CN107381551B - Manganese-embedded graphene and preparation method and application thereof - Google Patents

Manganese-embedded graphene and preparation method and application thereof Download PDF

Info

Publication number
CN107381551B
CN107381551B CN201710704271.9A CN201710704271A CN107381551B CN 107381551 B CN107381551 B CN 107381551B CN 201710704271 A CN201710704271 A CN 201710704271A CN 107381551 B CN107381551 B CN 107381551B
Authority
CN
China
Prior art keywords
mixture
manganese
graphene
sulfuric acid
concentrated sulfuric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710704271.9A
Other languages
Chinese (zh)
Other versions
CN107381551A (en
Inventor
杨中柱
郑颖
赵美莲
何巧
伍权
詹昌霖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu University of Traditional Chinese Medicine
Original Assignee
Chengdu University of Traditional Chinese Medicine
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu University of Traditional Chinese Medicine filed Critical Chengdu University of Traditional Chinese Medicine
Publication of CN107381551A publication Critical patent/CN107381551A/en
Application granted granted Critical
Publication of CN107381551B publication Critical patent/CN107381551B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Abstract

The invention discloses MnO3 +The application of the manganese-intercalated graphene serving as an intercalator in preparation of manganese-intercalated graphene. The invention also discloses manganese-embedded graphene and a preparation method and application thereof, and aims toAnd a low-density graphene oxide and a preparation method thereof. The method has mild reaction conditions, is operated at room temperature in the whole process, and does not need complicated operation and control of medium temperature, low temperature, high temperature and the like, wherein MnO is used3 +And concentrated sulfuric acid can be separated out of the reaction system in a liquid form, can be recycled, and can effectively reduce the cost.

