CN107867684A - A kind of preparation method of Fluorinated graphene oxide - Google Patents
A kind of preparation method of Fluorinated graphene oxide Download PDFInfo
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- CN107867684A CN107867684A CN201711135737.4A CN201711135737A CN107867684A CN 107867684 A CN107867684 A CN 107867684A CN 201711135737 A CN201711135737 A CN 201711135737A CN 107867684 A CN107867684 A CN 107867684A
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Abstract
The invention provides a kind of preparation method of Fluorinated graphene oxide, it is characterised in that including：Step 1：Concentrated sulfuric acid solution is placed in ice bath, the fluorinated volume for adding 1 mass parts is 20wt%~70wt% fluorographite powder, stirring, ultrasound, is again stirring for；Step 2：The oxidant of 3~15 mass parts is added, continues to stir；Step 3：By mixed solution water bath with thermostatic control at 30~60 DEG C, after 0.5~6h of water bath time, fluorinated graphite mixed liquor is obtained；Step 4：Deionized water is added dropwise into the fluorinated graphite mixed liquor obtained by step 3, then adds hydrogen peroxide, adds deionized water, stratification, then upper strata product is washed in the case where centrifugal rotational speed is 1000~4000r/min, until solution ph is 7, that is, obtains Fluorinated graphene oxide.Fluorinated graphene oxide quality prepared by the present invention is high, has good surface-active and preferably dispersiveness.
Description
Technical field
The present invention relates to a kind of preparation method of Fluorinated graphene oxide.
Background technology
Fluorinated graphene can be regarded as graphene by some or all of fluorination, the sp in graphite2Structure by part or
Person is all transformed into sp3, but laminated structure is still kept, it is most thin insulator, is properly termed as two-dimentional polytetrafluoroethylene (PTFE).Fluorination
Graphene has the advantages of two kinds of materials of graphene and polytetrafluoroethylene (PTFE) simultaneously, not only the chemical stability with polytetrafluoroethylene (PTFE)
And heat-resisting quantity, available for the production product such as non-stick pan and seal washer；There is the high intensity and Gao Bibiao of graphene again simultaneously
Area, available for products such as production semiconductors.The combination of two aspect advantages causes fluorinated graphene to have wide application prospect, it
It will not be by as thinner lighter polytetrafluoroethylene (PTFE) substitute, but any required ultra-thin, high intensity, chemistry can be used in
The occasion of property stabilization and high-temperaure coating.But because it has extremely low reactivity and extremely strong hydrophobicity, and easily
Reunite, significantly limit its application field, it is therefore necessary to try to overcome existing defect, prepare with certain surface activity with
And preferably dispersed fluorinated graphene.Especially, when preparing fluorinated graphene with fluorographite, due to dredging for fluorographite
It is water-based so that the chemical reagent of its surface wettability variation, the concentrated sulfuric acid and oxidant etc is difficult and fluorographite completely attaches to
Fully, the extent of reaction between them is so also just have impact on, so as to have impact on the product quality and performances of fluorinated graphene.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Fluorinated graphene oxide, fluorinated made from this method
Graphene have certain surface-active and preferably dispersiveness, oxygen fluorine ratio can by control oxidizer and oxidization time come
Control, and reaction condition is gentle, the reaction time is short, and synthesis device is simple, and energy consumption is low.
To achieve these goals, this invention takes following technical scheme：
A kind of preparation method of Fluorinated graphene oxide, it is characterised in that including：
Step 1：Concentrated sulfuric acid solution is placed in ice bath, the fluorinated volume for adding 1 mass parts is 20wt%~70wt% fluorine
Fossil ink powder, after stirring 0.5-1.5 hours, 15~40min of ultrasound, then it is placed in again in ice bath, continues to stir 10-50min；
Step 2：The oxidant of 3~15 mass parts is added, continues to stir；
Step 3：By mixed solution water bath with thermostatic control at 30~60 DEG C, after 0.5~6h of water bath time, oxyfluoride fossil is obtained
Black mixed liquor；
Step 4：Deionized water is added dropwise into the fluorinated graphite mixed liquor obtained by step 3, then adds hydrogen peroxide, then
Deionized water is added, stratification, is then washed upper strata product in the case where centrifugal rotational speed is 1000~4000r/min, directly
It is 7 to solution ph, that is, obtains Fluorinated graphene oxide.
