CN107381551A - A kind of embedding manganese graphene and preparation method and application - Google Patents
A kind of embedding manganese graphene and preparation method and application Download PDFInfo
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Abstract
The invention discloses MnO3 +As application of the intercalator in embedding manganese graphene is prepared.The invention also discloses a kind of embedding manganese graphene and its production and use, and a kind of graphene oxide of low-density and preparation method thereof.The reaction condition of the present invention is gentle, and whole process operates at room temperature, it is not necessary to the cumbersome operation and control such as medium temperature, low temperature and high temperature, wherein, MnO3 +Reaction system can be isolated in fluid form with the concentrated sulfuric acid, can recycle, extremely efficient reduce cost, moreover, the density of graphene oxide of the present invention is small, can be separated with similar floatation, simple and easy to do, the application being especially suitable in industry.
Description
Technical field
The present invention relates to a kind of embedding manganese graphene and preparation method and application.
Background technology
Graphene oxide, because of its larger surface area, unique two-dimensional structure and excellent properties, turn into the country in recent years
The focus of outer research, more and more extensive application is obtained, had much by the method that raw material prepares graphene oxide of graphite, its
In the most frequently used method be Hummers methods, be characterized in using KMnO4With the concentrated sulfuric acid graphene oxide is prepared as oxidant.
However, existing Hummers methods need cumbersome temperature control process, generally by three steps of low, medium and high temperature,
Energy consumption is higher；Meanwhile the addition of excessive potassium permanganate and the concentrated sulfuric acid adds the dosage of follow-up hydrogen peroxide, directly increases system
Standby cost；Moreover, traditional separation process needs to centrifuge, and the process that energy consumption is higher.
In order to overcome drawbacks described above, it is desirable to provide a kind of method for preferably preparing functionalization graphene, especially to oxygen
The existing preparation method of graphite alkene is further improved.
The content of the invention
In order to solve the above problems, the invention discloses MnO3 +As application of the intercalator in embedding manganese graphene is prepared,
Embedding manganese graphene and its production and use, and a kind of graphene oxide of low-density and preparation method thereof.
The invention discloses MnO3 +As application of the intercalator in embedding manganese graphene is prepared.
Intercalator：Graphite layers are completely embedded, and in order to promote its stripping, prepare graphene or stone with relatively low lamella
Black ene derivative increases its interlamellar spacing, this kind of polarity for being intercalation into piece interlayer point, it is necessary to polar molecule is intercalation into graphite layers
Son is intercalator.
The invention discloses a kind of embedding manganese graphene.
Wherein, described embedding manganese graphene is purple.
Wherein, described embedding manganese graphene includes following structure：
Wherein, R H, OH, HSO4、MnO4, the connected H of COOH or hydrogen bond2O；The intercalator MnO that the present invention uses3 +It is flat
Face structure, this allows for MnO3 +It just can relatively easily be embedded into graphite flake layer under relatively mild conditions as intercalator
Between.
The invention also discloses a kind of method for preparing embedding manganese graphene, comprise the following steps：
1., the pretreatment of graphite：At 25 ± 2 DEG C, graphite, sodium nitrate and the concentrated sulfuric acid are taken, mixes, obtains mixture A；
2., prepare MnO3 +：At 25 ± 2 DEG C, sodium nitrate, potassium permanganate and the concentrated sulfuric acid are taken, mixes, obtains mixture B；
③、MnO3 +Embedding manganese graphene is prepared as intercalator：At 25 ± 2 DEG C, mixture B is added in mixture A, entered
Row reaction, obtains embedding manganese graphene.
The present invention, which prepares the embedding possible mechanism of manganese graphene, is：Pretreated graphite powder, it is (similar that hydroxyl is contained on its surface
Expanded graphite powder), with MnO3 +Reaction, make the MnO of planar structure3 +Combined with hydroxyl oxygen and release hydrogen ion, MnO3 +Plane structure
Type is converted into-MnO4Tetrahedral structure and be connected to surface of graphene oxide so that graphite flake layer spacing increase, be advantageous to
MnO3 +Further intercalation.
Wherein, R H, OH, HSO4、MnO4, the connected H of COOH or hydrogen bond2O。
Wherein, step 1. in, the weight ratio of the graphite and sodium nitrate is 1：0.8~1.2, preferably 1：0.9~1.1；
The w/v of the graphite and the concentrated sulfuric acid is 1：40~50g/mL, preferably 1：44~48g/mL.
