite oxide into a reaction kettle, heating the equipment to 40 ℃, adding carbon dioxide into the reaction kettle by using a pump, enabling the pressure to reach 9MPa, ultrasonically stripping the graphite by using an ultrasonic probe for 20min, keeping the ultrasonic intensity at 150W, keeping the pressure and the temperature at 9MPa and 40 ℃ in the stripping process, opening a valve to discharge the carbon dioxide in the reaction kettle after ultrasonically stripping for 20min, opening the reaction kettle, and taking out a product to obtain the biological graphene oxide.
Example 2
A microbial graphene oxide is prepared by the following steps:
the first step is as follows: taking 90g of fermentation medium, adding 10g of graphite into the fermentation medium, and carrying out ultrasonic stirring and dispersion on the graphite for 2 hours at the temperature of 18 ℃, the ultrasonic power of 300W and the stirring speed of 150r/min to obtain graphite dispersion liquid; adding 0.18g of fungus immobilized material (poplar sawdust) into a fermentation culture medium to obtain 90g of fermentation liquid; then respectively sterilizing the graphite dispersion liquid and the fermentation liquor at 121 ℃ and 0.1MPa for 20min;
activating the penicillium on a PDA plate culture medium, beating the activated strain into a bacterial dish with the diameter of 6mm under the aseptic condition by using an aseptic puncher (with the inner diameter of 6 mm) after 3 days, inoculating 3 blocks of bacterial dishes into 100mL of fermentation culture medium inactivated for 20min at the temperature of 121 ℃ and the pressure of 0.1MPa, and performing shaking culture at the constant temperature of 25 ℃ and 180r/min for 30 hours to obtain a spore suspension;
thirdly, 10g of spore suspension is sucked and inoculated into 90g of inactivated fermentation liquor, and the mixture is cultured for 4 days at constant temperature under the conditions of 25 ℃ and 180r/min until hypha covers the surface of the immobilized material, so as to obtain fermentation liquor of the immobilized fungi;
fourthly, weighing 15g of sterilized graphite dispersion liquid, adding the weighed graphite dispersion liquid into the fermentation liquid of the immobilized fungi, continuously fermenting and culturing for 7 days at a constant temperature under the conditions of 25 ℃ and 180r/min, and then performing membrane filtration (0.22 micron) to obtain biological graphite oxide;
and fifthly, carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
The method specifically comprises the following steps: putting biological graphite oxide into a reaction kettle, heating the equipment to 43 ℃, adding carbon dioxide into the reaction kettle by using a pump, enabling the pressure to reach 10MPa, carrying out ultrasonic stripping on the graphite for 20min by using an ultrasonic probe, keeping the ultrasonic intensity at 150W, keeping the pressure and the temperature at 10MPa and 43 ℃ in the stripping process, confirming the coupling effect of the ultrasonic stripping effect and the supercritical carbon dioxide to strip the graphite into graphene, opening a valve to discharge the carbon dioxide in the reaction kettle after carrying out ultrasonic stripping for 20min, opening the reaction kettle, and taking out a product to obtain the biological graphite oxide.
Example 3
A microbial graphene oxide is prepared by the following steps:
the first step is as follows: taking 80g of fermentation medium, adding 20g of graphite into the fermentation medium, and carrying out ultrasonic stirring and dispersion on the graphite for 1.5 hours at the temperature of 20 ℃, the ultrasonic power of 300W and the stirring speed of 150r/min to obtain a graphite dispersion liquid; adding 0.18g of fungus immobilized material (cedar wood chips) into a fermentation culture medium to obtain 90g of fermentation liquor; then sterilizing the graphite dispersion liquid and the fermentation liquor for 20min at 121 ℃ and 0.1MPa respectively;
secondly, activating trichoderma added on a PDA plate culture medium, beating the activated strain into a bacterial disc with the diameter of 6mm under the aseptic condition by using an aseptic puncher (with the inner diameter of 6 mm) after 5 days, inoculating 3 bacterial discs into 100mL of fermentation culture medium inactivated for 20min at the temperature of 121 ℃ and the pressure of 0.1MPa, and culturing for 25 hours by using a constant-temperature shaking table under the conditions of 40 ℃ and 150r/min to obtain a spore suspension;
thirdly, 10g of spore suspension is sucked and inoculated into 90g of inactivated fermentation liquor, and the mixture is cultured for 5 days at constant temperature under the conditions of 40 ℃ and 150r/min until hypha covers the surface of the immobilized material, so as to obtain the fermentation liquor of the immobilized fungi;
step four, weighing 25g of sterilized graphite dispersion liquid, adding the graphite dispersion liquid into fermentation liquor of immobilized fungi, continuously fermenting and culturing for 10 days at constant temperature of 40 ℃ and 150r/min, and then performing membrane filtration (0.22 micron) to obtain biological graphite oxide;
and fifthly, carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
The method specifically comprises the following steps: putting biological graphite oxide into a reaction kettle, heating the equipment to 45 ℃, adding carbon dioxide into the reaction kettle by using a pump, enabling the pressure to reach 11MPa, carrying out ultrasonic stripping on the graphite by using an ultrasonic probe for 25min, keeping the ultrasonic intensity at 150W, keeping the pressure and the temperature at 11MPa and 45 ℃ in the stripping process, confirming that the coupling effect of the ultrasonic stripping effect and the supercritical carbon dioxide is stripped into graphene, opening a valve to discharge the carbon dioxide in the reaction kettle after carrying out ultrasonic stripping for 25min, opening the reaction kettle, and taking out a product to obtain the biological graphite oxide.