Preferably, the oxidant in described step 2 is potassium permanganate or the mixture of potassium permanganate and sodium nitrate.
Preferably, the ratio of the concentrated sulfuric acid in described step 1 and fluorographite powder is 30~150mL: 1g.
Preferably, the mixing time in described step 1 and step 2 is 0.5~6h.
Preferably, the ratio for the deionized water being added dropwise in the fluorographite powder in the step 1 and step 4 is 1g: 20
~100mL.
Preferably, the ratio of hydrogen peroxide added in the fluorographite powder in the step 1 and step 4 for 1g: 10~
70mL。
Preferably, the power of ultrasonic wave and frequency are all adjustable during ultrasound in the step 1, supersonic generator it is super
Frequency of sound wave is 20~60kHz, and ultrasonic intensity is 0.8~1.2W/cm2。
Preferably, the time stirred first in the step 1 is 1 hour, and continuation mixing time is 30min.
The present invention in fluorinated graphene structure by being further introduced into a small amount of oxy radical such as hydroxyl, epoxy radicals and carboxyl
Etc. obtained oxygen-containing fluorinated graphene, there is good surface-active and preferably dispersiveness, in coating material, microelectronics, electricity
The field such as pole material and polymer composites shows wider application prospect.
Fluorographite has hydrophobicity due to being grafted many F atoms on graphite, and particularly fluorinated volume is higher
When, the concentrated sulfuric acid is difficult infiltration fluorographite, it is difficult to which fluorographite to be preferably evenly dispersed in dense sulphur by way of stirring
In acid.The fact that present invention is directed to, when handling fluorographite powder with concentrated sulfuric acid solution, during which it has been specifically incorporated at ultrasonic wave
Manage this reaction system.Because ultrasonic wave is in communication process, particle produces vibration and along the direction of propagation in elastic fluid
Energy is transmitted, so as to produce mechanical effect, fuel factor and acoustic cavitation.These phenomenons are applied during ultrasonication,
Peptizaiton can not only be made：Ultrasonic wave can not only make the fluorographite powder particles aggregation depolymerization in the concentrated sulfuric acid, but also can be
Graphite fluoride Composite Deposition obtains the more uniform dispersion liquid of granularity in the concentrated sulfuric acid, can also utilize the cavitation of ultrasonic wave, can
Make to dissolve in fluorographite powder or the exclusion of air entrapment, so as to be advantageous to the contact between the concentrated sulfuric acid and fluorographite, add
Speed impregnation process of the concentrated sulfuric acid to fluorographite, beneficial to the progress of subsequent reactions.In addition, the cavitation of Ultrasonic Dyeing is made
With can also penetrate the separation layer of covering fluorographite, promote the concentrated sulfuric acid to the diffusion inside fluorographite, intercalation and reaction.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) method that the present invention prepares Fluorinated graphene oxide, it with reference to the side that Hummers methods prepare graphene oxide
Method, using fluorographite as raw material, it is aoxidized by improving Hummers methods, obtained Fluorinated graphene oxide have compared with
More oxy radicals, therefore with higher active and dispersed.
(2) method that the present invention prepares Fluorinated graphene oxide, its oxygen fluorine is than can be by controlling the dosage, anti-of oxidant
Controlled between seasonable.
(3) method that the present invention prepares Fluorinated graphene oxide, when handling fluorographite powder with concentrated sulfuric acid solution, during which
The method of ultrasonication has been specifically incorporated it, hence it is evident that be different from traditional method for preparing Fluorinated graphene oxide, reaction condition
Gently, it is simple to operate, cost is cheap, reaction is abundant.
(4) Fluorinated graphene oxide made from this method has preferable surface-active and dispersiveness, oxygen fluorine than controllable,
Product quality is high, and reaction condition is gentle, and synthesis device is simple, and energy consumption is low.
Brief description of the drawings
Fig. 1 is the AFM figures of the Fluorinated graphene oxide of the gained of embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.F and O element ratios are obtained with XPS measuring in each embodiment.Raw materials used each embodiment is commercial goods.