Description

Manganese-embedded graphene and preparation method and application thereof
Technical Field
The invention relates to manganese-embedded graphene and a preparation method and application thereof.
Background
Graphene oxide has become a hot spot of domestic and foreign research in recent years due to its large surface area, unique two-dimensional structure and excellent performance, and has been widely used, and many methods for preparing graphene oxide using graphite as a raw material exist, among which the most common method is Hummers method, which is characterized by using KMnO as a material4And concentrated sulfuric acid as an oxidant to prepare the graphene oxide.
However, the existing Hummers method needs a complicated temperature control process, which generally comprises three steps of low temperature, medium temperature and high temperature, so that the energy consumption is high; meanwhile, the addition of excessive potassium permanganate and concentrated sulfuric acid increases the subsequent hydrogen peroxide dosage, and directly increases the preparation cost; moreover, the traditional separation process requires centrifugation and is a process with high energy consumption.
In order to overcome the above defects, it is necessary to provide a better method for preparing functionalized graphene, and in particular, to further improve the existing preparation method of graphene oxide.
Disclosure of Invention
In order to solve the above problems, the present invention discloses MnO3 +The application of the manganese-embedded graphene serving as an intercalator in preparation of the manganese-embedded graphene, a preparation method and application of the manganese-embedded graphene, and the low-density graphene oxide and a preparation method of the low-density graphene oxide.
The invention discloses MnO3 +The application of the manganese-intercalated graphene serving as an intercalator in preparation of manganese-intercalated graphene.
Intercalation agent: the graphite layers are connected tightly, in order to promote the graphite layers to be stripped, the graphene or the graphene derivative with lower lamella is prepared, polar molecules need to be intercalated between the graphite layers to increase the interlayer spacing, and the polar molecules intercalated between the graphite layers are the intercalating agent.
The invention discloses manganese-embedded graphene.
Wherein the manganese-embedded graphene is purple.
Wherein, the manganese-embedded graphene comprises the following structure:
Figure BDA0001380981990000011
wherein R is H, OH, HSO4、MnO4COOH or hydrogen bonded H2O; intercalation agent MnO used in the invention3 +Is of planar construction, this results in MnO3 +Can be easily intercalated between graphite flake layers under relatively mild conditions as an intercalant.
The invention also discloses a method for preparing the manganese-embedded graphene, which comprises the following steps:
preprocessing graphite: taking graphite, sodium nitrate and concentrated sulfuric acid, and uniformly mixing at 25 +/-2 ℃ to obtain a mixture A;
② preparation of MnO3 +: at the temperature of 25 +/-2 ℃, taking sodium nitrate, potassium permanganate and concentrated sulfuric acid, and uniformly mixing to obtain a mixture B;
③、MnO3 +preparation of manganese-intercalated graphene as an intercalator: and adding the mixture B into the mixture A at 25 +/-2 ℃ for reaction to obtain the manganese-embedded graphene.
The possible mechanism for preparing manganese-embedded graphene according to the invention is: the pretreated graphite powder contains hydroxyl (similar to expanded graphite powder) on the surface and MnO3 +Reaction to make MnO of planar structure3 +Combined with hydroxy oxygen and giving off hydrogen ions, MnO3 +Is converted into-MnO4The tetrahedron structure is connected on the surface of the graphene oxide, so that the distance between the graphite sheets is increased, which is beneficial to MnO3 +And (5) further carrying out intercalation.
Figure BDA0001380981990000021
Wherein R is H, OH, HSO4、MnO4COOH or hydrogen bonded H2O。
In the step (i), the weight ratio of the graphite to the sodium nitrate is 1:0.8 to 1.2, preferably 1:0.9 to 1.1; the weight volume ratio of the graphite to the concentrated sulfuric acid is 1: 40-50 g/mL, preferably 1: 44-48 g/mL.
In the second step, the weight ratio of the sodium nitrate to the potassium permanganate is 1: 5-10, preferably 1: 5-6; the weight volume ratio of the sodium nitrate to the concentrated sulfuric acid is 1: 140-150 g/mL, preferably 1: 144-148 g/mL.