Example 4
A microbial graphene oxide is prepared by the following steps:
the first step is as follows: taking 70g of fermentation medium, adding 30g of graphite into the fermentation medium, and carrying out ultrasonic stirring and dispersion on the graphite for 1.5 hours at the temperature of 20 ℃, the ultrasonic power of 300W and the stirring speed of 150r/min to obtain a graphite dispersion liquid; adding 0.15g of fungus immobilized material (poplar chips) into a fermentation culture medium to obtain 92g of fermentation liquid; then sterilizing the graphite dispersion liquid and the fermentation liquor for 20min at 121 ℃ and 0.1MPa respectively;
activating mucor on a PDA plate culture medium, beating the activated strain into a bacterial disc with the diameter of 6mm under the aseptic condition by using an aseptic puncher (with the inner diameter of 6 mm) after 4 days, inoculating 3 bacterial discs into 100mL of fermentation culture medium inactivated for 20min at the temperature of 121 ℃ and the pressure of 0.1MPa, and performing constant-temperature shaking culture for 24 hours under the conditions of 28 ℃ and 180r/min to obtain a spore suspension;
thirdly, sucking 8g of spore suspension, inoculating the spore suspension into 92g of inactivated fermentation broth, and culturing for 6 days at constant temperature at 28 ℃ and 180r/min until hyphae cover the surface of the immobilized material to obtain immobilized fungus fermentation broth;
fourthly, weighing 36g of sterilized graphite dispersion liquid, adding the weighed graphite dispersion liquid into the fermentation liquid of the immobilized fungi, continuously fermenting and culturing for 7 days at a constant temperature under the conditions of 25 ℃ and 180r/min, and then performing membrane filtration (0.22 micron) to obtain biological graphite oxide;
and fifthly, carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
The method specifically comprises the following steps: putting biological graphite oxide into a reaction kettle, heating the equipment to 40 ℃, adding carbon dioxide into the reaction kettle by using a pump, enabling the pressure to reach 12MPa, carrying out ultrasonic stripping on the graphite for 20min by using an ultrasonic probe, keeping the ultrasonic intensity at 150W, keeping the pressure and the temperature at 12MPa and 40 ℃ in the stripping process, confirming the coupling effect of the ultrasonic stripping effect and the supercritical carbon dioxide to strip the graphite into graphene, opening a valve to discharge the carbon dioxide in the reaction kettle after carrying out ultrasonic stripping for 20min, opening the reaction kettle, and taking out a product to obtain the biological graphite oxide.