Embodiment 1
A kind of preparation method of Fluorinated graphene oxide, it is comprised the following steps that：
(1) concentrated sulfuric acid solution that the mass fraction that measures 30ml is more than 98% is added in flask, is placed in ice bath,
Then 1g fluorographite powder (fluorinated volume 30wt%) is added to above-mentioned solution, magnetic agitation 1h；Then it is ultrasonically treated
15min, the ultrasonic frequency of supersonic generator is 55kHz, ultrasonic intensity 0.9W/cm2；It is placed in again in ice bath afterwards,
Continue to stir 30min；
(2) is slowly added to 9g potassium permanganate solid into above-mentioned mixed liquor again, continues magnetic agitation 3h；
(3) mixed solution water bath with thermostatic control at 35 DEG C after water bath time 1h, is obtained fluorinated graphite mixed solution by；
(4) 50ml deionized water is added dropwise in fluorinated graphite mixed liquor obtained by step (3), then adds 20ml
Hydrogen peroxide (mass fraction 30%) adds a large amount of deionized waters, stratification, then will to remove unnecessary potassium permanganate
Upper strata product is washed in the case where centrifugal rotational speed is 1000~4000r/min, until solution ph is 7, that is, obtains fluorinated
Graphene, as shown in figure 1, can be obtained by AFM (AFM) analysis, obtained Fluorinated graphene oxide lamellar spacing is
1.258nm, product is close to individual layer.F: O=1.7: 1 is measured by x-ray photoelectron spectroscopy (XPS), it can thus be seen that obtained fluorine
Changing graphene oxide has a more oxy radical, therefore with higher active and dispersed.
Embodiment 2
The present embodiment 2 is substantially the same manner as Example 1, and difference is：In the present embodiment 2 described in step (1) " and then will
1g fluorographite powder (fluorinated volume 40wt%) is added to above-mentioned solution " instead of in embodiment 1 described in step (1) " so
1g fluorographite powder (fluorinated volume 30wt%) is added to above-mentioned solution afterwards ", it can be obtained by AFM (AFM) analysis,
Obtained Fluorinated graphene oxide lamellar spacing is 1.281nm, and product measures F close to individual layer by x-ray photoelectron spectroscopy (XPS):
O=2.1: 1, it can thus be seen that obtained Fluorinated graphene oxide has oxy radical.
Embodiment 3
The present embodiment 3 is substantially the same manner as Example 1, is in place of its feature：In the present embodiment 3 described in step (1)
" and then adding 1g fluorographite powder (fluorinated volume 50wt%) to above-mentioned solution " instead of in embodiment 1 institute in step (1)
" and then 1g fluorographite powder (fluorinated volume 30wt%) is added to above-mentioned solution " stated；Institute in step (1) in the present embodiment 3
State " and then 30min is ultrasonically treated, the ultrasonic frequency of supersonic generator is 45kHz, ultrasonic intensity 1.2W/cm2”
It instead of in embodiment 1 and " and then to be ultrasonically treated 15min, the ultrasonic frequency of supersonic generator is described in step (1)
55kHz, ultrasonic intensity 0.9W/em2”.It can be obtained by AFM (AFM) analysis, obtained Fluorinated graphene oxide
Lamellar spacing is 1.299nm, and product measures F: O=2.8: 1, it is possible thereby to see close to individual layer by x-ray photoelectron spectroscopy (XPS)
Go out, obtained Fluorinated graphene oxide has oxy radical.
Embodiment 4
The present embodiment 4 is substantially the same manner as Example 1, is in place of its feature：In the present embodiment 4 described in step (1)
" and then adding 1g fluorographite powder (fluorinated volume 60wt%) to above-mentioned solution " instead of in embodiment 1 institute in step (1)
" and then 1g fluorographite powder (fluorinated volume 30wt%) is added to above-mentioned solution " stated, by AFM (AFM) point
Analysis can obtain, and obtained Fluorinated graphene oxide lamellar spacing is 1.312nm, and product passes through x-ray photoelectron spectroscopy close to individual layer
(XPS) F: O=3.6: 1 is measured, it can thus be seen that the Fluorinated graphene oxide being made has oxy radical.