Wherein, step 2. in, the weight ratio of the sodium nitrate and potassium permanganate is 1：5~10, preferably 1：5~6；It is described
The w/v of sodium nitrate and the concentrated sulfuric acid is 1：140~150g/mL, preferably 1：144~148g/mL.
Wherein, step 1. and 2. in, the water content of the concentrated sulfuric acid is within 2%w/w, preferably 1%~2%w/w.
Wherein, step 3. in, the mixture B be by several times be added in mixture A, twice between time interval be
15~25 minutes, preferably 18~22 minutes, more preferably 20 minutes；The mixture B of 2~5 parts by volume is added to 20 every time
In the mixture A of~25 parts by volume；Step 3. in, mixture B total amount is 70~80 parts by volume；Preferably, mixture B's is total
Measure as 70~75 parts by volume.
Application of the above-mentioned embedding manganese graphene in graphene oxide is prepared.
The invention also discloses a kind of graphene oxide, density is 1.00~1.08g/mL.
The invention discloses a kind of method for preparing graphene oxide, comprise the following steps：
A, according to the method described above, embedding manganese graphene is prepared；
B, at 25 ± 2 DEG C, embedding manganese graphene is taken, hydrogen peroxide is added, obtains graphene oxide.
Wherein, in step b, the content of hydrogen peroxide in the hydrogen peroxide is 27.5%~30%w/w；The embedding manganese graphite
The w/v of alkene and hydrogen peroxide is 1：2~10g/mL, preferably 1：5~10g/mL.
The present invention uses the MnO with planar structure3 +As intercalator, its 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)
Reaction equation (1) and (2) are the dominant mechanism of currently available technology, and the present invention is in dense H2SO4Made in the case of excess
Standby, formula (3) prepares MnO for the present invention3 +Key reaction, it can be seen that the inventive method prepare MnO3 +The KMnO of consumption4's
Measure smaller, and reacted MnO3 +Reaction system can be isolated in fluid form with the concentrated sulfuric acid, can be recycled.
Compared with existing Hummers methods, the present invention is with MnO3 +Embedding manganese graphene is prepared as intercalator, further
Graphene oxide is prepared, its reaction condition is gentle, and whole process operates at room temperature, it is not necessary to which medium temperature, low temperature and high temperature etc. are cumbersome
Operation and control, wherein, MnO3 +Reaction system can be isolated in fluid form with the concentrated sulfuric acid, can be reused, extremely
Cost is significantly reduced, wastewater treatment is carried out without hydrogen peroxide etc., it is environment-friendly, moreover, graphene oxide of the present invention is close
Spend small, can be separated with similar floatation, simple and easy to do, the application being especially suitable in industry.
Obviously, according to the above of the present invention, according to the ordinary technical knowledge and customary means of this area, do not departing from
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The embodiment of form by the following examples, the above of the present invention is remake further specifically
It is bright.But the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following example.It is all to be based on the above of the present invention
The technology realized belongs to the scope of the present invention.
Brief description of the drawings
Fig. 1 is the outside drawing of embedding manganese graphene intermediate product obtained by the embodiment of the present invention 1；
Fig. 2 is the outside drawing that the embodiment of the present invention 6 is preparing graphene oxide；
Fig. 3 is the outside drawing that the embodiment of the present invention 6 reacts complete graphene oxide；
Fig. 4 is the outside drawing after the graphene oxide vacuum drying obtained by the embodiment of the present invention 6；
Fig. 5 is the MnO that experimental example 1 of the present invention is drawn3 +Concentration and the standard curve of obtained the maximum absorption at 458.5nm；
Fig. 6 is experimental example 2 of the present invention to graphene oxide examination of infrared spectrum figure；
Fig. 7 is the X ray X ray photoelectron spectroscopy figure measured by experimental example 2 of the present invention；
Fig. 8 is the atomic force microscopy diagram spectrum measured by experimental example 2 of the present invention；
Fig. 9 is the outside drawing of intermediate product obtained by comparative example 1；
Figure 10 is the outside drawing of graphene oxide obtained by comparative example 1；
Figure 11 is the outside drawing of graphene oxide obtained by comparative example 2.
Embodiment
The raw material that is used in the specific embodiment of the invention, equipment are known product, are obtained by buying commercially available prod.
The preparation of the embedding manganese graphene of the present invention of embodiment 1
(1) 0.5g graphite powders, 0.5g sodium nitrate and the 23mL concentrated sulfuric acids (98%w/w) are taken, utilizes magnetic stirrer
1.5h, mix, obtain mixture A.