Example 5
A microbial graphene oxide is prepared by the following steps:
the first step is as follows: taking 50g of fermentation medium, adding 50g of graphite into the fermentation medium, and carrying out ultrasonic stirring and dispersion on the graphite for 1.5 hours at the temperature of 4 ℃, the ultrasonic power of 300W and the stirring speed of 150r/min to obtain graphite dispersion liquid; adding 0.15g of fungus immobilized material (pine wood chips) into a fermentation medium to obtain 93g of fermentation liquid; then respectively sterilizing the graphite dispersion liquid and the fermentation liquor at 121 ℃ and 0.1MPa for 20min;
activating rhizopus on a PDA plate culture medium, beating the activated strain into a bacterium dish with the diameter of 6mm under the aseptic condition by using an aseptic puncher (with the inner diameter of 6 mm) after 3 days, inoculating 3 bacterium dishes into 100mL of fermentation culture medium inactivated for 20min at the temperature of 121 ℃ and the pressure of 0.1MPa, and carrying out constant-temperature shaking culture for 36 hours under the conditions of 28 ℃ and 210r/min to obtain a spore suspension;
thirdly, sucking 7g of spore suspension liquid, inoculating the spore suspension liquid into 93g of inactivated fermentation liquid, and culturing for 7 days at a constant temperature at the temperature of 28 ℃ and the speed of 210r/min until hypha covers the surface of the immobilized material to obtain the fermentation liquid of the immobilized fungi;
fourthly, weighing 30g of sterilized graphite dispersion liquid, adding the graphite dispersion liquid into the fermentation liquid of the immobilized fungi, continuously fermenting and culturing for 5 days at the constant temperature of 25 ℃ and 210r/min, and then performing membrane filtration (0.22 micron) to obtain biological graphite oxide;
and fifthly, carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
The method specifically comprises the following steps: putting biological graphite oxide into a reaction kettle, heating equipment to 45 ℃, adding carbon dioxide into the reaction kettle by using a pump, enabling the pressure to reach 15MPa, carrying out ultrasonic stripping on the graphite again by using an ultrasonic probe for 30min, keeping the ultrasonic intensity at 150W, keeping the pressure and the temperature at 15MPa and 45 ℃ in the stripping process, confirming the coupling effect of the ultrasonic stripping effect and the supercritical carbon dioxide to strip the graphite into graphene, opening a valve to discharge the carbon dioxide in the reaction kettle after carrying out ultrasonic stripping for 30min, opening the reaction kettle, and taking out a product to obtain the biological graphite oxide.
Example 6
A microbial graphene oxide, the preparation of which comprises the following steps:
the first step is as follows: taking 50g of fermentation medium, adding 50g of graphite into the fermentation medium, and carrying out ultrasonic stirring and dispersion on the graphite for 1.5 hours at the temperature of 4 ℃, the ultrasonic power of 300W and the stirring speed of 150r/min to obtain graphite dispersion liquid; adding 0.15g of fungus immobilized material (poplar chips) into a fermentation culture medium to obtain 93g of fermentation liquid; then sterilizing the graphite dispersion liquid and the fermentation liquor for 20min at 121 ℃ and 0.1MPa respectively;
activating rhizopus on a PDA plate culture medium, beating the activated strain into a bacterial dish with the diameter of 6mm under the aseptic condition by using an aseptic perforator (with the inner diameter of 6 mm) after 3 days, inoculating 3 bacterial dishes into 100mL of fermentation culture medium inactivated for 20min at the temperature of 121 ℃ and the pressure of 0.1MPa, and performing constant-temperature shaking culture for 36 hours under the conditions of 28 ℃ and 210r/min to obtain a spore suspension;
thirdly, sucking 7g of spore suspension liquid, inoculating the spore suspension liquid into 93g of inactivated fermentation liquor, and culturing for 7 days at constant temperature at the temperature of 28 ℃ and at the speed of 210r/min until hyphae cover the surface of the immobilized material to obtain fermentation liquor of the immobilized fungi;
fourthly, weighing 30g of sterilized graphite dispersion liquid, adding the graphite dispersion liquid into the fermentation liquid of the immobilized fungi, continuously fermenting and culturing for 5 days at the constant temperature of 25 ℃ and 210r/min, and then performing membrane filtration (0.22 micron) to obtain biological graphite oxide;
and fifthly, carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
The method specifically comprises the following steps: putting biological graphite oxide into a reaction kettle, heating the equipment to 45 ℃, adding carbon dioxide into the reaction kettle by using a pump, enabling the pressure to reach 15MPa, carrying out ultrasonic stripping on the graphite again by using an ultrasonic probe for 30min, keeping the ultrasonic intensity at 150W, keeping the pressure and the temperature at 15MPa and 45 ℃ in the stripping process, confirming that the coupling effect of the ultrasonic stripping effect and the supercritical carbon dioxide is stripped into graphene, opening a valve to discharge the carbon dioxide in the reaction kettle after carrying out ultrasonic stripping for 30min, opening the reaction kettle, and taking out a product to obtain the biological graphite oxide.
