CN107867684B - 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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- CN107867684B CN107867684B CN201711135737.4A CN201711135737A CN107867684B CN 107867684 B CN107867684 B CN 107867684B CN 201711135737 A CN201711135737 A CN 201711135737A CN 107867684 B CN107867684 B CN 107867684B
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- C01B2204/00—Structure or properties of graphene
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Abstract
The present invention provides a kind of preparation methods of Fluorinated graphene oxide characterized by comprising step 1: concentrated sulfuric acid solution being placed in ice bath, the fluorinated volume that 1 mass parts are added is the fluorographite powder of 20wt%~70wt%, and stirring is ultrasonic, 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, obtaining fluorinated graphite mixed liquor；Step 4: deionized water is added dropwise into the resulting fluorinated graphite mixed liquor of step 3, then hydrogen peroxide is added, add deionized water, stratification, then upper layer product is washed in the case where centrifugal rotational speed is 1000~4000r/min, until solution ph be 7 to get arrive Fluorinated graphene oxide.Fluorinated graphene oxide quality prepared by the present invention is high, has good surface-active and preferably dispersibility.
Description
Technical field
The present invention relates to a kind of preparation methods of Fluorinated graphene oxide.
Background technique
The sp that fluorinated graphene can be regarded as graphene by some or all of fluorination, 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 that two kinds of materials of graphene and polytetrafluoroethylene (PTFE) simultaneously, not only with the chemical stability of polytetrafluoroethylene (PTFE)
And heat-resisting quantity, it can be used for producing the products such as non-stick pan and seal washer；Simultaneously again with the high intensity and Gao Bibiao of graphene
Area can be used for producing the products such as semiconductor.The combination of two aspect advantages makes fluorinated graphene have wide application prospect, it
It will not be that but can be used in any required ultra-thin, high-intensitive, chemical by as thinner lighter polytetrafluoroethylene (PTFE) substitute
The occasion of property stabilization and high-temperaure coating.But since it is with extremely low reactivity and extremely strong hydrophobicity, and easily
Reunite, greatly limit their application field, it is therefore necessary to try to overcome existing defect, prepare with certain surface activity with
And the fluorinated graphene of preferably dispersibility.Particularly, when preparing fluorinated graphene with fluorographite, due to dredging for fluorographite
It is aqueous, so that the chemical reagent of its surface wettability variation, the concentrated sulfuric acid and oxidant etc is difficult and fluorographite completely attaches to
Sufficiently, the extent of reaction between them is also just affected in this way, to affect the product quality and performances of fluorinated graphene.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of Fluorinated graphene oxide, fluorinated made from this method
Graphene has a certain surface-active and preferably dispersibility, oxygen fluorine ratio can by control oxidizer and oxidization time come
Control, and reaction condition is mild, the reaction time is short, and synthesis device is simple, and low energy consumption.
To achieve the goals above, this invention takes following technical solutions:
A kind of preparation method of Fluorinated graphene oxide characterized by comprising
Step 1: concentrated sulfuric acid solution being placed in ice bath, the fluorinated volume that 1 mass parts are added is the fluorine of 20wt%~70wt%
Fossil ink powder, after stirring 0.5-1.5 hours, then 15~40min of ultrasound is placed in ice bath again, 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, obtaining oxyfluoride fossil
Black mixed liquor；
Step 4: deionized water is added dropwise into the resulting fluorinated graphite mixed liquor of step 3, hydrogen peroxide is then added, then
Deionized water is added, then stratification washs upper layer product in the case where centrifugal rotational speed is 1000~4000r/min, directly
To solution ph be 7 to get arrive Fluorinated graphene oxide.
Preferably, the oxidant in the step 2 is the mixture of potassium permanganate or potassium permanganate and sodium nitrate.
Preferably, the ratio of the concentrated sulfuric acid in the step 1 and fluorographite powder is 30~150mL: 1g.
Preferably, the mixing time in the 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 be 1g: 10~
70mL。
Preferably, the power of ultrasonic wave and frequency are all adjustable when 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 for the first time 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 oxygen-containing group such as hydroxyl, epoxy group and carboxyl
Etc. obtained oxygen-containing fluorinated graphene, there is good surface-active and preferably dispersibility, in coating material, microelectronics, electricity
The fields such as pole material and polymer composites show wider application prospect.