Wherein, in the first step and the second step, the water content of the concentrated sulfuric acid is within 2% w/w, and is preferably 1% -2% w/w.
In the third step, the mixture B is added into the mixture A in a plurality of times, and the time interval between the two times is 15-25 minutes, preferably 18-22 minutes, and more preferably 20 minutes; adding 2-5 parts by volume of the mixture B into 20-25 parts by volume of the mixture A each time; in the step III, the total amount of the mixture B is 70-80 parts by volume; preferably, the total amount of the mixture B is 70 to 75 parts by volume.
The manganese-embedded graphene is applied to preparation of graphene oxide.
The invention also discloses graphene oxide with the density of 1.00-1.08 g/mL.
The invention discloses a method for preparing graphene oxide, which comprises the following steps:
a. preparing manganese-embedded graphene according to the method;
b. and (3) taking the manganese-embedded graphene at the temperature of 25 +/-2 ℃, and adding hydrogen peroxide to obtain the graphene oxide.
Wherein, in the step b, the hydrogen peroxide content in the hydrogen peroxide is 27.5-30% w/w; the weight volume ratio of the manganese-embedded graphene to the hydrogen peroxide is 1: 2-10 g/mL, preferably 1: 5-10 g/mL.
The invention uses MnO with planar structure3 +As an intercalating agent, the preparation method is equation (3):
(1)2KMnO4+H2SO4＝Mn2O7+K2SO4+H2O(2:1)
(2)2KMnO4+2H2SO4＝MnO3 ++HSO4 -+HMnO4+K2SO4+H2O(1:1)
(3)KMnO4+3H2SO4＝K++MnO3 ++3HSO4 -+H3O+(1:3)
the main mechanism of the prior art is shown in the reaction formulas (1) and (2), and the invention is carried out in concentrated H2SO4Prepared in excess, formula (3) being MnO preparation according to the invention3 +It can be seen that the process of the inventionPreparation of MnO3 +Spent KMnO4In a small amount and MnO after the reaction3 +And concentrated sulfuric acid can be separated out of the reaction system in a liquid form and can be recycled.
Compared with the prior Hummers method, the invention uses MnO3 +The manganese-embedded graphene is prepared by taking the manganese-embedded graphene as an intercalation agent, and then graphene oxide is further prepared, the reaction condition is mild, the whole process is operated at room temperature, and the tedious operations and controls of medium temperature, low temperature, high temperature and the like are not needed, wherein MnO is3 +And concentrated sulfuric acid can be separated out of the reaction system in a liquid form and can be reused, so that the cost is effectively reduced, wastewater treatment by hydrogen peroxide and the like is not needed, the method is environment-friendly, and the graphene oxide has low density, can be separated by a similar flotation method, is simple and easy to implement, and is very suitable for industrial application.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is an external view of a manganese-intercalated graphene intermediate product obtained in example 1 of the present invention;
FIG. 2 is an appearance diagram of graphene oxide being prepared according to example 6 of the present invention;
FIG. 3 is an appearance diagram of a graphene oxide completely reacted in example 6 of the present invention;
FIG. 4 is an appearance diagram of the graphene oxide prepared in example 6 of the present invention after vacuum drying;
FIG. 5 shows MnO drawn in Experimental example 1 of the present invention3 +A standard curve of concentration versus maximum absorption at 458.5 nm;
FIG. 6 is a graph of IR spectrum measurements of graphene oxide in Experimental example 2 of the present invention;
FIG. 7 is a graph showing an X-ray surface photoelectron energy spectrum measured in Experimental example 2 of the present invention;
FIG. 8 is an atomic force microscope chromatogram obtained in Experimental example 2 of the present invention;
FIG. 9 is an appearance of an intermediate product obtained in comparative example 1;
FIG. 10 is an appearance diagram of graphene oxide prepared in comparative example 1;
fig. 11 is an appearance diagram of graphene oxide prepared in comparative example 2.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
Example 1 preparation of manganese-intercalated graphene of the invention
(1) 0.5g of graphite powder, 0.5g of sodium nitrate and 23mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture A.
(2) 0.5g of sodium nitrate powder, 3g of potassium permanganate and 73mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture B.