Embodiment 5
The present embodiment 5 is substantially the same manner as Example 1, is in place of its feature：In the present embodiment 5 described in step (3) " again
9g potassium permanganate solid is slowly added into above-mentioned mixed liquor, continues magnetic agitation 6h " and instead of step (3) in embodiment 1
Described in " be slowly added to 9g potassium permanganate solid into above-mentioned mixed liquor again, continue magnetic agitation 3h "；In the present embodiment 3
" and then 40min is ultrasonically treated, the ultrasonic frequency of supersonic generator is 50kHz, ultrasonic intensity described in step (1)
For 1.2W/cm2；" instead of in embodiment 1 described in step (1) " and then be ultrasonically treated 15min, supersonic generator it is super
Frequency of sound wave is 55kHz, ultrasonic intensity 0.9W/cm2”.It can be obtained by AFM (AFM) analysis, obtained fluorination
Graphene oxide layer thickness is 1.259nm, and product measures F: O=2.5: 1 close to individual layer by x-ray photoelectron spectroscopy (XPS),
It can thus be seen that the Fluorinated graphene oxide being made has more oxy radical.
Claims (8)
- A kind of 1. preparation method of Fluorinated graphene oxide, it is characterised in that including：Step 1：Concentrated sulfuric acid solution is placed in ice bath, the fluorinated volume for adding 1 mass parts is 20wt%~70wt% fluorination stone Ink powder, after stirring 0.5-1.5 hours, 15~40min of ultrasound, then it is placed in again in ice bath, continues to stir 10-50min；Step 2：The oxidant of 3~15 mass parts is added, continues to stir；Step 3：By mixed solution water bath with thermostatic control at 30~60 DEG C, after 0.5~6h of water bath time, obtain fluorinated graphite and mix Close liquid；Step 4：Deionized water is added dropwise into the fluorinated graphite mixed liquor obtained by step 3, then adds hydrogen peroxide, adds Deionized water, stratification, then upper strata product is washed in the case where centrifugal rotational speed is 1000~4000r/min, until molten Liquid pH value is 7, that is, obtains Fluorinated graphene oxide.
- 2. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that the oxygen in described step 2 Agent is potassium permanganate or the mixture of potassium permanganate and sodium nitrate.
- 3. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that dense in described step 1 The ratio of sulfuric acid and fluorographite powder is 30~150mL: 1g.
- 4. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that described step 1 and step 2 In mixing time be 0.5~6h.
- 5. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that the fluorination in the step 1 The ratio for the deionized water being added dropwise in graphite powder and step 4 is 1g: 20~100mL.
- 6. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that the fluorination in the step 1 The ratio of added hydrogen peroxide is 1g: 10~70mL in graphite powder and step 4.
- 7. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that the ultrasound in the step 1 When ultrasonic wave power and frequency it is all adjustable.
- 8. the preparation method of Fluorinated graphene oxide as claimed in claim 1, it is characterised in that the ultrasound in the step 1 The ultrasonic frequency of Shi Suoyong supersonic generators is 20~60kHz, and ultrasonic intensity is 0.8~1.2W/cm2。
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Cited By (3)
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| CN109082329A (en) * | 2018-07-23 | 2018-12-25 | 江苏大学 | A kind of ternary nano self-lubricating composite and preparation method thereof |
| CN109267316A (en) * | 2018-09-30 | 2019-01-25 | 河南工程学院 | A kind of preparation method of durability conduction and super-hydrophobic cotton/silk fabric |
| CN112812476A (en) * | 2021-02-04 | 2021-05-18 | 上海材料研究所 | Polytetrafluoroethylene composite material and preparation method and application thereof |
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| CN104085882A (en) * | 2014-06-24 | 2014-10-08 | 华南理工大学 | Preparation method of few-layer oxygen-containing fluorinated graphene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109082329A (en) * | 2018-07-23 | 2018-12-25 | 江苏大学 | A kind of ternary nano self-lubricating composite and preparation method thereof |
| CN109082329B (en) * | 2018-07-23 | 2021-04-20 | 江苏大学 | Ternary nano self-lubricating composite material and preparation method thereof |
| CN109267316A (en) * | 2018-09-30 | 2019-01-25 | 河南工程学院 | A kind of preparation method of durability conduction and super-hydrophobic cotton/silk fabric |
| CN109267316B (en) * | 2018-09-30 | 2021-07-23 | 河南工程学院 | Preparation method of durable conductive and super-hydrophobic cotton/silk fabric |
| CN112812476A (en) * | 2021-02-04 | 2021-05-18 | 上海材料研究所 | Polytetrafluoroethylene composite material and preparation method and application thereof |
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