Fluorographite has hydrophobicity, especially fluorinated volume higher due to being grafted many F atoms on graphite
When, the concentrated sulfuric acid is difficult to infiltrate fluorographite, is difficult by way of stirring preferably for fluorographite to be evenly dispersed in dense sulphur
In acid.During which the fact that present invention is directed to has been specifically incorporated at ultrasonic wave when handling fluorographite powder with concentrated sulfuric acid solution
Manage this reaction system.This is because ultrasonic wave, in communication process, particle generates vibration and along the direction of propagation in elastic fluid
Energy is transmitted, to generate mechanical effect, fuel factor and acoustic cavitation.These phenomenons are applied during ultrasonication,
Can not only peptizaiton 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 adds to be conducive to the contact between the concentrated sulfuric acid and fluorographite
Speed impregnation process of the concentrated sulfuric acid to fluorographite, conducive to the progress of subsequent reactions.In addition to this, the cavitation of Ultrasonic Dyeing is made
With can also penetrate the separation layer of covering fluorographite, promote the concentrated sulfuric acid to diffusion, intercalation and the reaction inside fluorographite.
Compared with prior art, the beneficial effects of the present invention are:
(1) method that the present invention prepares Fluorinated graphene oxide prepares the side of graphene oxide with reference to Hummers method
Method, using fluorographite as raw material, by improve Hummers method it is aoxidized, Fluorinated graphene oxide obtained have compared with
More oxygen-containing groups, therefore activity with higher and dispersibility.
(2) method that the present invention prepares Fluorinated graphene oxide, dosage, anti-of the oxygen fluorine than control oxidant can be passed through
It is 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 for being specifically incorporated ultrasonication, hence it is evident that be different from traditional method for preparing Fluorinated graphene oxide, reaction condition
Mildly, easy to operate, low in cost, reaction is sufficiently.
(4) Fluorinated graphene oxide made from this method has preferable surface-active and dispersibility, and oxygen fluorine ratio is controllable,
Product quality is high, and reaction condition is mild, and synthesis device is simple, and low energy consumption.
Detailed description of the invention
Fig. 1 is that the AFM of the resulting Fluorinated graphene oxide of embodiment 1 schemes.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.F and O element ratio is 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, the specific steps of which are as follows:
(1) concentrated sulfuric acid solution that measures that the mass fraction of 30ml is 98% or more 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 are 55kHz, ultrasonic intensity 0.9W/cm2；It is placed in ice bath again later,
Continue to stir 30min；
(2) is slowly added to the potassium permanganate solid of 9g 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) deionized water of 50ml is added dropwise into fluorinated graphite mixed liquor obtained by step (3) by, and 20ml is then added
Hydrogen peroxide (mass fraction 30%) adds a large amount of deionized waters to remove extra potassium permanganate, then stratification will
Upper layer product centrifugal rotational speed be 1000~4000r/min under washed, until solution ph be 7 to get arrive fluorinated
Graphene, as shown in Figure 1, can be obtained by atomic force microscope (AFM) analysis, Fluorinated graphene oxide lamellar spacing obtained is
1.258nm, product is close to single layer.F: O=1.7: 1 is measured by x-ray photoelectron spectroscopy (XPS), it can thus be seen that fluorine obtained
Changing graphene oxide has more oxygen-containing group, therefore activity with higher and dispersibility.
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 atomic force microscope (AFM) analysis,
Fluorinated graphene oxide lamellar spacing obtained is 1.281nm, and product measures F close to single layer, by x-ray photoelectron spectroscopy (XPS):
O=2.1: 1, it can thus be seen that Fluorinated graphene oxide obtained has oxygen-containing group.
Embodiment 3
The present embodiment 3 is substantially the same manner as Example 1, is in place of feature: in the present embodiment 3 described in step (1)
" and then 1g fluorographite powder (fluorinated volume 50wt%) is added to above-mentioned solution " is instead of institute in step (1) in embodiment 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 ultrasonic treatment 30min, the ultrasonic frequency of supersonic generator are 45kHz, ultrasonic intensity 1.2W/cm2”
Instead of in embodiment 1 described in step (1), " and then ultrasonic treatment 15min, the ultrasonic frequency of supersonic generator are
55kHz, ultrasonic intensity 0.9W/em2".It can be obtained by atomic force microscope (AFM) analysis, Fluorinated graphene oxide obtained
Lamellar spacing is 1.299nm, and product measures F: O=2.8: 1 close to single layer, by x-ray photoelectron spectroscopy (XPS), it is possible thereby to see
Out, Fluorinated graphene oxide obtained has oxygen-containing group.