(2) 0.5g sodium nitrate powder, 3g potassium permanganate and the 73mL concentrated sulfuric acids (98%w/w) are taken, is stirred using magnetic stirring apparatus
1.5h is mixed, mixes, obtains mixture B.
(3) take 4mL mixtures B to be added in said mixture A every time, be repeated once every 20 minutes, until mixture B
Add, then stir 4 hours, obtain the embedding manganese graphene of purple, as shown in Figure 1.
The preparation of the embedding manganese graphene of the present invention of embodiment 2
(1) 0.5g graphite powders, 0.45g sodium nitrate and the 22mL concentrated sulfuric acids (98%w/w) are taken, utilizes magnetic stirrer
1.5h, mix, obtain mixture A.
(2) 0.5g sodium nitrate powder, 2.5g potassium permanganate and the 70mL concentrated sulfuric acids (98%w/w) are taken, utilizes magnetic stirring apparatus
1.5h is stirred, mixes, obtains mixture B.
(3) take 3mL mixtures B to be added in said mixture A every time, be repeated once every 25 minutes, until mixture B
Add, then stir 5 hours, obtain the embedding manganese graphene of purple.
The preparation of the embedding manganese graphene of the present invention of embodiment 3
(1) 0.5g graphite powders, 0.55g sodium nitrate and the 24mL concentrated sulfuric acids (98%w/w) are taken, utilizes magnetic stirrer
1.5h, mix, obtain mixture A.
(2) 0.5g sodium nitrate powder, 5g potassium permanganate and the 75mL concentrated sulfuric acids (98%w/w) are taken, is stirred using magnetic stirring apparatus
1.5h is mixed, mixes, obtains mixture B.
(3) take 4mL mixtures B to be added in said mixture A every time, be repeated once every 22 minutes, until mixture B
Add, then stir 6 hours, obtain the embedding manganese graphene of purple.
The preparation of the embedding manganese graphene of the present invention of embodiment 4
(1) 0.5g graphite powders, 0.4g sodium nitrate and the 20mL concentrated sulfuric acids (98%w/w) are taken, utilizes magnetic stirrer
1.5h, mix, obtain mixture A.
(2) 0.5g sodium nitrate powder, 3g potassium permanganate and the 72mL concentrated sulfuric acids (98%w/w) are taken, is stirred using magnetic stirring apparatus
1.5h is mixed, mixes, obtains mixture B.
(3) take 2mL mixtures B to be added in said mixture A every time, be repeated once every 15 minutes, until mixture B
Add, then stir 7 hours, obtain the embedding manganese graphene of purple.
The preparation of the embedding manganese graphene of the present invention of embodiment 5
(1) 0.5g graphite powders, 0.6g sodium nitrate and the 25mL concentrated sulfuric acids (98%w/w) are taken, utilizes magnetic stirrer
1.5h, mix, obtain mixture A.
(2) 0.5g sodium nitrate powder, 4g potassium permanganate and the 74mL concentrated sulfuric acids (98%w/w) are taken, is stirred using magnetic stirring apparatus
1.5h is mixed, mixes, obtains mixture B.
(3) take 4mL mixtures B to be added in said mixture A every time, be repeated once every 18 minutes, until mixture B
Add, then stir 8 hours, obtain the embedding manganese graphene of purple.
Embodiment 6 prepares graphene oxide using embedding manganese graphene
The embedding manganese graphenes of 20g are taken, add 100mL hydrogen peroxide (30%w/w), obtain the graphene oxide of golden yellow, such as Fig. 2
Shown, the graphene oxide after reaction completely is as shown in Figure 3.The sample that prepared graphene oxide is obtained after vacuum dried
Product are spongy in golden yellow, as shown in Figure 4.
Embodiment 7 prepares graphene oxide using embedding manganese graphene
The embedding manganese graphenes of 20g are taken, add 40mL hydrogen peroxide (30%w/w), obtain the graphene oxide of golden yellow.Will be made
The sample obtained after standby graphene oxide is vacuum dried is in golden yellow spongy.
Embodiment 8 prepares graphene oxide using embedding manganese graphene
The embedding manganese graphenes of 20g are taken, add 200mL hydrogen peroxide (27.5%w/w), obtain the graphene oxide of golden yellow.Will
The sample obtained after prepared graphene oxide is vacuum dried is in golden yellow spongy.