The bio-graphene oxide obtained in example 1 was subjected to transmission electron microscope and AFM tests, and the graphene oxide obtained in examples 1 to 5 was subjected to BET specific surface area tests. Fig. 1 is a TEM photograph of graphene oxide, and fig. 2 is an AFM test image of graphene oxide. The specific surface area test results are shown in Table 1.
Table 1 specific surface area test results of graphene oxide obtained in examples 1 to 6
As can be seen from the specific surface area test results shown in Table 1, the specific surface area of the graphene oxide obtained by the method is remarkably improved, and the graphene oxide has better performance. As can be seen from the transmission electron microscope image in fig. 1, the graphene is transparent and has wrinkles, the number of layers of the oxidized graphene is significantly reduced relative to that of graphite, and the number of layers of the oxidized graphene is less than 4. As can be seen from the AFM image of fig. 2, the particle size of the obtained graphene oxide is 1 micron or less, and is mostly 400 to 500nm, and is significantly smaller than the particle size of the expanded graphite, which is 2 to 30 microns, and it can be verified that the graphene is corroded and is in a weakly oxidized state.
The above embodiments are merely illustrative of the present application and are not intended to be limiting, industrial-scale amplification and the like may be performed on the basis of the present application, and modifications that do not contribute to the inventive concept may be made to the present embodiment as required by those skilled in the art after reading the present specification, but are protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. A method for preparing graphene in a green and macro manner through biological fermentation is characterized by comprising the following steps:
s1: dispersing expanded graphite into a fermentation culture medium to obtain graphite dispersion liquid; adding the fungus immobilized material into a fermentation medium to obtain a fermentation liquid; respectively sterilizing the graphite dispersion liquid and the fermentation liquid;
s2: activating fungi, adding into fermentation medium, and performing constant temperature shaking culture at 25-55 deg.C and 150-220r/min for 24-36 hr to obtain spore suspension;
s3: adding the spore suspension into the fermentation liquid, and culturing at constant temperature of 25-55 deg.C and 150-220r/min for 4-7 days until the mycelium covers the surface of the immobilized material to obtain immobilized fungus fermentation liquid;
s4: adding the graphite dispersion liquid into fermentation liquor of immobilized fungi, fermenting and culturing for 5-10 days at constant temperature of 25-55 ℃ and 150-220r/min, and then performing membrane filtration to obtain biological graphite oxide;
s5: and (3) carrying out supercritical carbon dioxide stripping and impurity removal on the biological graphite oxide to obtain the biological graphene oxide.
2. The method for preparing graphene in a greening and macro-scale manner through biological fermentation according to claim 1, wherein the method comprises the following steps: in the graphite dispersion liquid of S1, the mass fraction of graphite is 10-50%.
3. The method for preparing graphene in a green and macro manner through biological fermentation according to claim 1, which is characterized in that: the sterilization conditions in S1 are: sterilizing at 121 deg.C under 0.1MPa for 20min.
4. The method for preparing graphene in a greening and macro-scale manner through biological fermentation according to claim 1, wherein the method comprises the following steps: and in S3, the spore suspension accounts for 5-10% of the total mixed mass of the spore suspension and the fermentation liquor.
5. The method for preparing graphene in a greening and macro-scale manner through biological fermentation according to claim 1, wherein the method comprises the following steps: and in S4, the adding amount of the graphite dispersion liquid accounts for 10-30% of the total mixed mass of the graphite dispersion liquid and the fermentation liquor of the immobilized fungi.
6. The method for preparing graphene in a greening and macro-scale manner through biological fermentation according to claim 1, wherein the method comprises the following steps: s5 specifically comprises the following steps: introducing carbon dioxide into the biological graphite oxide, controlling the pressure to be 7-15MPa, then ultrasonically stripping the graphite for 20-30min by using an ultrasonic probe, keeping the pressure and the temperature at 7-15MPa and 40-60 ℃ in the stripping process, and discharging the carbon dioxide to obtain the microbial graphene oxide.
7. The method for preparing graphene in a greening and macro-scale manner through biological fermentation according to claim 1, wherein the method comprises the following steps: the fungus in S2 is white rot fungus.
8. The method for preparing graphene in a greening and macro-scale manner through biological fermentation according to claim 7, wherein the method comprises the following steps: the white-rot fungi is one of penicillium, aspergillus, trichoderma, mucor and rhizopus.
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