Embodiment 4
The present embodiment 4 is substantially the same manner as Example 1, is in place of feature: in the present embodiment 4 described in step (1)
" and then 1g fluorographite powder (fluorinated volume 60wt%) is added to above-mentioned solution " is instead of institute in step (1) in embodiment 1
" and then 1g fluorographite powder (fluorinated volume 30wt%) is added to above-mentioned solution " stated, by atomic force microscope (AFM) point
Analysis can obtain, and Fluorinated graphene oxide lamellar spacing obtained is 1.312nm, and product passes through x-ray photoelectron spectroscopy close to single layer
(XPS) F: O=3.6: 1 is measured, it can thus be seen that the Fluorinated graphene oxide being made has oxygen-containing group.
Embodiment 5
The present embodiment 5 is substantially the same manner as Example 1, is in place of feature: in the present embodiment 5 described in step (3) " again
It is slowly added to the potassium permanganate solid of 9g into above-mentioned mixed liquor, continues magnetic agitation 6h " instead of step (3) in embodiment 1
Described in " be slowly added to the potassium permanganate solid of 9g into above-mentioned mixed liquor again, continue magnetic agitation 3h "；In the present embodiment 3
Described in step (1) " and then ultrasonic treatment 40min, the ultrasonic frequency of supersonic generator are 50kHz, ultrasonic intensity
For 1.2W/cm2；" instead of in embodiment 1 described in step (1) " and then ultrasonic treatment 15min, supersonic generator it is super
Frequency of sound wave is 55kHz, ultrasonic intensity 0.9W/cm2".It can be obtained by atomic force microscope (AFM) analysis, fluorination obtained
Graphene oxide layer measures F: O=2.5: 1 close to single layer, by x-ray photoelectron spectroscopy (XPS) with a thickness of 1.259nm, product,
It can thus be seen that the Fluorinated graphene oxide being made has more oxygen-containing group.
Claims (7)
1. a kind of preparation method of Fluorinated graphene oxide characterized by comprising
Step 1: concentrated sulfuric acid solution being placed in ice bath, the fluorinated volume that 1 mass parts are added is the fluorination stone of 20wt%~70wt%
Ink powder, after stirring 0.5-1.5 hours, then 15~40min of ultrasound is placed in ice bath again, continues to stir 10-50min；Described
The ultrasonic frequency of supersonic generator used is 20~60kHz when ultrasonic, and ultrasonic intensity is 0.8~1.2W/cm2；
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, it is mixed to obtain fluorinated graphite
Close liquid；
Step 4: deionized water is added dropwise into the resulting fluorinated graphite mixed liquor of step 3, hydrogen peroxide is then added, adds
Then deionized water, stratification wash upper layer product in the case where centrifugal rotational speed is 1000~4000r/min, until molten
Liquid pH value be 7 to get arrive Fluorinated graphene oxide.
2. the preparation method of Fluorinated graphene oxide as described in claim 1, which is characterized in that the oxygen in the step 2
Agent is the mixture of potassium permanganate or potassium permanganate and sodium nitrate.
3. the preparation method of Fluorinated graphene oxide as described in claim 1, which is characterized in that dense in the step 1
The ratio of sulfuric acid and fluorographite powder is 30~150mL:1g.
4. the preparation method of Fluorinated graphene oxide as described in claim 1, which is characterized in that the step 1 and step 2
In mixing time be 0.5~6h.
5. the preparation method of Fluorinated graphene oxide as described in claim 1, which is characterized 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 described in claim 1, which is characterized 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 described in claim 1, which is characterized in that the ultrasound in the step 1
When ultrasonic wave power and frequency it is all adjustable.
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| 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 |
| CN112812476B (en) * | 2021-02-04 | 2022-09-23 | 上海材料研究所 | Polytetrafluoroethylene composite material and preparation method and application thereof |
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| CN104071765A (en) * | 2014-06-30 | 2014-10-01 | 张至 | Preparation method of oxidized graphite fluoride |
| CN104085882A (en) * | 2014-06-24 | 2014-10-08 | 华南理工大学 | Preparation method of few-layer oxygen-containing fluorinated graphene |
| CN106421804A (en) * | 2016-10-21 | 2017-02-22 | 曲阜师范大学 | Fluorinated graphene nanometer medicine carrier, 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 |
| CN104071765A (en) * | 2014-06-30 | 2014-10-01 | 张至 | Preparation method of oxidized graphite fluoride |
| CN106421804A (en) * | 2016-10-21 | 2017-02-22 | 曲阜师范大学 | Fluorinated graphene nanometer medicine carrier, and preparation method and application thereof |
Non-Patent Citations (1)
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| Preparation and liquid-phase exfoliation of graphite fluoroxide towards graphene fluoroxide;Shijing Yan et al.;《RSC Adv.》;20130827;第3卷;第21869-21876页 |
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