(3) 4mL of mixture B was added to the mixture A, and the addition was repeated every 20 minutes until the mixture B was added, and then stirred for 4 hours to obtain purple manganese-intercalated graphene as shown in FIG. 1.
Example 2 preparation of manganese-intercalated graphene according to the invention
(1) 0.5g of graphite powder, 0.45g of sodium nitrate and 22mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture A.
(2) 0.5g of sodium nitrate powder, 2.5g of potassium permanganate and 70mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and are mixed uniformly to obtain a mixture B.
(3) 3mL of mixture B was added to mixture A, repeated every 25 minutes until mixture B was added, and stirred for 5 hours to give a purple manganic-intercalated graphene.
Example 3 preparation of manganese-intercalated graphene of the invention
(1) 0.5g of graphite powder, 0.55g of sodium nitrate and 24mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture A.
(2) 0.5g of sodium nitrate powder, 5g of potassium permanganate and 75mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture B.
(3) 4mL of mixture B was added to mixture A, repeated every 22 minutes until mixture B was added, and stirred for 6 hours to give a purple manganic-intercalated graphene.
Example 4 preparation of manganese-intercalated graphene according to the invention
(1) 0.5g of graphite powder, 0.4g of sodium nitrate and 20mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture A.
(2) 0.5g of sodium nitrate powder, 3g of potassium permanganate and 72mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture B.
(3) 2mL of mixture B was added to mixture A, and this was repeated every 15 minutes until mixture B was added, and then stirred for 7 hours to give a purple manganic-intercalated graphene.
Example 5 preparation of manganese-intercalated graphene of the invention
(1) 0.5g of graphite powder, 0.6g of sodium nitrate and 25mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture A.
(2) 0.5g of sodium nitrate powder, 4g of potassium permanganate and 74mL of concentrated sulfuric acid (98% w/w) are stirred for 1.5h by a magnetic stirrer and mixed uniformly to obtain a mixture B.
(3) 4mL of mixture B was added to mixture A, repeated every 18 minutes until mixture B was added, and stirred for 8 hours to give a purple manganic-intercalated graphene.
Example 6 preparation of graphene oxide Using manganese-intercalated graphene
Taking 20g of manganese-embedded graphene, adding 100mL of hydrogen peroxide (30% w/w) to obtain golden yellow graphene oxide, as shown in fig. 2, and obtaining the graphene oxide after the reaction is completed as shown in fig. 3. A sample obtained by vacuum drying the prepared graphene oxide is golden yellow sponge-shaped, as shown in fig. 4.
Example 7 preparation of graphene oxide Using manganese-intercalated graphene
And adding 40mL of hydrogen peroxide (30% w/w) into 20g of manganese-embedded graphene to obtain golden yellow graphene oxide. And drying the prepared graphene oxide in vacuum to obtain a sample in a golden yellow sponge shape.
Example 8 preparation of graphene oxide Using manganese-intercalated graphene
And adding 200mL of hydrogen peroxide (27.5% w/w) into 20g of manganese-embedded graphene to obtain golden yellow graphene oxide. And drying the prepared graphene oxide in vacuum to obtain a sample in a golden yellow sponge shape.
Example 9 preparation of graphene oxide Using manganese-intercalated graphene
And adding 80mL of hydrogen peroxide (28% w/w) into 20g of manganese-embedded graphene to obtain golden yellow graphene oxide. And drying the prepared graphene oxide in vacuum to obtain a sample in a golden yellow sponge shape.
Example 10 preparation of graphene oxide Using manganese-intercalated graphene
And adding 150mL of hydrogen peroxide (29% w/w) into 20g of manganese-embedded graphene to obtain golden yellow graphene oxide. And drying the prepared graphene oxide in vacuum to obtain a sample in a golden yellow sponge shape.
The beneficial effects of the invention are demonstrated by means of experimental examples as follows:
experimental example 1
1. Drawing MnO3 +Standard curve
(1) 0.0998g of potassium permanganate is accurately weighed in a 10mL cuvette with a plug by using an analytical balance, the volume is adjusted to 10.00mL by using 98% concentrated sulfuric acid, the mixture is uniformly vibrated, and the ultrasonic treatment is carried out for 30 s.