Embodiment 9 prepares graphene oxide using embedding manganese graphene
The embedding manganese graphenes of 20g are taken, add 80mL hydrogen peroxide (28%w/w), obtain the graphene oxide of golden yellow.Will be made
The sample obtained after standby graphene oxide is vacuum dried is in golden yellow spongy.
Embodiment 10 prepares graphene oxide using embedding manganese graphene
The embedding manganese graphenes of 20g are taken, add 150mL hydrogen peroxide (29%w/w), obtain the graphene oxide of golden yellow.By institute
The sample obtained after the graphene oxide of preparation is vacuum dried is in golden yellow spongy.
Beneficial effects of the present invention are proved below by way of the mode of experimental example：
Experimental example 1
1st, MnO is drawn3 +Standard curve
(1) accurately weigh 0.0998g potassium permanganate using assay balance in 10mL to have in plug cuvette, with 98% dense sulphur
Acid is settled to 10.00mL, and concussion is uniform, ultrasonic 30s.
(2) the above-mentioned μ l of solution 1000 are taken respectively, and 500 μ l, 250 μ l, 125 μ l, 63 μ l, 30 μ l, being configured to concentration is
0.009714mol/L, 0.004857mol/L, 0.002435mol/L, 0.001218mol/L, 0.0006988mol/L,
0.0002914mol/L solution, it is put into ultraviolet specrophotometer and determines obtained the maximum absorption at 458.5nm, obtain MnO3 +Concentration
With the standard curve of obtained the maximum absorption at 458.5nm, as shown in Figure 5.
2nd, MnO in supernatant liquor is determined3 +Material amount
The supernatant liquor of mixture B obtained by step (2) in Example 1, that is, the supernatant liquor before reaction, Yi Jishi
The μ l of supernatant liquor 300 after reaction terminates in step (3) in example 1 are applied in 10 milliliters of colorimetric cylinders, add diluting concentrated sulfuric acid constant volume
To 10.00 milliliters, overturn and be well mixed, take out into cuvette, measure its 458.5nm absorbance.
The 458.5nm absorbances that will be measured, compare the MnO of above-mentioned drafting3 +Concentration and the mark of obtained the maximum absorption at 458.5nm
Directrix curve, as a result show, before reaction, the manganese content of reactant is 0.01903mol, remaining 0.008749mol at the end of reaction.
We are by MnO3 +Reaction system is isolated in fluid form with the concentrated sulfuric acid, is recycled, is extremely efficient reduced
Cost, the amount that this method saves the material of reaction reagent are 45.94%.
The sign of the graphene oxide of experimental example 2 and test
1st, examination of infrared spectrum
Examination of infrared spectrum is carried out to the graphene oxide obtained by the embodiment of the present invention 2, as a result as shown in Figure 6.As a result
Show in 1630cm-1、1430cm-1And 1178cm-1There is absworption peak at place.1630cm in infrared spectrum-1The absworption peak at place, shows oxygen
Graphite alkene has typical carbonyl structure；1430cm in infrared spectrum-1The absworption peak at place, show that graphene oxide has hydroxyl
Based structures.In 1178cm-1The infrared absorption at place shows with epoxy functionality.Its infrared spectrum meets typical graphite oxide
Alkene feature.
2nd, X ray X ray photoelectron spectroscopy
The C1s spectrum analysis of the graphene oxide solid show that the graphene oxide carbon element content is 58.51%, oxygen member
Cellulose content is 36.29%, C:O is 1.61, has obvious graphene oxide feature, as shown in Figure 7.
3rd, atomic force microscopy diagram spectrum
AFM (AFM) test is carried out to the graphene oxide obtained by the present invention, test result is as shown in Figure 8.
Graphene oxide layer thickness of the present invention is 1.131nm, about layer 2-3 overlapping.
Comparative example 1
1st, intermediate product is prepared
The dosage of the concentrated sulfuric acid in step (1) is changed to 0mL, other conditions are constant, the method for repeating embodiment 1, obtain brown
The intermediate product of color oily, as shown in Figure 9.
2nd, graphene oxide is prepared
Using the intermediate product of above-mentioned brown oil as raw material, the method for repetition embodiment 1, it is miscellaneous with black to obtain khaki
The graphene oxide of matter, poor product quality, as shown in Figure 10.
Comparative example 2
1st, intermediate product is prepared
The time interval that step (3) mixture B is added to mixture A is changed to 40 minutes, and other conditions are constant, repeats to implement
The method of example 1, obtains intermediate product.