(2) Taking 1000 μ L, 500 μ L, 250 μ L, 125 μ L, 63 μ L and 30 μ L of the above solutions respectively, preparing into solution with concentration of 0.009714mol/L, 0.004857mol/L, 0.002435mol/L, 0.001218mol/L, 0.0006988mol/L and 0.0002914mol/L, and measuring in ultraviolet spectrophotometer for 45 mol/LMaximum absorption value at 8.5nm to obtain MnO3 +A standard curve of concentration versus maximum absorption at 458.5nm is shown in FIG. 5.
2. Determination of MnO in supernatant3 +Amount of substance (a)
And (3) taking 300 mu l of the supernatant of the mixture B obtained in the step (2) in the example 1, namely the supernatant before the reaction and 300 mu l of the supernatant after the reaction in the step (3) in the example 1 into a 10ml colorimetric tube, adding concentrated sulfuric acid to dilute to 10.00ml, uniformly mixing by inversion, taking out the mixture into a cuvette, and measuring the 458.5nm absorbance of the mixture.
Comparing the measured absorbance at 458.5nm with the MnO drawn above3 +The results of a standard curve of the concentration and the maximum absorption at 458.5nm show that the manganese content of the reactant before the reaction is 0.01903mol and 0.008749mol remain at the end of the reaction.
We will MnO3 +And concentrated sulfuric acid is separated out of the reaction system in a liquid form and recycled, so that the cost is effectively reduced, and the method saves 45.94% of substances of reaction reagents.
Experimental example 2 characterization and testing of graphene oxide
1. Infrared Spectrum testing
The infrared spectrum test of the graphene oxide prepared in example 2 of the present invention is performed, and the result is shown in fig. 6. The results showed 1630cm-1、1430cm-1And 1178cm-1Has an absorption peak. 1630cm in the infrared spectrum-1The absorption peak indicates that the graphene oxide has a typical carbonyl structure; 1430cm in the infrared spectrum-1The absorption peak indicates that the graphene oxide has a hydroxyl group structure. At 1178cm-1Infrared absorption of (a) indicates the presence of epoxy functional groups. The infrared spectrum of the graphene oxide material conforms to the characteristic of typical graphene oxide.
2. X-ray surface photoelectron spectroscopy
The C1s spectrogram analysis of the graphene oxide solid shows that the graphene oxide has the characteristics of obvious graphene oxide, wherein the carbon element content of the graphene oxide is 58.51%, the oxygen element content of the graphene oxide is 36.29%, and the C: O content of the graphene oxide is 1.61, and is shown in figure 7.
3. Atomic force microscope atlas
The graphene oxide obtained by the present invention was subjected to an Atomic Force Microscope (AFM) test, and the test results are shown in fig. 8. The thickness of the graphene oxide sheet layer is 1.131nm and is about the superposition of 2-3 layers.
Comparative example 1
1. Preparation of intermediate products
The procedure of example 1 was repeated, with the amount of concentrated sulfuric acid used in step (1) changed to 0mL and other conditions unchanged, to give an intermediate product as a brown oil, as shown in FIG. 9.
2. Preparation of graphene oxide
The method of example 1 is repeated with the brown oily intermediate as the raw material to obtain earthy yellow graphene oxide with black impurities, and the product quality is poor, as shown in fig. 10.
Comparative example 2
1. Preparation of intermediate products
The procedure of example 1 was repeated with the time interval between the addition of mixture B to mixture A in step (3) changed to 40 minutes and the other conditions unchanged to give an intermediate product.
2. Preparation of graphene oxide
The method of example 1 was repeated using the intermediate product as a raw material to obtain earthy yellow graphene oxide, which is poor in product quality, as shown in fig. 11.
It can be seen from comparative examples 1 and 2 that the manganese-intercalated graphene and the graphene oxide of the present invention can be prepared only under the specific mixture ratio and reaction conditions of the present invention.
In conclusion, the reaction conditions are mild, the whole process is operated at room temperature, and the tedious operations and controls of medium temperature, low temperature, high temperature and the like are not needed, wherein MnO is used3 +And concentrated sulfuric acid can be separated out of the reaction system in a liquid form and can be reused, so that the cost is effectively reduced, and the graphene oxide has low density, can be separated by a similar flotation method, is simple and easy to implement, and is very suitable for industrial application.

Claims (16)

1. The manganese-embedded graphene is purple, and comprises the following structure:
Figure DEST_PATH_IMAGE001
wherein R is H, OH, HSO4、MnO4COOH or hydrogen bonded H2O；
The preparation method of the manganese-embedded graphene comprises the following steps:
Figure DEST_PATH_IMAGE002
and pretreatment of graphite: taking graphite, sodium nitrate and concentrated sulfuric acid, and uniformly mixing at 25 +/-2 ℃ to obtain a mixture A;
Figure 189114DEST_PATH_IMAGE003
preparation of MnO3 +: at the temperature of 25 +/-2 ℃, taking sodium nitrate, potassium permanganate and concentrated sulfuric acid, and uniformly mixing to obtain a mixture B; the weight ratio of the sodium nitrate to the potassium permanganate is 1: 5-10, and the weight volume ratio of the sodium nitrate to the concentrated sulfuric acid is 1: 140-150 g/mL;
Figure DEST_PATH_IMAGE004
、MnO3 +preparation of manganese-intercalated graphene as an intercalator: and adding the mixture B into the mixture A at 25 +/-2 ℃ for reaction to obtain the manganese-embedded graphene.
2. The manganese-embedded graphene according to claim 1, wherein: step (ii) of
Figure 391075DEST_PATH_IMAGE002
Wherein the weight ratio of the graphite to the sodium nitrate is 1: 0.8-1.2, and the weight-volume ratio of the graphite to the concentrated sulfuric acid is 1: 40-50 g/mL; and/or, step(s)
Figure 967550DEST_PATH_IMAGE003
The weight ratio of the sodium nitrate to the potassium permanganate is 1: 5-6, and the weight volume ratio of the sodium nitrate to concentrated sulfuric acid is 1: 144-148 g/mL; and/or, step(s)
Figure 972546DEST_PATH_IMAGE002
And
Figure 849235DEST_PATH_IMAGE003
wherein the concentrated sulfuric acid has a water content of 2% w/w or less.
3. The manganese-embedded graphene of claim 2, wherein: step (ii) of
Figure 219168DEST_PATH_IMAGE002
Wherein the weight ratio of the graphite to the sodium nitrate is 1: 0.9-1.1, and the weight-volume ratio of the graphite to the concentrated sulfuric acid is 1: 44-48 g/mL; step (ii) of
Figure 220622DEST_PATH_IMAGE002
And
Figure 216259DEST_PATH_IMAGE003
wherein the water content of the concentrated sulfuric acid is 1-2% w/w.
4. The manganese-embedded graphene according to claim 1, wherein: step (ii) of
Figure 494925DEST_PATH_IMAGE004
The mixture B is added into the mixture A in a plurality of times, and the time interval between the two times is 15-25 minutes; and/or, step(s)
Figure 285027DEST_PATH_IMAGE004
Adding 2-5 parts by volume of the mixture B into 20-25 parts by volume of the mixture A each time; and/or, step(s)
Figure 773777DEST_PATH_IMAGE004
Wherein the total amount of the mixture B is 70-80 parts by volume; and/or, step(s)
Figure 55329DEST_PATH_IMAGE004
The reaction time is 4-8 hours.
5. The manganese-embedded graphene of claim 4, wherein: step (ii) of
Figure 437769DEST_PATH_IMAGE004
The mixture B is added into the mixture A in a plurality of times, and the time interval between the two times is 18-22 minutes; step (ii) of
Figure 336455DEST_PATH_IMAGE004
Wherein the total amount of the mixture B is 70 to 75 parts by volume.
6. The manganese-embedded graphene according to claim 5, wherein: step (ii) of
Figure 125550DEST_PATH_IMAGE004
The mixture B is added to the mixture A in portions, the time interval between two portions being 20 minutes.
7. A method for preparing manganese-embedded graphene is characterized by comprising the following steps: it comprises the following steps:
Figure 259728DEST_PATH_IMAGE002
and pretreatment of graphite: taking graphite, sodium nitrate and concentrated sulfuric acid, and uniformly mixing at 25 +/-2 ℃ to obtain a mixture A;
Figure 450669DEST_PATH_IMAGE003
preparation of MnO3 +：2At the temperature of 5 +/-2 ℃, taking sodium nitrate, potassium permanganate and concentrated sulfuric acid, and uniformly mixing to obtain a mixture B; the weight ratio of the sodium nitrate to the potassium permanganate is 1: 5-10, and the weight volume ratio of the sodium nitrate to the concentrated sulfuric acid is 1: 140-150 g/mL;