2nd, graphene oxide is prepared
Using above-mentioned intermediate product as raw material, the method for repetition embodiment 1, khaki graphene oxide, product matter are obtained
Amount is poor, as shown in figure 11.
Understood that only under the specific proportioning and reaction condition of the present invention, this hair could be made by comparative example 1 and comparative example 2
Bright embedding manganese graphene and graphene oxide.
To sum up, reaction condition of the invention is gentle, and whole process operates at room temperature, it is not necessary to which medium temperature, low temperature and high temperature etc. are numerous
Trivial operation and control, wherein, MnO3 +Reaction system can be isolated in fluid form with the concentrated sulfuric acid, can be reused,
Cost is extremely efficient reduced, moreover, the density of graphene oxide of the present invention is small, can be separated with similar floatation,
Application that is simple and easy to do, being especially suitable in industry.
Claims (10)
1.MnO3 +As application of the intercalator in embedding manganese graphene is prepared.
A kind of 2. embedding manganese graphene.
3. embedding manganese graphene according to claim 2, it is characterised in that：Described embedding manganese graphene is purple.
4. the embedding manganese graphene according to Claims 2 or 3, it is characterised in that：Described embedding manganese graphene includes following knot
Structure：
Wherein, R H, OH, HSO4、MnO4, the connected H of COOH or hydrogen bond2O。
A kind of 5. method for preparing embedding manganese graphene described in claim 2~4 any one, it is characterised in that：It includes following
Step：
1., the pretreatment of graphite：At 25 ± 2 DEG C, graphite, sodium nitrate and the concentrated sulfuric acid are taken, mixes, obtains mixture A；
2., prepare MnO3 +：At 25 ± 2 DEG C, sodium nitrate, potassium permanganate and the concentrated sulfuric acid are taken, mixes, obtains mixture B；
③、MnO3 +Embedding manganese graphene is prepared as intercalator：At 25 ± 2 DEG C, mixture B is added in mixture A, carried out anti-
Should, obtain embedding manganese graphene.
6. the method according to claim 5 for preparing embedding manganese graphene, it is characterised in that：Step 1. in, the graphite with
The weight ratio of sodium nitrate is 1:0.8~1.2, the w/v of the graphite and the concentrated sulfuric acid is 1:40~50g/mL；Preferably,
The weight ratio of the graphite and sodium nitrate is 1:0.9~1.1, the w/v of the graphite and the concentrated sulfuric acid is 1:44~48g/
ML, and/or, step 2. in, the weight ratio of the sodium nitrate and potassium permanganate is 1:5~10, the sodium nitrate and the concentrated sulfuric acid
W/v is 1:140~150g/mL；Preferably, the weight ratio of the sodium nitrate and potassium permanganate is 1:5~6, the nitre
The w/v of sour sodium and the concentrated sulfuric acid is 1:144~148g/mL, and/or, step 1. and 2. in, the concentrated sulfuric acid it is aqueous
Amount is within 2%w/w；Preferably, the water content of the concentrated sulfuric acid is 1%~2%w/w.
7. the method according to claim 5 for preparing embedding manganese graphene, it is characterised in that：Step 3. in, the mixture B
Be by several times be added in mixture A, twice between time interval be 15~25 minutes；Preferably, the mixture B is point
It is secondary to be added in mixture A, twice between time interval be 18~22 minutes；It is furthermore preferred that the mixture B is by several times
Be added in mixture A, twice between time interval be 20 minutes, and/or, step 3. in, every time by 2~5 parts by volume
Mixture B be added in the mixture A of 20~25 parts by volume, and/or, step 3. in, the total amount of the mixture B for 70~
80 parts by volume；Preferably, the total amount of the mixture B is 70~75 parts by volume, and/or, step 3. in, the time of the reaction
For 4~8 hours.
8. application of the embedding manganese graphene in graphene oxide is prepared described in claim 2~4 any one.
A kind of 9. method for preparing graphene oxide, it is characterised in that：It comprises the following steps：
A, according to claim 5~12 any one described in method, embedding manganese graphene is prepared；
B, at 25 ± 2 DEG C, embedding manganese graphene is taken, hydrogen peroxide is added, obtains graphene oxide.
10. the method according to claim 14 for preparing graphene oxide, it is characterised in that：In step b, the hydrogen peroxide
In content of hydrogen peroxide be 27.5%~30%w/w, and/or, the w/v of the embedding manganese graphene and hydrogen peroxide is
1：2~10g/mL；Preferably, the w/v of the embedding manganese graphene and hydrogen peroxide is 1：5~10g/mL.
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