Figure 520257DEST_PATH_IMAGE004
、MnO3 +preparation of manganese-intercalated graphene as an intercalator: adding the mixture B into the mixture A at 25 +/-2 ℃ for reaction to obtain manganese-embedded graphene;
the manganese-embedded graphene is purple, and comprises the following structure:
Figure 45916DEST_PATH_IMAGE005
wherein R is H, OH, HSO4、MnO4COOH or hydrogen bonded H2O。
8. The method of preparing manganese-embedded graphene according to claim 7, wherein: step (ii) of
Figure 937780DEST_PATH_IMAGE002
Wherein the weight ratio of the graphite to the sodium nitrate is 1: 0.8-1.2, and the weight-volume ratio of the graphite to the concentrated sulfuric acid is 1: 40-50 g/mL; and/or, step(s)
Figure 294812DEST_PATH_IMAGE003
The weight ratio of the sodium nitrate to the potassium permanganate is 1: 5-6, and the weight volume ratio of the sodium nitrate to concentrated sulfuric acid is 1: 144-148 g/mL; and/or, step(s)
Figure 73981DEST_PATH_IMAGE002
And
Figure 86937DEST_PATH_IMAGE003
wherein the concentrated sulfuric acid has a water content of 2% w/w or less.
9. The method of preparing manganese-embedded graphene according to claim 8, wherein: step (ii) of
Figure 782491DEST_PATH_IMAGE002
Wherein the weight ratio of the graphite to the sodium nitrate is 1: 0.9-1.1, and the weight-volume ratio of the graphite to the concentrated sulfuric acid is 1: 44-48 g/mL; step (ii) of
Figure 994030DEST_PATH_IMAGE002
And
Figure 952890DEST_PATH_IMAGE003
wherein the water content of the concentrated sulfuric acid is 1-2% w/w.
10. The method of preparing manganese-embedded graphene according to claim 7, wherein: step (ii) of
Figure 453141DEST_PATH_IMAGE004
The mixture B is added into the mixture A in a plurality of times, and the time interval between the two times is 15-25 minutes; and/or, step(s)
Figure 483545DEST_PATH_IMAGE004
Adding 2-5 parts by volume of the mixture B into 20-25 parts by volume of the mixture A each time; and/or, step(s)
Figure 752852DEST_PATH_IMAGE004
Wherein the total amount of the mixture B is 70-80 parts by volume; and/or, step(s)
Figure 942001DEST_PATH_IMAGE004
The reaction time is 4-8 hours.
11. The method of preparing manganese-embedded graphene according to claim 10, wherein: step by stepMethod for preparing a Chinese medicinal composition
Figure 663969DEST_PATH_IMAGE004
The mixture B is added into the mixture A in a plurality of times, and the time interval between the two times is 18-22 minutes; step (ii) of
Figure 622698DEST_PATH_IMAGE004
Wherein the total amount of the mixture B is 70 to 75 parts by volume.
12. The method of preparing manganese-embedded graphene according to claim 11, wherein: step (ii) of
Figure 497244DEST_PATH_IMAGE004
The mixture B is added to the mixture A in portions, the time interval between two portions being 20 minutes.
13. Use of the manganese-embedded graphene of any one of claims 1 to 6 in the preparation of graphene oxide.
14. A method for preparing graphene oxide is characterized in that: it comprises the following steps:
a. the method according to any one of claims 7 to 12, wherein manganese-embedded graphene is prepared;
b. and (3) taking the manganese-embedded graphene at the temperature of 25 +/-2 ℃, and adding hydrogen peroxide to obtain the graphene oxide.
15. The method for preparing graphene oxide according to claim 14, wherein: in the step b, the content of hydrogen peroxide in the hydrogen peroxide is 27.5-30% w/w, and/or the weight volume ratio of the manganese-embedded graphene to the hydrogen peroxide is 1: 2-10 g/mL.
16. The method for preparing graphene oxide according to claim 15, wherein: in the step b, the weight volume ratio of the manganese-embedded graphene to the hydrogen peroxide is 1: 5-10 g/mL.
CN201710704271.9A 2016-08-18 2017-08-16 Manganese-embedded graphene and preparation method and application thereof Active CN107381551B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610688729 2016-08-18
CN2016106887291 2016-08-18

Publications (2)

Publication Number Publication Date
CN107381551A CN107381551A (en) 2017-11-24
CN107381551B true CN107381551B (en) 2020-09-04

Family

ID=60352996

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710704271.9A Active CN107381551B (en) 2016-08-18 2017-08-16 Manganese-embedded graphene and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107381551B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112028061A (en) * 2019-06-04 2020-12-04 成都中医药大学 Graphene oxide prepared by illumination method
CN113265451B (en) * 2020-02-14 2023-08-29 成都中医药大学 Method for improving real-time fluorescence quantitative PCR specificity
CN113265448A (en) * 2020-02-14 2021-08-17 成都中医药大学 Method for improving sensitivity and specificity of real-time fluorescence PCR (polymerase chain reaction) based on graphene oxide

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012047316A1 (en) * 2010-05-21 2012-04-12 Ada Technologies, Inc. High performance carbon nano-tube composites for electrochemical energy storage devices
CN101948108B (en) * 2010-10-02 2012-05-09 上海交通大学 Preparation method of oxidized graphite paper
CN102992303A (en) * 2012-07-09 2013-03-27 中国地质大学（武汉） Preparation method of few-layer graphene by gradient oxidation process
CN104229786A (en) * 2014-09-18 2014-12-24 苏州经贸职业技术学院 Preparation method for graphene with high electric conductivity
CN105502370B (en) * 2016-01-05 2017-10-17 新疆大学 A kind of solid-phase reduction process of graphene oxide

Also Published As

Publication number Publication date
CN107381551A (en) 2017-11-24

Similar Documents

Publication Publication Date Title
CN107381551B (en) Manganese-embedded graphene and preparation method and application thereof
CN104876199B (en) A kind of ultrasound peels off the method that black phosphorus prepares the black scale of few layer
US10472242B2 (en) Method for preparing graphene by using high speed homogenization pretreatment and high pressure homogenation
Hanifah et al. Synthesis of graphene oxide nanosheets via modified hummers’ method and its physicochemical properties
CN105833834B (en) Reduced graphene/ferroso-ferric oxide/noble metal nano composite material, preparation method and applications
Gao et al. Freestanding atomically-thin cuprous oxide sheets for improved visible-light photoelectrochemical water splitting
KR20160071939A (en) Partially oxidized graphene and method for preparation thereof
KR20090103614A (en) Continuous methods and apparatus of functionalizing Carbon Nanotube
CN105460919B (en) A method of graphene quantum dot is prepared based on ozone oxidation
CN106219528B (en) A kind of method of controllable preparation graphene oxide and graphene oxide quantum dot
CN101318644A (en) Novel method for coating carbon nano-tube with silicon dioxide
CN106248605B (en) The construction of graphene oxide degree of oxidation standard curve and quantitative detecting method
Seitzhanova et al. The characteristics of graphene obtained from rice husk and graphite
KR20160048378A (en) Manufacturing method of graphene oxide using ultrasonication and apparatus for the same
Yin et al. Study on carbon nanotube reinforced phenol formaldehyde resin/graphite composite for bipolar plate
CN106276885B (en) The fast preparation method of high conductivity nitrogen-doped graphene
CN102502610A (en) Simple method for preparing a large amount of graphene
DE4300598A1 (en) SiO¶2¶ aerogels containing carbon particles and process for their preparation
CN106587033A (en) Graphene preparation method
CN114162820A (en) Preparation method of MXene organic solvent dispersion liquid
CN105084347A (en) Graphene preparation method
CN105948117A (en) Hydrothermal method for preparing HfO2 nano-particles
CN109607519B (en) Preparation method of high-water-solubility low-oxygen graphene
CN105936505B (en) A kind of preparation method of single-layer graphene
CN105692704B (en) A kind of preparation method of heatproof iron oxide yellow

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant